Patent Application
20190177518
The invention relates to ethylene alpha-olefin copolymers having low metal contents. Low metal content ethylene alpha-olefin copolymers are advantageous since metals are often detrimental components in applications where ethylene alpha-olefin copolymers are used, such as, for example, in lubricating oils.
Ethylene alpha-olefin copolymers have been developed to improve low temperature viscometrics, as well as to provide shear stability. Metallocene catalyst systems are commonly used to prepare ethylene alpha-olefin copolymers. However, metal from the metallocene catalysts may appear in the copolymer products and can cause problems in downstream uses of the copolymers. For example, such metals may contribute to detrimental oxidation in finished lubricating oils when employed under typical engine operating conditions.
US 2014/0087985 A3 discloses a polymer dispersant which may be used in a fuel or a lubricant. The polymer may be an ethylene propylene copolymer terminated with a macromonomer containing vinylidene and has up to 95% allyl groups. The polymer may be prepared using a metallocene catalyst and may comprise less than 100 ppmw of aluminum contributed by the metallocene catalyst.
U.S. Pat. No. 9,416,206 B2 discloses ethylene propylene copolymer compositions containing 25 ppmw or less of Group IV metals derived from a catalyst.
There remains a need for ethylene alpha-olefin copolymers that can be employed to make components for lubricating oil compositions and which have low residual metal contents from the catalyst(s) employed to make the copolymer.
The present invention generally relates to ethylene-C3-C10 alpha olefin copolymers, copolymer-derived dispersants and lubricating oils or fuel compositions incorporating the copolymer-derived dispersants, and to methods for making them.
In one aspect, the present invention is directed to a copolymer derived from ethylene units and units of one or more C3-C10 alpha-olefins. The copolymer has a number average molecular weight of less than 5,000 g/mol as measured by gel permeation chromatography (GPC). The ethylene content of the copolymer is less than 80 mol %. 70 mol % or greater of the copolymer has a carbon-carbon double bond in a terminal monomer unit and at least 70 mol % of the terminal monomer units that have a carbon-carbon double bond have a terminal group selected from a vinylidene group and a tri-substituted isomer of the terminal vinylidene group. Further, the copolymer has a metal content of 25 ppmw or less, based on the total weight of the copolymer.
In the foregoing embodiment, the metal content of the copolymer that is optionally derived from the metallocene catalyst may be 10 ppmw or less, or may be 5 ppmw or less, or may be 1 ppmw or less, based on the total weight of the copolymer.
In each of the foregoing embodiments, the copolymer may contain 25 ppmw or less, or 10 ppmw or less, or 5 ppmw or less, or 1 ppmw or less of one or more of zirconium, boron and aluminum, based on the total weight of the copolymer. In each of the foregoing embodiments, the total metal or ash content may be a total content of Zr, Ti, Al and B, optionally derived from a single-site catalyst and an optional co-catalyst. In each of the foregoing embodiments, the total metal or ash content of the copolymer may be 10 ppmw or less, or 5 ppmw or less, or 1 ppmw or less, based on the total weight of the copolymer.
In each of the foregoing embodiments, the copolymer may have a zirconium content of 25 ppmw or less, or 10 ppmw or less, or 5 ppmw or less, or 1 ppmw or less, based on the total weight of the copolymer. In each of the foregoing embodiments, the copolymer may have a boron content of 25 ppmw or less, or 10 ppmw or less, or 5 ppmw or less, or 1 ppmw or less, based on the total weight of the copolymer. In each of the foregoing embodiments, the copolymer may have an aluminum content of 25 ppmw or less, or 10 ppmw or less, or 5 ppmw or less, or 1 ppmw or less, based on the total weight of the copolymer.
In each of the foregoing embodiments, the copolymer may have a fluorine content of less than 10 ppmw, or less than 8 ppmw, or less than 5 ppmw, based on the total weight of the copolymer.
In each of the foregoing embodiments, the copoly mer may have an average ethylene derived unit run length (nc2) which is less than 2.8, as determined by 13C NMR spectroscopy. The average ethylene-derived unit run length nc2 is defined as the total number of ethylene-derived units in the copolymer divided by the number of runs of one or more sequential ethylene-derived units in the copolymer.
In each of the foregoing embodiments, the average ethylene derived unit run length nc2 may also satisfy the relationship shown by the expression below:
wherein:
In each of the foregoing embodiments, the copolymer may have an average ethylene derived unit run length of less than 2.6, or less than 2.4, or less than 2.2, or less than 2.
In each of the foregoing embodiments, the copolymer may have a crossover temperature of −20° C. or lower, or −25° C. or lower, or −35° C. or lower, or −40° C. or lower, or −50° C. or lower, or −60° C. or lower, or −70° C. or lower.
In each of the foregoing embodiments, the ethylene content of the copolymer may be at least 10 mol % and less than 70 mol %. In each of the foregoing embodiments, the ethylene content of the copolymer may be less than 70 mol %, or less than 65 mol %, or less than 60 mol %., or less than 55 mol %, or less than 50 mol %, or less than 45 mol %, or less than 40 mol %. In each of the foregoing embodiments, the ethylene content of the copolymer may be at least 10 mol % and less than 80 mol %, or at least 20 mol % and less than 70 mol %, or at least 30 mol % and less than 65 mol %, or at least 40 mol % and less than 60 mol %.
In each of the foregoing embodiments, the C3-C10 alpha-olefin content of the copolymer may be at least 40 mol % of propylene. In each of the foregoing embodiments, the C3-C10 alpha-olefin content of the copolymer may be at least 20 mol %, or at least 30 mol %, or at least 35 mol %, or at least 40 mol %, or at least 45 mol %, or at least 50 mol %, or at least 55 mol %, or at least 60 mol %.
In each of the foregoing embodiments, the terminal vinylidene group or the tri-substituted isomer of the terminal vinylidene group is selected from one or more groups having the following structural formulas (A)-(C):
wherein R represents a C1-C8 alkyl group and
In each of the foregoing embodiments, the copolymer may have a polydispersity index of less than or equal to 4, or less than or equal to 3, or less than or equal to 2, or less than or equal to 1.
In each of the foregoing embodiments, the number average molecular weight of the copolymer may be less than 4,000 g/mol, or less than 3,500 g/mol, or less than 3,000 g/mol, or less than 2,500 g/mol, or less than 2,000 g/mol, or less than 1,500 g/mol, or less than 1,000 g/mol. In each of the foregoing embodiments, the number average molecular weight of the copolymer may be between 800 and 4,000 g/mol.
In each of the foregoing embodiments, less than 20% of the unit triads in the copolymer may be ethylene-ethylene-ethylene triads, or less than 10% of unit triads in the copolymer may be ethylene-ethylene-ethylene triads, or less than 5% of unit triads in the copolymer may be ethylene-ethylene-ethylene triads.
Each of the foregoing copolymers of ethylene and C3-C10 alpha-olefins may be suitable for use as plasticizers, particular for plasticizing polyolefins.
Additional details and advantages of the disclosure will be set forth in part in the description which follows, and/or may be learned by practice of the disclosure. The details and advantages of the disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.
Ethylene C3-C10 alpha, olefin copolymers having low metal and/or fluorine contents are described herein. Specifically, the ethylene-C3-C10 alpha olefin copolymers herein have a metal content of 25 ppmw or less and/or a low content of fluorine of less than 10 ppmw, each based on a total weight of the copolymer. The copolymer may comprise ethylene-derived units and C3-C10 alpha-olefin-derived units.
Various embodiments will now be described in greater detail below, including specific embodiments, versions and examples, but the inventions are not limited to these embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the inventions, when the information in this patent is combined with available information and technology.
The following definitions of terms are provided in order to clarify the meanings of certain terms as used herein.
When a polymer or copolymer is referred to as comprising an ethylene unit or an olefin unit, the ethylene or olefin unit present in the polymer or copolymer is the polymerized or oligomerized form of the ethylene or olefin, respectively. The term, “polymer” is meant to encompass bomopolymers and copolymers. The term, “copolymer” includes any polymer having two or more units from different monomers in the same chain, and encompasses random copolymers, statistical copolymers, interpolymers, and block copolymers. When a copolymer is said to comprise a certain percentage of an ethylene or olefin unit, that percentage is based on the total amount of units in the copolymer components.
A “polyolefin” is a polymer comprising at least 50 mol % of one or more olefin monomers. Preferably, a polyolefin comprises at least 60 mol %, or at least 70 mol %, or at least 80 mol %, or at least 90 mol %, or at least 95 mol %, or 100 mol % of one or more olefin monomers. Preferably, the olefin monomers are selected from ethylene to ethyleneo olefins, or ethylene to C16 olefins, or ethylene to C10 olefins. More preferably the olefin monomers are selected from ethylene, propylene, 1-butene, 1-hexene, and 1-octene. Polyolefins may also comprise up to 50 mol % of one or more diene monomers.
The nomenclature “Cx” where x is an integer means there are “x carbons” in the compound; for example, a “C5 alpha-olefin” is an alpha-olefin with 5 carbon atoms.
For purpose of this invention and the claims thereto, unless otherwise noted, physical and chemical properties described herein are measured using the test methods described under the Experimental Methods section.
All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”
The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
When the word “about” is used herein in reference to a number, it should be understood that still another embodiment of the invention includes that number not modified by the presence of the word “about.”
It should also be understood that, unless clearly indicated to the contrary, in any methods claimed herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited.
In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedure, Revision 07.2015, Section 2111.03.
An ethylene unit generally refers to an —CH2CH2— unit within a copolymer chain. Ethylene units result from copolymerization of ethylene monomers. Alpha-olefin units generally refer to a unit such as the propylene unit —CH2CH2CH2— and similarly result from copolymerization of alpha-olefin monomers. The term “olefin” is given its ordinary meaning in the art, e.g., referring to a family of organic compounds which are alkenes having the chemical formula CxH2x, where x is the carbon number, and wherein the alkenes have a double bond within their structure. The term “alpha-olefin” is given its ordinary meaning in the art and refers to olefins having a double bond within their structure at the primary or alpha position.
The terms “oil composition,” “lubrication composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “lubricating composition,” “fully formulated lubricant composition,” “lubricant,” “crankcase oil,” “crankcase lubricant,” “engine oil,” “engine lubricant,” “motor oil,” and “motor lubricant” are considered synonymous, fully interchangeable terminology referring to the finished lubrication product comprising a major amount of a base oil plus a minor amount of an additive composition.
As used herein, the terms “additive package,” “additive concentrate,” “additive composition,” “engine oil additive package,” “engine oil additive concentrate,” “crankcase additive package,” “crankcase additive concentrate,” “motor oil additive package,” “motor oil concentrate,” are considered synonymous, fully interchangeable terminology referring the portion of the lubricating oil composition excluding the major amount of base oil stock mixture. The additive package may or may not include the viscosity index improver or pour point depressant.
The term “overbased” relates to metal salts, such as metal salts of sulfonates, carboxylates, salicylates, and/or phenates, wherein the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its “normal,” “neutral” salt). The expression “metal ratio,” often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is one and in an overbased salt, MR, is greater than one. They are commonly referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, and/or phenols.
As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, and substituted hydrocarbon substituents containing one or more of halo groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen and nitrogen, and wherein no more than two non-hydrocarbon substituents are present for every ten carbon atoms in the hydrocarbyl group.
As used herein, the term “percent by weight,” unless expressly stated otherwise, means the percentage the recited component represents to the weight of the entire composition.
The terms “soluble,” “oil-soluble,” or “dispersible” used herein may, but does not necessarily, indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. The foregoing terms do mean, however, that they are, for instance, soluble, suspendable, dissolvable, or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
The term “TBN” as employed herein is used to denote the Total Base Number in mg KOH/g as measured by the method of ASTM D2896.
The term “alkyl” as employed herein refers to straight, branched, cyclic, and/or substituted saturated chain moieties of from about 1 to about 100 carbon atoms.
The term “alkenyl” as employed herein refers to straight, branched, cyclic, and/or substituted unsaturated chain moieties of from about 3 to about 10 carbon atoms.
The term “aryl” as employed herein refers to single and multi-ring aromatic compounds that may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.
An ethylene-derived unit generally refers to a —CH2CH2— unit within a copolymer chain, which is derived from an ethylene molecule during copolymerization, with a similar definition applying to C3-C10 alpha-olefin-derived unit or any other specified derived unit. The term “olefin” is given its ordinary meaning in the art, e.g., referring to a family of organic compounds which are alkenes with a chemical formula CxH2x, where x is the carbon number, and having a double bond within its structure. The term “alpha-olefin” is given its ordinary meaning in the art and refers to olefins having a double bond within its structure at the primary or alpha position.
According to one or more embodiments, ethylene-C3-C10 alpha olefin copolymers are generally disclosed. The copolymer may comprise ethylene-derived units and C3-C10 alpha-olefin-derived units, wherein the C3-C10 alpha-olefin has a carbon number of three to ten. Thus, the carbon number of the C3-C10 alpha-olefin may be 3, 4, 5, 6, 7, 8, 9, or 10. For example, according to some embodiments, the C3-C10 alpha-olefin-derived units are propylene-derived units. In some embodiments, the C3-C10 alpha-olefin-derived units may be 1-butylene-, 1-pentene-, 1-hexene-, 1-heptene-, 1-octene-, 1-nonene-, or 1-decene-derived units.
Low Metal and/or Fluorine Content
Low metal content copolymers are desirable for many uses due to the harmful effects of metals in various environments. For example, metals or ash can have an adverse impact on after-treatment devices employed in various types of engines. It is also desirable to ensure that the copolymers have a low fluorine content since fluorine is ecologically undesirable in many environments.
There are several methods to achieve a low metal content in the copolymer as described herein. The present invention incorporates methods known by those skilled in the art to purify and remove impurities. For example, in Giuseppe Forte and Sara Ronca, “Synthesis of Disentangled Ultra-High Molecular Weight Polyethylene: Influence of Reaction Medium on Material Properties,” International Journal of Polymer Science, vol. 2017, Article ID 7431419, 8 pages, 2017. doi: 10.1155/2017/7431419, methods for purifying a polyethylene compound are disclosed. The method of purify ing the copolymer comprises dissolving the copolymer in acidified methanol (CH3OH/HCl) to a DCM (dichloromethane) solution of the polymer/catalyst mixture. This results in precipitation of the “purified” polymer, while the catalyst and other byproducts remain in solution. The copolymer may then be filtered and washed out with additional methanol, and oven dried under vacuum at 40° C.
According to one or more embodiments, the copolymer may be purified to achieve a low metal content by passing the polymer/catalyst mixture through an adsorption column. The adsorption column contains an adsorber, preferably, activated alumina.
In a more preferred embodiment, the copolymer may be purified to achieve a low metal content by stripping the polymer compositions using toluene and a rotavap with a temperature-controlled oil bath.
In an alternative embodiment, the copolymer does not require a purification step. In this embodiment, the copolymer of the present invention is preferably copolvmerized using a catalyst having a catalyst productivity of from 200-1500 kg copolymer/gram of single-site catalyst, or from 350-1500 kg copolymer/gram of single-site catalyst, or from 500-1200 kg copolymer/gram of single-site catalyst, or from 500-800 kg copolymer/gram of single-site catalyst. Suitable single-site catalyst systems having these productivities may be selected from those known in the art. The catalysts may be selected for the production of copolymers having Mn's in the range of 700-1400 g/mol, or from 550-650 g/mol. Selection of a suitable single-site catalyst may eliminates the need for a wash step to achieve the low metal content of the copolymer.
Catalyst productivity, expressed as the kg polymer produced per gram of catalyst, may be improved by efficient catalyst systems. The present invention incorporates the use of catalyst systems known by those skilled in the art which are capable of achieving high catalyst productivities. For example, U.S. Pat. No. 9,441,063 relates to catalyst compositions containing activator-supports and half-metallocene titanium phosphinimide complexes or half-metallocene titanium iminoimidazolidides capable of producing polyolefins with high catalyst productivities of at least up to 202 kg polymer/g catalyst (551 kg polymer/g cat/hr with a 22 min residence time, See Example 5 and Table 1, Columns 47 and 48.) Also, U.S. Pat. No. 8,614,277 relates to methods for preparing isotactic polypropylene and ethylene-propylene copolymers. U.S. Pat. No. 8,614,277 provides catalyst systems suitable for preparing copolymers at catalyst productivity levels greater than 200 kg polymer/g catalyst. The catalysts provided therein are metallocenes comprising zirconium as their central atom, (See the examples in Tables 1a-1c).
The copolymer may comprise a metal or ash content of 25 ppmw or less, based on the total weight of the copolymer. Preferably, the metal or ash content of the copolymer is 10 ppmw or less, or more preferably 5 ppmw or less, or even more preferably 1 ppmw or less, based on the total weight of the copolymer. Typically, the metal or ash content of the copolymer is derived from the single-site catalyst and optional co-catalyst(s) employed in the copolymerization reactor.
These single-site catalysts may include metallocene catalysts. Zr and Ti metals are typically derived from such metallocene catalysts. Various co-catalysts may be employed in combination with the single-site catalyst. Such co-catalysts may include boron and aluminum metals, as well as ecologically undesirable fluorine atoms or compounds. Thus, the metal or ash content of the copolymers of the present invention is the total metal or ash including Zr, Ti, Al and/or B. Various suitable catalyst systems are described elsewhere herein.
The copolymers may have a fluorine content of less than 10 ppmw, or less than 8 ppmw, or less than 5 ppmw, based on the total weight of the copolymer. Typically, the fluorine will come from co-catalyst systems based on boron compounds such as pefluoroaiyl boranes.
One important characteristic of the copolymer described herein is the crossover temperature or onset temperature of the copolymer. The copolymer is generally viscoelastic; in other words, its mechanical properties are between those of a purely elastic solid and those of a purely viscous liquid. The viscoelastic behavior of the copolymer may be characterized as the combination of an elastic portion (referred to as either an elastic modulus or a storage modulus), and a viscous portion (referred to as either a viscous modulus or a loss modulus). The values of these moduli are used to characterize the viscoelastic properties of the copolymer at a given temperature. Both the storage modulus and the loss modulus are dependent on temperature, although each may change at a different rate as a function of temperature. Thus, the copolymer may exhibit more elasticity or more viscosity, depending on the temperature. The crossover temperature is defined herein as the temperature at which the storage modulus equals the loss modulus. The crossover temperature may also be referred to as the onset temperature.
Oscillatory rheology is a technique that may be used to determine values (generally expressed in units of pressure) for the storage modulus and loss modulus. The basic principle of an oscillatory rheometer is to induce a sinusoidal shear deformation in the sample (e.g., a sample of copolymer) and measure the resultant stress response. In a typical experiment, the sample is placed between two plates. While the top plate remains stationary, a motor rotates the bottom plate, thereby imposing a time dependent strain on the sample. Simultaneously, the time dependent stress is quantified by measuring the torque that the sample imposes on the top plate.
Measuring this time dependent stress response reveals characteristics about the behavior of the material. If the material is an ideal elastic solid, then the sample stress is proportional to the strain deformation, and the proportionality constant is the shear modulus of the material. In this case, the stress is always exactly in phase with the applied sinusoidal strain deformation. In contrast, if the material is a purely viscous fluid, the stress in the sample is proportional to the rate of strain deformation, where the proportionality constant is the viscosity of the fluid. In this case, the applied strain and the measured stress are out of phase.
Viscoelastic materials show a response that contains both in-phase and out-of-phase contributions. These contributions reveal the extents of solid-like and liquid-like behavior. A viscoelastic material will show a phase shift with respect to the applied strain deformation that lies between that of solids and liquids. These can be decoupled into an elastic component (the storage modulus) and a viscosity component (the loss modulus). The viscoelastic behavior of the system can thus be characterized by the storage modulus and the loss modulus, which respectively characterize the solid-like and fluid-like contributions to the measured stress response.
As mentioned above, the values of the storage modulus and loss modulus are temperature dependent. At warmer temperatures, the value of the loss modulus for the copolymer is greater than the value of the storage modulus. However, as the temperature decreases, the copolymer may behave more like an elastic solid, and the degree of contribution from the storage modulus approaches that from the loss modulus. As the temperature lowers, eventually, at a certain temperature the storage modulus of the copolymer crosses over the loss modulus and becomes the predominant contributor to the viscoelastic behavior of the copolymer. According to one or more embodiments, a lower crossover temperature of the copolymer correlates to better low temperature performance of oils into which the copolymer is incorporated.
According to one or more embodiments, the copolymer may have a crossover temperature of −20° C. or lower, −25° C. or lower, −30° C. or lower, −35° C. or lower, −40° C. or lower, −50° C. or lower, −60° C. or lower, or −70° C. or lower as determined by oscillatory rheometry. Other values are also possible. An advantageous crossover temperature for the copolymer may be achieved through controlling characteristics of the copolymer during its manufacture. One such characteristic is the average ethylene unit run length in the copolymer.
According to one or more embodiments, the ethylene units and C3-C10 alpha-olefin units within the copolymer may be arranged to provide good low temperature performance. One important characteristic of the arrangement of the ethylene and C3-C10 alpha-olefin units is the average ethylene unit run length. The average ethylene-derived unit run length nc2 is defined as the total number of ethylene-derived units in the copolymer divided by a number of runs of one or more sequential ethylene-derived units in the copolymer. Thus, the average ethylene unit run length is an average of the number of ethylene units in each sequence of ethylene units in the copolymer. For example, in the sequence of units C3-C10 alpha-olefin-ethylene-ethylene-C3C10 alpha-olefin the ethylene unit run length is two since there are two ethylene units in the ran of ethylene units of this sequence. Thus, in a copolymer having the following two sequences (A) and (B), the ethylene unit run lengths are 2 and 3, respectively and the average ethylene unit ran length is 2.5: (A) C3-C10 alpha-olefin-ethylene-ethylene-C3-C10 alpha-olefin, and (B) C3-C10 alpha-olefin-ethylene-ethylen-ethylene-C3-C10 alpha-olefin. In a copolymer molecule comprising a chain of ethylene and C3-C10 alpha-olefin units, the units are not distributed uniformly within the copolymer chain. The average ethylene unit run length may be determined by dividing the total number of ethylene units by the number of ethylene unit runs in the copolymer. For example, a copolymer having a total of four ethylene units and three runs of ethylene units has an average ethylene unit run length of 4/3=1.33.
Methods for determining values of the average ethylene unit ran length are known in the art and comprise established spectroscopic procedures using 13C nuclear magnetic resonance methods as described, for example, in “Carbon-13 NMR in Polymer Science,” ACS Symposium Series 103, American Chemical Society, Washington, D.C. 1978 at p. 97 and in “Polymer Sequence Determination Carbon-13 NMR Method,” J. C. Randall, Academic Press, New York, N.Y. at p. 53.
Where the arrangement of the units in the copolymer chains is purely random, each unit has a chance of appearing in a certain position proportional to the remaining molar percentage of the monomer corresponding to that unit that is present in the monomer mixture, regardless of whether the immediately preceding unit is the same or different. Thus, an expected average ethylene unit run length for a purely random unit distribution can be calculated as a function of the molar percentage of ethylene monomer. This value is referred to herein as the statistically-expected random average ethylene unit run-length.
According to one or more embodiments, the copolymer may be synthesized by a process through which the average ran length of one of the copolymer units is less than the statistically-expected random average unit run length for a given molar percentage of the monomer of that unit present in the reaction mixture. For example, considering a copolymer of ethylene and propylene units, one or more catalysts and/or co-catalysts may be chosen such that during copolymer chain formation, a propylene unit is favored to bond to a preceding ethylene unit, while an ethylene unit is favored to bond to a preceding propylene unit, as discussed further below. As a result of this choice, the average ethylene unit run length in the copolymer can be reduced to be less than the statistically-expected random average unit run length for the given molar percentage of ethylene monomers in the reaction mixture. Where the average ran length is less than the statistically-expected random average unit run-length, the copolymer is referred to as being between “statistical” and “alternating”, where “alternating” refers to a copolymer wherein the ethylene and propylene units always alternate. Alternatively, where the average unit run length is greater than the statistically-expected random average unit run-length, the copolymer is said to between “statistical” and “blocky.”
According to one or more embodiments, an average ethylene unit run length in the copolymer is, at least in part, a function of the percentage of ethylene units in the copolymer, and the chosen catalyst(s) and co-catalyst(s). For example, a higher percentage of ethylene units in the copolymer will result in a higher average ethylene unit run length. The choice of catalyst and co-catalyst may be used to affect the average ethylene unit run length, in situations where the catalyst affects the relative insertion rate of insertion of the different units of the copolymer.
During polymer chain formation, the reaction rate at which an ethylene monomer bonds to a preceding ethylene unit at the end of the growing copolymer chain is referred to as the ethylene-ethylene reaction rate constant (“kpEE”). The reaction rate at which a propylene (or other alpha-olefin monomer) bonds to an ethylene unit at the end of the growing copolymer chain is referred to as the ethylene-propylene reaction rate constant (“kpEP”). The reactivity ratio of ethylene (“rE”) refers to the ratio of the ethylene-ethylene reaction rate constant to the ethylene-propylene reaction rate constant, kpEE/kpEP.
Likewise, the reaction rate at which a propylene (or other alpha-olefin) monomer bonds to a propylene unit at the end of the growing copolymer chain is referred to as the propylene-propylene reaction rate constant (“kpPP”). The reaction rate at which an ethylene monomer bonds to a propylene unit at the end of the growing copolymer chain is referred to as the ethylene-propylene reaction rate constant (“kpPE”). The reactivity ratio of propylene (“rP”) refers to the ratio of the propylene-propylene reaction rate constant to the propylene-ethylene reaction rate constant, kpPP/kpPE.
The lower each of the reactivity ratios (rE or rP) are, the more likely it is that a different unit will follow the preceding unit and thus the resulting copolymer chain will tend to have an alternating character, with a lower average ethylene unit run length than the statistically-expected random average ethylene unit run-length. According to one or more embodiments, selection of an appropriate catalyst, as well as control of other process parameters, may reduce one or more of the reactivity ratios for various units/monomers and may therefore also reduce the average ethylene unit run length.
A lower average ethylene unit run length may provide certain advantages. For example, it may result in a lower crossover temperature for the copolymer, thereby improving one or more aspects of performance such as cold-weather performance of a polyolefin plasticized with the copolymer. In general, the shorter the average ethylene unit run length, the lower the crossover temperature of the copolymer, which ultimately results in a better low temperature performance for polyolefins plasticized with the copolymer.
According to one or more embodiments, a copolymer comprising ethylene and C3-C10 alpha-olefin units is selected to have an average ethylene unit run length that is less than the statistically-expected random average ethylene unit run-length for the given molar percentage of ethylene units in the copolymer. The formulae (2)-(5) below can be used to calculate the statistically-expected random average ethylene unit run-length for the given molar percentage of ethylene units in the copolymer. For example, as shown in
According to one or more embodiments, the copolymer may have an average ethylene unit run length that is less than 3.0, less than 2.9, less than 2.8, less than 2.7, less than 2.6, less than 2.5, less than 2.4, less than 2.3, less than 2.1, or less than 2.0. In such embodiments, the average ethylene unit run length may also be selected to be is less than the statistically-expected random average ethylene unit run-length for the given molar percentage of ethylene units in the copolymer.
Copolymers of ethylene and propylene produced with perfectly alternating microstructures do not have a distribution of ethylene unit run lengths, as every sequence of ethylene units is exactly the same length. The ethylene unit run length for a perfectly alternating microstructure is calculated from Equation (1).
Copolymers that do not have a perfectly alternating microstructure have a distribution of ethylene unit run lengths, and the prediction for a purely statistical microstructure of a copolymer represents the average ethylene unit run length for the distribution of ethylene unit run lengths in that copolymer. The average ethylene unit run length for copolymers produced with a purely statistical microstructure can be calculated using Bernoullian statistics, as shown in Equation (2). The mole fraction of ethylene incorporated in the polymer, xethhylene, as measured by 1H-NMR spectroscopy, is used to calculate the fraction of EEE, EEP and PEP triads in the copolymer (there are also EPE, PPE and PPP triads) in a purely statistical polymer using Equations (3)-(5) given below.
E represents an ethylene unit and P represents a propylene unit and thus the triad “EPE” represents the three unit triad ethylene-propylene-ethylene.
The experimental ethylene incorporation in mol % was determined by 1H-NMR using a standard technique known to those of ordinary skill in the art. The experimental average ethylene unit run length was determined by 13C-NMR using the standard technique discussed above. A comparison of the experimentally determined average ethylene unit ran length and the calculations for the alternating and statistical results are shown in
Increasing the ethylene content of the copolymer increases the plasticization efficiency, plasticization durability, and oxidative stability of the plasticizer but also decreases the amount of structure forming that may occur at lower temperatures. It is unexpected that the particular combination of properties and microstructure of the copolymer of the present invention provides adequate plasticization efficiency, plasticization durability, and oxidative stability while at the same time providing a good low temperature performance.
The results shown in
The copolymerization reaction can be controlled to provide the desired copolymers of the invention. Parameters such as the reaction temperature, pressure, mixing, reactor heat management, feed rates of one or more of the reactants, types, ratio, and concentration of catalyst and/or co-catalyst and/or scavenger as well as the phase of the feed components can be controlled to influence the structure of the copolymer obtained from the reaction. Thus, a combination of several different reaction conditions can be controlled to produce the desired copolymer.
For example, it is important to run the copolymerization reaction with appropriate heat management. Since the copolymerization reaction is exothermic, in order to maintain a desired set point temperature in the reactor heat must be removed. This can be accomplished by, for example, two different methods often practiced in combination. Heat can be removed by cooling the feed stream to the reactor to a temperature well below the reaction set point temperature (even sometimes cryogenically) and therefore allowing the feed stream to absorb some of the heat of reaction through a temperature rise. In addition, heat can be removed from the reactor by external cooling, such as a cooling coil and/or a cooling jacket. The lower the set point temperature in the reactor, the more demand there is for heat removal. The higher the reaction temperature, the less heat needs to be removed, or alternatively or in combination, the more concentrated the copolymer can be (higher productivity) and/or the shorter the residence time can be (smaller reactor). The results characterizing the deviation of the a verage ethylene unit run length from a purely statistical microstructure are shown in
As the reaction temperature was increased beyond 135° C., it appears that control of the microstructure may be lost and the copolymer typically becomes worse than statistical. As a result, the low temperature properties of the copolymer may be compromised. Without being bound by theory, the reduced control of the microstructure of copolymers produced at higher temperatures is believed to be due to a drop in the reaction kinetics of comonomer incorporation relative to ethylene incorporation. The more difficult it is for the comonomer to incorporate in the copolymer, the less regularly the comonomer breaks up the runs of ethylene units in the chain during copolymerization. Some strategies for improving the incorporation of comonomer at higher reaction temperatures include increasing the ratio of monomers of C3-C10 alpha-olefin/ethylene in the reactor, increasing the Al/Zr ratio in the catalyst or by making changes in the catalyst architecture.
Thus, in some embodiments of the invention, reaction temperatures of 60-135° C. are employed for the copolymerization reaction, or, more preferably, reaction temperatures of 62-130° C., or 65-125° C., or preferably 68-120° C. or 70-90° C., are employed for the copolymerization reaction.
A preferred Al/Zr ratio in the catalyst system may be less than 10,000:1, less than 1,000:1, less than 100:1, less than 10:1, less than 5:1, or less than 1:1. For boron-containing technology, a preferred Al/Zr ratio in the catalyst is less than 100:1, less than 50:1, less than 10:1, less than 5:1, less than 1:1, less than 0.1:1 and a preferred B/Zr ratio is less than 10:1, less than 5:1, less than 2:1, less than 1.5:1, less than 1.2:1, or less than 1:1.
Low temperature properties of the copolymer can be correlated to the microstructure of the copolymer. Low temperature performance of the pure copolymer is measured by Oscillatory Rheometry. The point at which storage modulus is equal to the loss modulus, the crossover or onset temperature, is an indication of the temperature at which the copolymer will begin to exhibit unfavorable structure forming. The crossover temperature is the point at which the structure formed in the polymer exceeds the liquid-like character of the polymer. This temperature has been shown to be predictive for determining the impact of the copolymer structure on low temperature performance as a polyolefin plasticizer.
The impact of average ethylene unit run length on crossover temperature is shown in
In some embodiments, the sequential arrangement of units in the copolymer may, alternatively, be described with reference to the triad distribution. The triad distribution refers to the statistical distribution of the possible combinations of three units in a row in the copolymer chain. Taking as an example an ethylene-propylene copolymer, where “E” represents an ethylene unit and “P” represents a propylene-derived unit, the potential combinations of unit triads are: EEE, EEP, PEP, EPE, PPE, and PPP. According to one or more embodiments, the percentage of EEE units based on the total number of unit triads in the copolymer is preferably less than 20%, less than 10%, or less than 5%. The percentage of EEE units is indicative of a relatively short average ethylene unit run length in such copolymers.
The method used for calculating the triad distribution of ethylene-propylene copolymers is described in J. C. Randall JMS-Review Macromolecules Chem Physics ethylene9, 201 (1989) and E. W. Hansen, K. Redford Polymer Vol. 37, No. 1, 19-24 (1996). After collecting 13C(1H) NMR data under quantitative conditions, eight regions (A-H), shown in Table 1 are integrated. The equations of Table 2 are applied and the values normalized. For the examples described herein, the D, E, and F regions were combined due to peak overlap in the NMR spectra. The symbol “k” represents a normalization constant and T=the total intensity.
The number average molecular weight of the copolymer can be determined by 1H-NMR or gel permeation chromatography (GPC), as described in U.S. Pat. No. 5,266,223, with the GPC method being preferred. The GPC method additionally provides molecular weight distribution information; see W. W. Yau, J. J. Kirkland and D. D. Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979. According to some embodiments, the copolymer may have a number average molecular weight of less than 5,000 g/mol, of less than 4,500 g/mol, of less than 4,000 g/mol, of less than 3,500 g/mol, of less than 3,000 g/mol, of less than 2,800 g/mol, of less than 2,500 g/mol, of less than 2,000 g/mol, of less than 1,500 g/mol, or of less than 1,000 g/mol as determined by GPC. According to some embodiments, the copolymer may have a number average molecular weight of greater than 200 g/mol, 500 g/mol, of greater than 800 g/mol, of greater than 1,000 g/mol, as determined by GPC. Combinations of all of the above-referenced end points to form ranges are also possible and are disclosed herein. Other values are also possible.
The polydispersity index (PDI) of the copolymer is a measure of the variation in the length, in units, of the individual chains of the copolymer. The polydispersity index is determined by dividing the weight average molecular weight (Mw) of the copolymer by the number average molecular weight (Mn) of the copolymer. The term number average molecular weight (determined by, e.g., 1H-NMR or GPC) is given its ordinary meaning in the art and is defined as the sum of the products of the weight of each polymer chain and the number of polymer chains having that weight, divided by the total number of polymer chains. The weight average molecular weight of the copolymer is given its ordinary meaning in the art and is defined as the sum of the products of the weight squared of each polymer chain and the total number of polymer chains having that weight, divided by the sum of the products of the weight of each polymer chain and the number of polymer chains having that weight. According to one or more embodiments, the PDI of the copolymer (Mw/Mn) may be less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1.
In some embodiments, it is desirable to provide copolymers that have a lower kinematic viscosity without reducing the molecular weight of the copolymer. This goal can be achieved in certain embodiments by controlling the microstructure of the copolymer as discussed above.
Viscosity and Complex Viscosity
One goal of embodiments herein is the provision of a copolymer with a lower viscosity and higher molecular than a comparable copolymer. For example, referring to
The copolymer may comprise a certain mole percentage (mol %) of ethylene or ethylene units. According to some embodiments, the molar percentage of ethylene in the copotymer, is at least 10 mol %, at least 20 mol %, at least 30 mol %, at least 40 mol %, at least 45 mol %, at least 50 mol %, at least 55 mol %, at least 60 mol %, at least 65 mol %, at least 70 mol %, or at least 75 mol %. According to some embodiments, the molar percentage of ethylene units in the copolymer is less than 80 mol %, less than 75 mol %, less than 70 mol %, less than 65 mol %, less than 60 mol %, less than 55 mol %, less than 50 mol %, less than 45 mol %, less than 40 mol %, less than 30 mol %, or less than 20 mol %. Combinations of each of the above-mentioned end points to form ranges are also possible and are disclosed herein. Other ranges are also possible.
C3-C10 Alpha Olefin Comonomer Content
The copolymer may comprise a certain mole percentage of C3-C10 alpha-olefin units. According to some embodiments, the molar percentage of the C3-C10 alpha-olefin units the copotymer, relative to the total units within the copolymer, is at least 20 mol %, at least 25 mol %, at least 30 mol %, at least 35 mol %, at least 40 mol %, at least 45 mol %, at least 50 mol %, at least 55 mol %, at least 60 mol %, at least 65 mol %, at least 70 mol %, or at least 80 mol %. According to some embodiments, the C3-C10 alpha-olefin content of the copolymer is less than 90 mol %, less than 80 mol %, less than 70 mol %, less than 65 mol %, less than 60 mol %, less than 55 mol %, less than 50 mol %, less than 45 mol %, less than 40 mol %, less than 35 mol %, less than 30 mol %, less than 25 mol %, or less than 20 mol %, less than 90 mol %. Combinations of any the above referenced limits can be made to form ranges and are possible and disclosed herein. Other ranges are also possible.
In many applications for plasticizers known in the art, it may be desirable to provide a polymerizable plasticizer, a functionalizable plasticizer or a reactive plasticizer. For one or more of these purposes, it is desirable to include unsaturation in the copolymers of the present invention.
In the embodiments of the invention, the copolymer comprises a plurality of copolymer molecules, 70 mol % or greater of the copolymer has a carbon-carbon double bond in a terminal monomer unit. According to some embodiments, more than 75 mol %, more than 80 mol %, more than 85 mol %, more than 90 mol %, more than 95 mol %, or more than 97 mol %, of the copolymer has a carbon-carbon double bond in a terminal monomer unit. The percentage of polymeric chains exhibiting terminal unsaturation may be determined by FTIR spectroscopic analysis, titration, or 13C NMR. See, e.g., U.S. Pat. No. 5,128,056.
In the embodiments of the invention, the copolymer may terminate, at one end, with either an ethylene unit or a C3-C10 alpha-olefin unit. The terminal unsaturation mentioned above is located within a terminal group of the copolymer molecule. If the terminal group containing the terminal unsaturation is an ethylene unit, the terminal unsaturation is present in either a vinyl group or a di-substituted isomer of a vinyl group. If the terminal group containing the terminal unsaturation is a C3-C10 alpha-olefin unit, the terminal unsaturation is present in either a vinylidene group or a tri-substituted isomer of a vinylidene group.
In some embodiments, more than 70 mol %, more than 75 mol %, more than 80 mol %, more than 85 mol %, more than 90 mol %, or more than 95 mol % of the terminal unsaturation is located within a C3-C10 alpha-olefin terminal unit. In such case, the terminal group has one or more of the following structural formulas (I)-(III):
For each of Formulas (I)-(III), R represents a C1-C8 alkyl group that corresponds to the appropriate alkyl group for that particular C3-C10 alpha-olefin unit, e.g., a methyl group if the alpha olefin is propylene, an ethyl group if the alpha olefin is 1-butene, etc., and
indicates the bond that is the point of attachment of the group (I), (II) or (III) to the remaining portion of the copolymer molecule.
As used herein, the terms “terminal vinylidene” and “terminal vinylidene group” refer to the structure represented by Formula (I). As used herein, the terms “tri-substituted isomer of terminal vinylidene” and “tri-substituted isomer of terminal vinylidene group” refer to one of the structures represented by the Formulas (II) and (III).
Terminal vinylidene, tri-substituted isomers of terminal vinylidene, as well as other types of terminal unsaturation in the copolymers can be detected by 1H-NMR. From the integrated intensity of each signal, the amount of each terminal group can be determined as discussed in US 2016/0257862.
There are many tests that can be used to evaluate the chemical compatibility of thermoplastic materials. Three major groups of tests for chemical compatibility include retention of physical/mechanical properties, visual evaluations and creep and creep rupture. Physical properties such as change in volume, weight, dimensions, or hardness are particularly useful when evaluating chemical compatibility. Tests monitoring the change in weight or hardness would be a good indication of chemical compatibility. Plasticization allows movement of the individual molecular chains causing the polymer to become increasingly flexible as more plasticizer is absorbed. As in the case with solvation, change in weight, hardness, and in addition, dimension and volume are good indicators of chemical compatibility.
Mechanical properties such as tensile strength and elongation, impact, and flexural strength can be very good indicators of chemical compatibility. In this type of testing the properties are performed initially and again after time has elapsed. Plasticization tends to soften polymers, increasing the ductility and thus causing an increase in the tensile elongation while at the same time lowering tensile strength. The changes that occur are dependent on the amount of plasticizer present and thus results can be affected by other factors. Chemical compatibility effects that can be difficult to determine by other methods such as Environmental Stress Cracking (ESC) can be established by testing retention of tensile properties.
Visual evaluations can be used in conjunction with almost any test method when determining chemical compatibility. One such test method is ASTM D543, which combines visual evaluations with other tests. There are, however, test methods where visual evaluations and ratings are the primary result, ASTM D1693, is designed for use with ethylene type plastics and involves bending test specimens in a fixture, nicking the specimens to initiate a controlled imperfection, and optionally applying chemical agents. The specimens are then evaluated for crack growth and results determined based on the number and severity of the cracks. ASTM D1 693 is limited to flexible materials, primarily opaque, and to the observance of cracking.
Polymers can exhibit elastic deformation and reduction in strength when solvation/plasticization occurs. Creep measurements are therefore useful in determining compatibility with solvents or plasticizers. ASTM D2990 is a suitable test for creep measurements.
Estimation of the solubility parameter is another suitable way to determine chemical compatibility. The solubility parameter and molar volume of each monomer can be estimated from the structure of the monomer. Specifically, the estimation method of Fedors, R. F., “A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids,” Pol. Eng. Sci., 14, 147-154 (1974) is employed for the copolymers of the present application. This method employs the formula:
wherein the group contributions are as given in Table 3 below.
The group contributions shown in Table 3 are added for each monomer unit to obtain the total for each copolymer. For copolymers, the following equation of Schneier. B., “An Equation for Calculating the Solubility Parameter of Random Copolymers,” Pol. Lett., 10, 245-251 (1972) can be used.
wherein 1, 2, and x are monomer 1, monomer 2, and the mixture, respectively, V is the molar volume, δ is the solubility parameter, and X is the mole weight fraction. The mole weight fraction is:
where M is the monomer molecular weight and n is the number of moles of each monomer. Vx is taken as the molar average of the two monomer molar volumes:
wherein the total solubility parameters are as given in Table 4 below.
In some embodiments the plasticizer has a difference of no more than 2 (cal cm−3)1/2 in the solubility parameter as compared to the solubility parameter of the polyolefin or other polymer into which the plasticizer is to be incorporated. Another way to calculate the solubility parameter for homopolymers is described in Small, P. A., “Some Factors Affecting the Solubility of Polymers,” J. Appl. Chem., 3, 71-79 (1953).
Various properties of the plasticizers of the present invention can be determined and/or evaluated based on the information given in, “Principles of Plasticization,” Immergut, E. II. and Mark, H. P., (1965), doi: 10.1021/ba-1965-0048.ch001, the disclosure of which is incorporated by reference herein in its entirety for providing information for determining and evaluating properties of plasticizers.
A suitable method for the production of the copolymers of the invention includes a step of reacting ethylene and at least one C3-C10 alpha-olefin using a coordination polymerization catalyst and a co-catalyst at a temperature of from 60° C. to 135° C. for a time sufficient to produce a copolymer comprising ethylene units and C3-C10 alpha-olefin units. The reaction conditions are preferably controlled such that copolymer has a number average molecular weight of less than 5,000 g/mol; 70 mol % of the copolymer terminates in a terminal vinylidene group or a tri-substituted isomer of a terminal vinylidene group; the copolymer has an average ethylene unit run length of less than 4, as determined through NMR spectroscopy; the copolymer has an ethylene content of less than 80 mol %; and the copotymer has a crossover temperature of −20° C. or lower.
A metallocene comprises cyclopentadienyl anions (“Cp”) bound to a metal center. The C3-C10 alpha-olefin content can be controlled through the selection of the metallocene catalyst component and by controlling the partial pressure or relative feed rates of the various monomers. The metallocene catalysts employed in the production of the reactant polymers are organometallic coordination compounds which are cyclopentadienyl derivatives of a Group 4b metal of the Periodic Table of the Elements (56th Edition of Handbook of Chemistry and Physics, CRC Press [1975]) and include mono, di and tricyclopentadienyls and their derivatives of the transition metals. Particularly desirable are the metallocene of a Group 4b metal such as titanium, zirconium, and hafnium. The aluminoxanes employed in forming the reaction product with the metallocenes are themselves the reaction products of an aluminum trialkyl with water.
In certain embodiments, the coordinated metallocene may comprise a zirconium. For example, the coordinated metallocene may comprise Cp2ZrCl2. In addition, a co-catalyst may optionally be employed. The co-catalyst may comprise an aluminoxane such as methylaluminoxane.
The copolymer may be produced in a reactor. Parameters that may be controlled during the copolymerization reaction include at least pressure and temperature. The reaction may be operated continuously, semi-continuously, or batchwise. The ethylene may be delivered to the reactor as ethylene gas through a metered feed. The C3-C10 alpha-olefin may be delivered to the reactor through a separate metered feed. The catalyst and optional co-catalyst may be delivered to the reactor in solution. The weight percentage of either the catalyst or the co-catalyst in the solution delivered to the reactor may be less than 20 wt. %, less than 15 wt. %, less than 10 wt. %, less than 8 wt. %, less than 6 wt. %, less than 5 wt. %, less than 4 wt. %, less than 3 wt. %, less than 2 wt. %, or less than 1 wt. %, according to different embodiments. The ethylene, C3-C10 alpha-olefin, solvent and catalyst and optional co-catalyst may then be mixed in the reactor. Skilled persons are familiar with many suitable reactions, reactors and reaction conditions for copolymerization of ethylene and C3-C10 alpha-olefins. Examples of several processes for forming the copolymer are described in the examples below.
The catalyst may comprise a granular support based especially on a refractory oxide such as, for example, silica and/or alumina. Such a catalyst can be prepared by a method comprising bringing the granular support into contact with (a) a dialkylmagnesium and optionally a trialkylaluminium, (b) a halogenated hydrocarbon e.g. a monohalogenated hydrocarbon, (c) and a tetravalent titanium compound. Such a method is described in European Patent Application EP-A-453,088.
The catalyst may also contain a magnesium chloride support and in particular a preactived support such as that described in European Patent Application EP-A-336,545. A catalyst of this type can be prepared by a method comprising bringing a magnesium chloride support into contact with (a) an organometallic compound which is a reducing agent for titanium, (b) a tetravalent titanium compound and c) optionally one or more electron-donor compounds. Such a method is described in French Patent Application FR-A-2,669,640.
The catalyst may be used in the form of a solid as it is or in the form of a prepolymer, especially when it is used in a gas phase polymerization. The prepolymer is obtained by bringing the catalyst into contact with one or more of olefins e.g. containing from 2 to 8 carbon atoms such as, for example, ethylene or a mixture of ethylene with C3-C8 olefin(s) in the presence of an organometallic cocatalyst. In general, the prepolymer obtained contains from 0.1 to 200 g preferably from 10 to 100 g of polymer per millimole of titanium.
The catalyst may be employed with an organometailic cocatalyst which may be chosen from organoaluminium, organomagnesium and organozinc compounds. In most cases the organometallic cocatalyst is an alkylaluminium such as, for example, trimethylaluminium, triethylaluminium, tri-n-octylaluminium or else a mixture of these compounds.
The copolymers can alternatively be polymerized using catalysts prepared by the admixture of certain boron compounds with a salt of a metal selected from Groups 4a, 5a, 6a and 8, of the Mendeleeff Periodic Table. These compounds of boron are the hydrides and hydrocarbon derivatives of boron. The boron hydride used in preparing such catalytic compositions is usually diborane (B H although other hydrides of boron can also be used including, for example, pentaborane, hexaborane, and decaborane.
Hydrocarbon derivatives of boron which may be used include alkyl borons, cycloalkyl borons, aryl borons and the like. Examples of alkyl borons which can be used include, trimethyl boron, triethylboron, tripropyl boron, tributyl boron, tridecyl boron and the like. Examples of aryl borons include triphenyl boron, tritolyl boron, tri-p-xylyl boron, trinaphthyl boron and the like. Mixed hydride-hydrocarbon derivatives of boron can also be used, e.g. symmetrical or asymmetrical dimethyldiborane, methyldiborane and the like. Also the hydrocarbon-halogen derivatives of boron, e, g. dimethylboron bromide, dimethylboron iodide, diphenylboron bromide or chloride, etc can be used. Exemplary boron catalysts can be found in, for example, U.S. Pat. Nos. 3,166,536; 3,160,672 and 2,840,551.
In some embodiments, the microstructure of the copolymer may be desirably influenced by spatially distributing the composition uniformly within the reactor. Methods of ensuring uniformity of the spatial distribution include, but are not limited to, agitation, selection of particular feed locations for feeding the monomers, solvent and catalyst components and particular methods of introducing one or more of the various components. Additional factors that may impact compositional uniformity in the reactor include operation within a particular temperature and/or pressure range that provides a single fluid phase within the reactor. In some embodiments this may involve ensuring that the reactor temperature and pressure conditions remain above the entire vapor-liquid phase behavior envelope of the feed composition. It is also envisioned that premixing of two or more of the feed components may be employed and the premixing time and mixing intensity of the feed components may be useful for control of spatial uniformity within the reactor, at least in some cases. In certain embodiments it may also be desirable to ensure that no pockets of vapor exist within the reactor that would create a composition gradient either at a vapor-liquid interface or within the liquid.
Some strategies for improving the incorporation of comonomer at higher reaction temperatures include increasing the ratio of monomers of C3-C10 alpha-olefin/ethylene in the reactor, increasing the Al/Zr ratio in a zirconium-containing coordination metallocene catalyst or by making changes in the catalyst architecture.
Temperature control may be used to influence the reactivity ratios in a manner that leads to microstructures with better than statistical microstructures and/or to microstructures tending toward alternating microstructures. Typically, lower temperature are advantageous for achieving a better than statistical microstructure and/or a microstructure that tends toward alternation of the ethylene and C3-C10 alpha-olefin units. Some or all of the above may be important for controlling the microstructure within the copolymer chains as well as controlling variations of the C3-C10 alpha-olefin unit composition from chain to chain.
According to one or more embodiments, the copolymer described herein may be functionalized. The invention provides functionalized derivatives of the copolymers described above, and provides for compositions comprising the same. The functionalized copolymers of this invention may exhibit lower viscosities for better melt flows and lower operating temperatures in various processing applications. The invention also relates to methods of using these functionalized copolymers in applications requiring particular processing elements and/or specific physical properties in the final product. In still another aspect, the invention relates to the articles prepared from these functionalized copolymers. These functionalized copolymers and polymeric blends containing the same, may be employed in the preparation of solid articles, such as moldings, films, sheets, and foamed objects. These articles may be prepared by molding, extruding, or other processes. The functionalized copolymers are useful in adhesives, tie layers, laminates, polymeric blends, and other end uses. The resulting products may be used in the manufacture of components for automobiles, such as profiles, bumpers and trim parts, or may be used in the manufacture of packaging materials, electric cable insulation, coatings and other applications.
The ethylene/C3-C10 alpha-olefin copolymers can be functionalized by incorporating at least one functional group in the copolymer structure. Exemplary functional groups may include, for example, ethyienically unsaturated mono- and di-functional carboxylic acids, ethylenically unsaturated mono- and di-functional carboxylic acid anhydrides, salts thereof and esters thereof and epoxy-group containing esters of unsaturated carboxylic acids. Such functional groups may be incorporated into the copolymer by reaction with some or all of the unsaturation in the copolymer
Examples of the unsaturated carboxylic acids, dicarboxylic acids which may be present in the functionalized copolymer are those having about 3 to about 20 carbon atoms per molecule such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid. Unsaturated dicarboxylic acids having about 4 to about 10 carbon atoms per molecule and anhydrides thereof are especially preferred. Compounds that can be reacted with the unsaturation in the copolymer include for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, cyclohex-4-ene-1,2-di-carboxylic acid, bicyclo[2,21]hept-5-ene-2,3-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, allylsuccinic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride and bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride. One particularly useful functional group may be introduced using maleic anhydride.
The ethylene/C3-C10 alpha-olefin copolymers can be functionalized by an ene reaction of the alkenyl group of the copolymer and an enophile containing a multiple bond.
The amount of the functional group present in the functionalized copolymer can vary. The functional group can typically be present in an amount of at least about 0.3 weight percent, or at least 1.0 weight percent, preferably at least about 5 weight percent, and more preferably at least about 7 weight percent. The functional group will typically be present in an amount less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent, or less than about 10 weight percent and more preferably less than about 5 weight percent. A desirable range can be any combination of any lower wt. % limit with any upper wt. % limit described herein provided the lower limit is less than the upper limit, each of which combinations of upper and lower limits are disclosed herein.
Polymers Plasticized with the Copolymers
The ethylene/C3-C10 alpha olefin copolymers described herein are blended with at least one polyolefin to prepare the plasticized compositions of this invention.
Suitable polyoleffns include homopolymers or copolymers of one or more olefins selected from C2 to C20 linear, branched, cyclic, and aromatic-containing monomers, specifically including ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 5-ethyl-1-nonene, vinylcyclohexane, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantane, styrene, alpha-methylstyrene, para-alkylstyrenes such as paramethyl styrene, 4-phenyl-1-butene, allyl benzene, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene. For example, the polyolefin may be poly(4-methyl-pentene-1) homopolymer, or a copolymer of 4-methyl-penten-1 and another olefin.
Preferred polyolefins include polyethylene homopolymers, polypropylene homopolymers, polybutene homopolymers, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, propylene-butene copolymers, propylene-hexene copolymers, propylene-octene copolymers, and copolymers of one or more olefins selected from C2 to C4 olefins with one or more cornonomers selected from diolefins and oxygen-containing olefins (examples being ethylene-propylene-diene and ethylene-vinyl acetate copolymers). The polyolefin component may be a blend of one or more polyolefins, or a blend of polymers comprising at least 50 wt. % of one or more polyolefins.
In certain embodiments, the polyolefin is selected from the general class of polyolefins known as “polyethylene” (i.e., ethylene homopolymers, ethylene copolymers, and blends thereof). These include plastomers having a density of less than 0.91 g/cm; low density polyethylene having a density of more than 0.91 g/cm3 to less than 0.94 g/cm3; and high density polyethylene (HDPE) having a density of 0.94 g/cm3 or more. A polyethylene material comprises at least 50 mole %, or 60 mol %, or at least 70 mol %, or at least 80 mol %, or at least 90 mol %, or at least 95 mol %, or 100 mole % ethylene units. Polyethylene copolymers may be random copolymers, statistical copolymers, block copolymers, and blends thereof. Comonomers are preferably selected from C3 to C20 alpha-olefins, or from C3 to C10 alplia-olefins, or from 1-butene, 1-hexene, and 1-octene; and preferably are present from 0.1 to 20 wt. %, or from 0.5 to 10 wt. %, or from 1 to 5 wt. %, or from 2 to 35 wt. %, or from 5 to 30 wt. %, or from 15 to 25 wt. %. Polyethylene copolymers may comprise up to 50 mol % diene.
In other embodiments, the polyolefin is selected from the general class of polyolefins known as “polypropylene” (i.e., propylene homopolymers, copolymers, and blends thereof). These include isotactic polypropylene (iPP), highly isotactic polypropylene, syndiotactic polypropylene (sPP), homopolymer polypropylene (hPP, also called propylene homopolymer or homopolypropylene), so-called random copolymer polypropylene. A polypropylene material comprises at least 50 mol %, or 60 mol %, or at least 70 mol %, or at least 80 mol %, or at least 90 mol %, or at least 95 mol %, or 100 mol % propylene units. Polypropylene copolymers may be random copolymers, statistical copolymers, block copolymers, impact copolymers, and blends thereof. Comonomers are preferably selected from ethylene and C4 to C20 alpha-olefins, or from ethylene and C4 to C10 alpha-olefins, or from ethylene, 1-butene, 1-hexene, and 1-octene; and preferably are present from 0.1 to 20 wt. %, or from 1 to 10 wt. %, or from 2 to 5 wt. %, or from 2 to 35 wt. %, or from 5 to 30 wt. %, or from 15 to 25 wt. %. Polypropylene copolymers may also comprise up to 50 mol % diene.
In other embodiments, the polyolefin is selected from the general class of polyolefins known as “polybutene” (i.e., butene-1 homopolymers, copolymers, and blends thereof). The homopolymer may be atactic, isotactic, or syndiotactic polybutene, and blends thereof. The copolymer can be a random copolymer, a statistical copolymer, a block copolymer, and blends thereof. Random copolymers include those where the comonomer is selected from ethylene, propylene, 1-hexene, and 1-octene. Blends include impact copolymers, elastomers and plastomers, any of which may be physical blends or in situ blends with the polybutene. Poly(l-butene) homopolymers and 1-butene/ethylene copolymers are commercially available from Basell Polyolefins.
In other embodiments, the polyolefin is selected from the general class of polyolefins known as “ethylene-propylene (EP) elastomers” which are copolymers of ethylene and propylene and optionally one or more diene monomer(s), and also known in the art as EPM or EPDM elastomers. EP elastomers have little to no crystallinity with a heat of fusion of 20 J/g or less, a density of 0.86 g/cm3 or less, an ethylene content from 35 to 85 mol %, a diene content of 0 to 5 mol %, a minimum propylene content of 15 mol %, and a mol ecular weight of at least 50 kg/mol.
Suitable polyolefins may comprise up to 20 wt. %, or up to 10%, or up to 1 wt. % diene (i.e., diolefin) monomers. Examples include alpha-omega diene (i.e., di-vinyl) monomers such as 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, and 1,13-tetradecadiene, as well as cyclic dienes such as cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, and dicyclopentadiene.
Other suitable polyolefins are described in WO 03/040201, WO 03/040095, WO 03/040202, WO 03/040233, WO 2009/020706, and WO 03/040442.
The method of making the polyolefin is not critical, as it can be made by slurry, solution, gas phase, high pressure or other suitable processes, and by using catalyst systems appropriate for the polymerization of polyethylenes, such as chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof, or by free-radical polymerization. Catalyst systems suitable to make polyethylene are well known in the art; see, for example Metallocene-Based Polyolefins (Wiley & Sons, 2000).
In one or more embodiments, one or more of the ethylene/C3-C10 alpha olefin plasticizer components of the invention is present in an amount of from a low of 0.5 wt. %, or 1 wt. %, or 2 wt. %, or 3 wt. %, or 4 wt. %, or 5 wt. %, to a high of 50 wt. %, or 45 wt. %, or 40 wt. %, or 35 wt. %, or 30 wt. %, or 25 wt. %, or 20 wt. %, or 15 wt. %, or 10 wt. %, or 5 wt. %, based on total weight of plasti cizer component(s) and polyolefin(s), wherein a desirable range can be any combination of any lower wt. % limit with any upper wt. % limit described herein provided the lower limit is less than the upper limit, in other embodiments, the composition includes the at least one ethylene/C3-C10 alpha olefin plasticizer in an amount of about 1 to 40 wt. %, or 2 to 30 wt. %, or 4 to 20 wt. %, based on the total weight of the composition.
In one or more embodiments, one or more polyolefin component is present in an amount of from a low of 50 wt. %, or 55 wt. %, or 60 wt. %, or 65 wt. %, or 70 wt. %, or 75 wt. %, or 80 wt. %, or 85 wt. %, or 90 wt. %, or 95 wt. % to a high of 99 wt. %, or 95 wt. %, or 90 wt. %, or 85 wt. %, or 80 wt. %, or 75 wt. %, or 70 wt. %, or 65 wt. %, or 60 wt. %, based on total weight of ethylene/C3-C10 alpha olefin plasticizer component(s) and polyolefin(s), wherein a desirable range can be any combination of any lower wt. % limit with any upper wt. % limit described herein provided the lower limit is less than the upper limit. In other embodiments, the composition includes at least one polyolefin in an amount of about 60 to 99 wt. %, or 70 to 98 wt. %, or 80 to 96 wt. %, based on the total weight of the composition.
Additives commonly used in the polyolefin industry to impart certain desirable properties may be present in the polyolefin compositions of the present invention. Such additives are described in Plastics Additive Handbook, 5th Ed,; H, Zweifel, Ed. (Hanser-Gardner, 2001) and include antioxidants (including organic phosphites, hindered amines, and phenolics), stabilizers (including UV stabilizers and other UV absorbers), nucleating agents (including clarifying agents, metal salts such as sodium benzoate, sorbitol derivatives, and metal phosphates), pigments, dyes, color masterbatches, processing aids, waxes, oils, lubricants, surfactants, slip agents (including metal salts of fatty acids such as zinc stearate and fatty acid amides such erucamide), tackifiers, block, antiblock, neutralizers (such as hydro talcite), acid scavengers, anticorrosion agents, cavitating agents, blowing agents, quenchers, antistatic agents, fire retardants, cure or cross linking agents or systems (such as elemental sulfur, organo-sulfur compounds, organic peroxides, and di- or tri-amines), coupling agents (such as silane), and combinations thereof. The additives may be present in amounts known in the art to be effective, preferably at 0.01 to 10 wt. % (100 to 100,000 ppm), or 0.02 to 1 wt. % (200 to 10,000 ppm), or 0.025 to 0.5 wt. % (250 to 5,000 ppm), or 0.05 to 0.25 wt. % (500 to 2,500 ppm), or 0.1 to 5 wt. % (1,000 to 50,000 ppm), based upon the weight of the composition (where ppm is parts-per-million by weight).
Fillers may be present in the polyolefin compositions of the present invention. Desirable fillers include but not limited to: natural or synthetic mineral aggregates (including talc, wollastonite, and calcium carbonate), fibers (including glass fibers, carbon fibers, or polymeric fibers), carbon black, graphite, natural and synthetic clays (including nanoclays and organoclays), sand, glass beads, and any other porous or nonporous fillers and supports known in the art, utilized alone or admixed to obtain desired properties. The filler may be present at 0.1 to 50 wt. %, or 1 to 40 wt. %, or 2 to 30 wt. %, or 5 to 20 wt. %, based on the weight of the total composition. Filler content is equated with the wt. % ash content as determined by the ISO 3451-1 (A) test method. Blending
The ethylene/C3-C10 alpha olefin plasticizer(s), polyolefin(s), and optional additives can be combined using any suitable means. Those skilled in the art will be able to determine the appropriate procedure to balance the need for intimate mixing with the desire for process economy. For example, one or more polyolefin component can be in the form of pellets or reactor granules, which are combined with the copolymer plasticizer(s) and optional additives by simple physical blending of constituent pellets and/or granules, since the forming of articles includes a (re)melting and mixing of the raw material(s). The polyolefin components may be in any physical form when blended with the ethylene/C3-C10 alpha olefin plasticizer(s) and optional additives. For example, they may be in the form of reactor granules (i.e., granules of polymer that are isolated from the polymerization reactor prior to any processing procedures), or in the form of pellets that are formed from melt extrusion of the reactor granules. The polyolefin(s), ethylene/C3-C10 alpha olefin plasticizer, and optional additives can be blended by any suitable means known to those skilled in the art such as, for example, the blending processes described in WO 2009/020706.
The compositions of the present invention can be useful for the fabrication of shaped articles made or formed by any useful discrete molding or continuous extrusion means for forming and shaping polyolefins known in the art, including: compression molding, injection molding, co-injection molding, gas-assisted injection molding, blow molding, multi-layer blow molding, injection blow molding, stretch blow molding, extrusion blow molding, transfer molding; cast molding, rotational molding, foam molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming matched-die molding, thermoforming, vacuum forming, film blowing, film or sheet casting, sheet extrusion, profile extrusion or co-extrusion, fiber spinning, fiber spunbonding, fiber melt blowing, lamination, calendering, coating, pultrusion, protrusion, draw reduction, foaming, or other forms of processing such as described in, for example, Plastics Processing (Radian Corporation, Noyes Data Corp. 1986), or combinations thereof.
The plasticized compositions of the present invention can be useful for consumer goods, industrial goods, construction materials, packaging materials, appliance components, electrical components, and automotive components. Non-limiting examples of desirable articles of manufacture made from compositions of the invention include films, tapes, sheets, fibers, tubing, pipes, hoses, belts, coatings, fabrics (woven and nonwoven), tarps, agricultural barriers, packaging (durable and disposable), kitchen devices and household appliances (washing machines, refrigerators, blenders, air conditioners, etc.), furniture (indoor and outdoor, such as tables, chairs, benches, shelving, etc.), sporting equipment (skis, surfboards, skateboards, skates, boots, sleds, scooters, kayaks, paddies, etc.), solid wheels, stadium seating, amusement park rides, personal protective equipment (safety helmets, shin guards, etc.), emergency response equipment, cookware, utensils, trays, pallets, carts, tanks, tubs, pond liners, storage containers (crates, pails, jars, bottles, etc.), toys, child car seats and booster chairs, medical devices and components (including syringe parts and catheters), luggage, tool housings (for drills, saws, etc.), wire and cable jackets, electronics housings and components (for televisions, computers, phones, hand-held devices, media players, stereos, radios, clocks, etc.), building construction materials (flooring, siding, roofing, counter tops, seals, joints, isolators, etc.), lighting, gardening equipment (handles on shovels, wheelbarrows, etc.), playground equipment, motor housings, pump housings, battery housings, instrument housings, switches, knobs, buttons, handles, pet supplies, laboratory supplies, personal hygiene devices (razors, brashes, hairdryers, etc.), cleaning supplies (brooms, dust pans, etc.), musical instrument cases, statues, trophies, artwork, costume jewelry, picture frames, eyeglass frames, plant pots, and firearm components.
Plasticized polyolefin compositions of the present invention provide for improved plasticization durability of the plasticizer relative to comparable compositions made using conventional plasticizers. Improved plasticization durability is advantageous for successful long-term property retention. In certain embodiments, useful plasticized polyolefin compositions may exhibit a reduced TGA Volatility, Plasticized polyolefin compositions of the present invention provide for lower glass transition temperatures relative to comparable compositions made using a conventional plasticizer. A lower Tg is advantageous for improved low temperature flexibility and toughness. Plasticized polyolefin compositions of the present invention may also provide for lower melt viscosity relative to comparable compositions made using a conventional plasticizer. A lower melt viscosity (e.g., MI or MFR) is advantageous for improved low temperature flexibility and toughness.
Functionalization to make Dispersants
According to one or more embodiments, the copolymer described herein may be functionalized through a variety of mechanisms to produce dispersants useful in lubricating oils or dispersants useful in fuels (also known as fuel detergents). Dispersants are typically polymeric materials with an oleophilic component providing oil solubility and a polar component providing dispersancy. Dispersante used in lubricating oils typically are hydrocarbon polymers modified to contain nitrogen- and ester-based groups. In some cases, the dispersante may include hydrocarbon polymers such as the copolymers described herein. Dispersante may be used to maintain, in a suspension in oil, any insolubles formed by oxidation, etc. during use, which may prevent sludge flocculation and precipitation. The amount of dispersant employed may be dictated and controlled, for example, by the effectiveness of the particular material in achieving its dispersant function Thus, in some cases, a dispersant can be formed by reaction of a copolymer having an end group as discussed herein with a suitable functional moiety.
According to one or more embodiments, dispersants disclosed herein may reduce the total amount of dispersant needed in a lubricating oil formulation necessary to meet certain industry standard performance criteria. According to one or more embodiments, lubricating oils that comprise the dispersante are disclosed herein. Lubricating oils comprising the dispersante disclosed herein may exhibit improved cold weather performance, as evidenced, for example, by meeting standards associated with the MRV test. Methods for making and using the copolymers, dispersante, and lubricating oils are also generally described.
According to one or more embodiments, an ethylene-C3-C10 alpha olefin copolymer may serve as the hydrocarbon tail or backbone for a dispersant incorporated into a lubricating oil showing good low temperature performance, as demonstrated by, for example, passing the MRV test for engine oil lubricants. Dispersants are typically polymeric materials with an oleophilic component providing oil solubility and a polar component providing dispersancy. Thus, for example, when used in a lubricating oil, a dispersant may facilitate passage of a MRV test. The lubricating oil's viscosity may be less than 60,000 cP at one or more temperatures as outlined in the MRV test, e.g., temperatures of less than −20° C., less than −25° C., less than −30° C., less than −35° C., less than −40° C., less than −45° C., less than −50° C., less than −55° C., less than −60° C., less than −65° C., etc.
In some embodiments, the ethylene-C3-C10 alpha copolymer useful for making dispersants has a number average molecular weight as measured by GPC less than 5000, less than 3500, or less than 2500; an ethylene content less than 80 mol %, less than 70 mol %, or 30-60 mol %; a terminal unsaturation of 70 mol % or greater, 85 mol % or greater, or 95 mol % or greater; at least 70 mol %, at least 80 mol %, or at least 90 mol % of the unsaturation is a terminal group having a terminal vinylidene or a tri-substituted isomer of the terminal vinylidene; an average ethylene run length nc2, as determined by 13C NMR spectroscopy, of less than 2.6, less than 2.5, or less than 2.4; and a cross over temperature less than −20° C., less than −30° C. or less than −40° C. Some copolymers may have, in various embodiments, one, two, three, four, or more of any of the above recitations. In some further embodiments, the above-described copolymer is used to prepare dispersante through one of the following chemical mechanisms, e.g., a succinimide-succinimide approach, a Koch-approach, a Mannich-approach, a hydroformylation-reductive-amination approach, or a halogenation-amination approach.
The dispersants described herein, such as hydrocarbyl amines, amides, carboxylic acids and functionalized glycols, imidazolines, succinimides, succinamides, triazines, succinic ester/acid or ester/amide, Mannich product, alkyl sulphonic acids, esters, hydrocarbyl hydroxy benzoates, betaines, and quaternary ammonium salts, etc., can be prepared, for example, by functionalizing the copolymer described above through a variety of well-known chemical mechanisms to incorporate one or more functional portion into the copolymer via the terminal double bond (see, e.g., the discussion of Formulas (A)-(C) above). Accordingly, the copolymers described herein can be used to produce suitable dispersants by functionalizing the terminal double bond portions of the copolymers to form functionalized copolymer molecules, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, or more than 95% of which are derived from functionalizing the terminal double bond of Formulas (A), (B), and/or (C). For example, the functionalized portion may be produced by any chemical derivatization of atoms or chemical moiety of the copolymer discuss herein, for example, carbon-carbon bond groups (e.g., alkenyl, alkynyl), carbon-nitrogen bond groups, carbon-oxygen bond groups, carbon-sulfur bond groups, and the like. Examples of chemical derivatization include, for example, imidization, succinimide formation (succinimide approach), a Koch reaction (Koch-approach), a Mannich reaction (Mannich-approach), a hydroformylation-reductive-amination approach, or a halogenation-amination approach, e.g., as described below. Methods of functionalizing copolymers as taught, for example, in U.S. Pat. No. 5,936,041.
Succinimide-functionalization refers to a process wherein the copolymer described herein is converted to a hydrocarbyl succinic acid or anhydride, i.e., the copolymer backbone substituted with one or more succinic acid or anhydride groups, which subsequently is reacted with a polyamine to form a hydrocarbyl succinimide. Hydrocarbyl succinic acid or anhydride can be made by derivatizing the terminal double bond with an unsaturated organic acid reagent via thermal ene reaction and/or halogenation-condensation. See, e.g., U.S. Pat. No. 7,897,696. In the hydrocarbyl succinic acid or anhydride, the ratio of succinic moiety: copolymer backbone is 0.8:1 to 2:1, preferably 1:1 to 1.6:1, more preferably 1.2:1-1.5:1.
The unsaturated organic acidic reagent of the disclosed process refers to an unsaturated substituted or un-substituted carboxylic acid reagent, for example maleic or fumaric reactants of the general formula:
wherein X and X′ are he same or different, provided that at least one of X arid X′ is a group that is capable of reacting to esterify alcohols, forming amides or amine salts with ammonia or amines, forming metal salts with reactive metals or basically reacting metal compounds, or otherwise functioning as an acylating agent. Typically, X and/or X′ is —OH, —O-hydrocarbyl, —NH2, and taken together X and X′ can be —O— so as to form an anhydride, in some cases, X and X′ are such that both carboxylic functions can enter into acylation reactions.
Maleic anhydride is a suitable unsaturated acidic reactant. Other suitable unsaturated acidic reactants include electron-deficient olefins such as monophenyl maleic anhydride; monomethyl maleic anhydride, dimethyl maleic anhydride, N-phenyl maleimide and other substituted maleimides; isomaleimides; fumaric acid, maleic acid, alkyl hydrogen maleates and fumarates, dialkyil fumarates and maleates, fumaronilic acids and maleanic acids; and maleonitrile and fumaronitrile.
The percent actives of the hydrocarbyl succinic anhydride can be determined using a chromatographic technique. This method is described in column 5 and 6 in U.S. Pat. No. 5,334,321.
Conversion of hydrocarbyl succinic acid or anhydride to a succinimide is well known in the art and may be accomplished through the reaction of a polyamine with the hydrocarbyl succinic acid or anhydride, wherein the polyamine has at least one basic nitrogen in the compound, as described in U.S. Pat. No. 3,215,707 and U.S. Pat. No. 4,234,435. Suitable polyamines may have at least three nitrogen atoms and about 4 to 20 carbon atoms. One or more oxygen atoms may also be present in the polyamine.
A particularly suitable group of polvamines for use in the present disclosure are polyalkylene polyamines, including alkylene diamines. Such polyalkylene polyamines may contain from about 2 to about 12 nitrogen atoms and from about 2 to about 24 carbon atoms. Preferably, the alkylene groups of such polyalkylene polyamines may contain from about 2 to about 6 carbon atoms, more preferably from about 2 to about 4 carbon atoms.
Particularly suitable polyalkylene polyamines are those having the formula: H2N—(R1NH)a—H wherein R1 is a straight- or branched-chain alkylene group having from about 2 to about 6 carbon atoms, preferably about 2 to about 4 carbon atoms, most preferably about 2 carbon atoms, i.e., ethylene (—CH2CH2—); and a is an integer from 1 to about 10, preferably 1 to about 4, and more preferably about 3.
Examples of suitable polyalkylene polyamines include, but are not limited to, ethylenediamine, propylenediamine, isopropylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, dipropylenetriamine, dimethylaminopropylamine, diisopropylenetriarnine, dibutylenetriamine, di-sec-butylenetriatnine, triethylenetetraamine, tripropylenetetraamine, triisobutylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropylamine, and mixtures thereof.
Particularly suitable polyalkylene polyamines are ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, and pentaethylenehexamine.
Many of the polyamines suitable for use in the present disclosure are commercially available and others may be prepared by methods which are well known in the art. For example, methods for preparing amines and their reactions are detailed in Sidgewick's “The Organic Chemistry of Nitrogen,” Clarendon Press, Oxford, 1966; Noller's “Chemistry of Organic Compounds,” Saunders, Philadelphia, 2nd Ed., 1957; and Kirk-Othmer's “Encyclopedia of Chemical Technology,” 2nd Ed., especially Volume 2, pp. 99-116.
The reaction of polyamine and hydrocarbyl succinic acid or anhydride affords mono-succinimide, bis-succinimide, tris-succinimide, or other succinimides depending on the charge ratio of polyamine and succinic acid or anhydride. In some embodiment, the ratio between hydrocarbyl succinic acid/anhydride and polyamine is 1:1 to 3.2:1, or 2.5:1 to 3:1, or 2.9:1 to 3:1, or 1.6:1 to 2.5:1, or 1.6:1 to 2:1, or 1.6:1 to 1.8:1, 1.3:1 to 1.6:1, 1.4:1 to 1.6:1, or 1;1 to 1.3:1, or 1.2:1 to 1.3:1.
In some embodiments, a derivatized copolymer is prepared by a process comprising: (1) coupling an ethylene-C3-C10 alpha olefin copolymer described herein with an unsaturated mono- or dicarboxylic acid or anhydride to form a copolymer substituted with mono- or dicarboxylic acid or anhydride; (2) reacting the copolymer substituted with mono- or dicarboxylic acid or anhydride with a primary amine-eontaining compound; and (3) optionally post-treating the reaction product of step (2).
In some embodiments, a derivatized copolymer is prepared by a process comprising: reacting an alkylphenol, an aldehyde, and an amine compound, wherein the alkylphenol is prepared from a substituted or unsubstituted hydroxyaromatic compound and an ethylene-C3-C10 alpha olefin copolymer described herein.
The hydroformylation-reductive-amination reaction involves reacting an aldehyde or ketone with an amino compound under condensation conditions sufficient to give an imine intermediate, which is subsequently reacted under hydrogenation conditions sufficient to give an amine dispersant. In some embodiments of this invention, the copolymer having terminal double bond described herein is converted to an aldehyde or ketone by hydroformylation of the terminal double bond. The resulting aldehyde or ketone may be reacted with amine under reductive amination reaction condition to provide a dispersant. Processes for hydroformylation and reductive amination reaction are known in the art, as described in, for example, U.S. Patent Application Publication 20140087985, which is incorporated herein by reference in its entirety and for all purposes.
In some embodiments, a derivatized copolymer is prepared by a process comprising: (1) hydroformylating an ethylene-C3-C10 alpha olefin copolymer described above to form a copolymer having a terminal aldehyde moiety; and (2) reacting the copolymer prepared by step (1) with an amine compound under reductive condition.
The halogenation-amination reaction involves first halogenation of the terminal double bond of the copolymer, and then reacting the halogen substituted copolymer with amine to provide an amine dispersant. See, e.g., U.S. Pat. No. 5,225,092.
In some embodiments, a derivatized copolymer is prepared by a process comprising: (1) reacting an ethylene-C3-C10 alpha olefin copolymer described herein with a halogenating agent for form a halogen-containing copolymer; and (2) coupling the halogen-containing copolymer of step (1) with an amine compound.
Amine or amino compounds useful for the Koch reaction, Mannich reaction, hydroformylation-reductive-amination reaction, and halogenation-amination reaction can be ammonia, alkyl mono-amine, dialkyl mono-amine, or polyamine described above. Unless specified otherwise, the amino groups in the amine compounds can be primary amines, secondary amines, tertiary amines or any mixture thereof. These amines may be hydroearbyl amines or may be hydrocarbyl amines including one or more of other groups, e.g., hydroxy, alkoxy, amide, nitrile, imidazoline, and the like.
Primary amine-containing compounds refers to amine or amino compounds described above that contain at least one primary amine group, i.e., —NH2.
It will be appreciated that other dispersants can be prepared from terminal unsaturated polymers by known chemical reaction at the terminal double bond of a copolymer. Therefore, this invention also includes, in various embodiments, such methods and dispersants prepared therefrom.
As non-limiting examples, a dispersant may be formed by reacting a copolymer as discussed herein with a suitable functional group, for example, via a terminal double bond, to produce a compound such as:
In these structures, R1 may be a hydrocarbyl radical derived from the copolymer; R2 may be a divalent C1-C6 alkylene; R3 may be a divalent C1-C6 alkylene; each of R4 and R5, independently,
may be H, C1-C6 alkyl, or, together with the N to which they are attached, form a 5 or 6-membered ring optionally fused with an aromatic or non-aromatic ring; R6 may be H or C1-C6 alkyl, or —CH2—(NH—R2)n—NR4R5; Y may be a covalent bond or C(O); and n may be 0, 1, 2, 3, 4, 5, 6, 7, or 8. These compounds are formed by functionalization reactions such as those described above, e.g., using succinimide functionalization, the Koch reaction, the reductive amination reaction, the halogen-amination reaction, or the Mannich reaction.
Referring to Formula (I) above, the functionalized copolymer can be mono-succinimide, i.e., NR4R5 together is NH2, or bis-succinimide, i.e., NR4R5 together is:
wherein R1 is hydrocarbyl derived from the copolymer as described above.
Referring to Formula (III), the functionalized copolymer can have one of the following structures:
Following are sentences describing additional embodiments of the invention.
1. A dispersant prepared by a process comprising: functionalizing a copolymer derived from ethylene and one or more C3-10 alpha-olefins, wherein the copolymer has a number average molecular weight of less than 5,000 g/mol as measured by GPC; wherein the ethylene content of the copolymer is less than 80 mol %; wherein 70 mol % or greater of the copolymer has a carbon-carbon double bond in a terminal monomer unit, and at least 70 mol % of the terminal monomer units that have a carbon-carbon double bond have a terminal group selected from a vinylidene group and a tri-substituted isomer of a vinylidene group; and wherein the copolymer has an average ethylene run length nc2, as determined by 13C NMR spectroscopy, of less than 2.6, the average ethylene-derived unit run length nc2 is defined as the total number of ethylene-derived units in the copolymer divided by a number of runs of one or more sequential ethylene-derived units in the copolymer, and the average ethylene-derived unit ran length nc2 and also satisfies the relationship shown by the expression below:
2. The dispersant of sentence 1, wherein the copolymer has a crossover temperature at —25° C. or lower, or −35° C. or lower.
3. The dispersant of any preceding sentence, wherein the copolymer has a crossover temperature at −40° C. or lower.
4. The dispersant of any preceding sentence, wherein the ethylene content is less than 60 mol %.
5. The dispersant of any preceding sentence, wherein the ethylene content is less than 50 mol %.
6. The dispersant of any preceding sentence, wherein at least 10% and less than 70% of the total number of units in the copolymer are ethylene-derived units.
7. The dispersant of any preceding sentence, wherein at least 85 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
8. The dispersant of any preceding sentence, wherein at least 95 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
9. The dispersant of any preceding sentence, wherein the copolymer has an average ethylene run length of less than 2.4.
10. The dispersant of any preceding sentence, wherein the copolymer has an average ethylene run length of less than 2.2.
11. The dispersant of any preceding sentence, wherein the copolymer has a polydispersity index of less than or equal to 4.
12. The dispersant of any preceding sentence, wherein the copolymer has a polydispersity index of less than or equal to 3.
13. The dispersant of any preceding sentence, wherein the copolymer is an ethylene-propylene copolymer, wherein the ethylene content is 30-80 mol % and the propylene content is 20-70 mol %.
14. The dispersant of any preceding sentence, wherein the copolymer is an ethylene-propylene copolymer, wherein the ethylene content is 40-60 mol % and the propylene content is 40-60 mol %.
15. The dispersant of any preceding sentence, wherein the copolymer is an ethylene-propylene copolymer, wherein the ethylene content is about 40-50 mol % and the propylene content is about 50-60 mol %.
16. The dispersant of any preceding sentence, wherein the number average molecular weight of the copolymer is less than 3,500 g/mol.
17. The dispersant of any preceding sentence, wherein the number average molecular weight of the copolymer is less than 3,500 g/mol.
18. The dispersant of any preceding sentence, wherein the dispersant is post-treated.
19. The dispersant of any preceding sentence, wherein the dispersant is posted treated with anhydride, a boron compound, or a mixture thereof.
20. The dispersant of any preceding sentence, wherein the dispersant has one of the following formulas:
wherein R1 is an hydrocarbyl radical derived from the copolymer; R2 is a divalent C1-C6 alkylene; R3 is a divalent C1-C6 alkylene; each of R4 and R5, independently, is H, C1-C6 alkyl,
or, together with the N to which they are attached to, form a 5 or 6-membered ring optionally fused with an aromatic or non-aromatic ring; R6 is H or C1-C6 alkyl, or —CH2—(NH—R2)n—NR4R5; Y is a covalent bond or C(O); and n is 0, 1, 2, 3, 4, 5, 6, 7, or 8.
21. The dispersant of any preceding sentence, wherein the vinylidene group and the tri-substituted isomer of a vinylidene group of the copolymer has one or more of the following structural formulas (A)-(C):
wherein R represents a C1-C8 alkyl group and
indicates the bond is attached to the remaining portion of the copolymer.
22. A lubricating oil, comprising: a major amount of a base oil; 3-20 wt. % a viscosity index improver; 0-1 wt. % a pour point depressant; and 0.2-20 wt. % of the dispersant of any previous sentence.
23. The lubricating oil of sentence 22, wherein the lubricating oil has a mini-rotary viscometer (MRV) value of 60,000 cP or less at −30° C. as determined by the ASTM D4684 test.
24. The lubricating oil of any one of sentences 22 or 23, wherein the lubricating oil has a mini-rotary viscometer (MRV) value of 60,000 cP or less at −40° C. as determined by the ASTM D4684 test.
25. The lubricating oil of any one of sentences 22-24, wherein the dispersant comprises less than 10 wt. % of the lubricating oil.
26. A fuel composition or fuel additive composition, comprising the dispersant of sentence 20.
27. The fuel composition or fuel additive composition of sentence 26, the dispersant having one of the following formulas:
wherein R1 is an hydrocarbyl radical derived from the copolymer; R2 is a divalent C1-C6 alkylene; R3 is a divalent C1-C6 alkylene; each of R4 and R5, independently, is H, C1-C6 alkyl,
or, together with the N to which they are attached to, form a 5 or 6-membered ring optionally fused with an aromatic or non-aromatic ring; R6 is H or C1-C6 alkyl, or —CH2—(NH—R2)n—NR4R5; Y is a covalent bond or C(O); and n is 0, 1, 2, 3, 4, 5, 6, 7, or 8.
28. A copolymer derived from ethylene and one or more C3-10 alpha-olefins, wherein the copolymer has a number average molecular weight of less than 5,000 g/mol as measured by GPC; wherein the ethylene content of the copolymer is less than 80 mol %; wherein 70 mol % or greater of the copolymer has a carbon-carbon double bond in a terminal monomer unit, and at least 70 mol % of the terminal monomer units that have a carbon-carbon double bond have a terminal group selected from a vinylidene group and a tri-substituted isomer of a vinylidene group; and wherein a storage modulus of the copolymer is equal to a loss modulus of the copolymer at a temperature of −30° C. or lower, the values of the storage modulus and the loss modulus of the copolymer being determined by oscillatory rheometry.
29. The copolymer of sentence 28, wherein the vinylidene group and the tri-substituted isomer of a vinylidene group of the copolymer has one or more of the following structural formulas (A)-(C):
indicates the bond is attached to the remaining portion of the copolymer.
30. The copolymer of sentence 28, wherein the copolymer has an average ethylene run length (nC2) of less than 2.6, as determined by 13C NMR spectroscopy.
31. The copolymer of sentence 30, wherein the copolymer has an average ethylene run length (nC2) satisfying the relationship shown by the expression below:
32. The copolymer of any one of sentences 28 or 29, wherein the copolymer has a crossover temperature of −20° C. or lower.
33. The copolymer of any one of sentences 28-32, wherein the ethylene content is less than 70 mol %.
34. The copolymer of any one of sentences 28-33, wherein less than 65% of the total number of units in the copolymer are ethylene-derived units.
35. The copolymer of any one of sentences 28-34, wherein less than 60% of the total number of units in the copolymer are ethylene-derived units.
36. The copolymer of any one of sentences 28-35, wherein less than 55% of the total number of units in the copolymer are ethylene-derived units.
37. The copolymer of any one of sentences 28-36, wherein less than 50% of the total number of units in the copolymer are ethylene-derived units.
38. The copolymer of any one of sentences 28-37, wherein less than 45% of the total number of units in the copolymer are ethylene-derived units.
39. The copolymer of any one of sentences 28-38, wherein less than 40% of the total number of units in the copolymer are ethylene-derived units.
40. The copolymer of any one of sentences 28-39, wherein at least 10% and less than 80% of the total number of units in the copolymer are ethylene-derived units.
41. The copolymer of any one of sentences 28-40, wherein at least 20% and less than 70% of the total number of units in the copolymer are ethylene-derived units.
42. The copolymer of any one of sentences 28-41, wherein at least 30% and less than 65% of the total number of units in the copolymer are ethylene-derived units.
43. The copolymer of any one of sentences 28-42, wherein at least 40% and less than 60% of the total number of units in the copolymer are ethylene-derived units.
44. The copolymer of any one of sentences 28-43, wherein at least 20% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
45. The copolymer of any one of sentences 28-44, wherein at least 30% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
46. The copolymer of any one of sentences 28-45, wherein at least 35% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
47. The copotymer of any one of sentences 28-46, wherein at least 40% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
48. The copolymer of any one of sentences 28-47, wherein at least 45% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
49. The copolymer of any one of sentences 28-48, wherein at least 50% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
50. The copolymer of any one of sentences 28-49, wherein at least 55% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
51. The copolymer of any one of sentences 28-50, wherein at least 60% of the total number of units in the copolymer are C3-C10 alpha-olefin-derived units.
52. The copotymer of any one of sentences 28-51, wherein at least 75 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
53. The copolymer of any one of sentences 28-52, wherein at least 80 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
54. The copolymer of any one of sentences 28-53, wherein at least 85 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
55. The copolymer of any one of sentences 28-54, wherein at least 90 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
56. The copolymer of any one of sentences 28-55, wherein at least 95 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
57. The copolymer of any one of sentences 28-56, wherein the copolymer has an average ethylene-derived unit run length of less than 2.8.
58. The copolymer of any one of sentences 28-57, wherein the copolymer has an average ethylene-derived unit run length of less than 2.6.
59. The copolymer of any one of sentences 28-58, wherein the copolymer has an average ethylene-derived unit run length of less than 2.4.
60. The copolymer of any one of sentences 28-59, wherein the copolymer has an average ethylene-deri ved unit run length of less than 2.2.
61. The copolymer of any one of sentences 28-60, wherein the copolymer has an average ethylene-derived unit run length of less than 2.
62. The copolymer of any one of sentences 28-61, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of −25° C. or lower.
63. The copolymer of any one of sentences 28-62, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of −30° C. or lower.
64. The copolymer of any one of sentences 28-63, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of −35° C. or lower.
65. The copolymer of any one of sentences 28-64, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of −40° C. or lower.
66. The copolymer of any one of sentences 28-65, wherein the copolymer has a polydispersity index of less than or equal to 4.
67. The copolymer of any one of sentences 28-66, wherein the copolymer has a polydispersity index of less than or equal to 3.
68. The copolymer of any one of sentences 28-67, wherein the copolymer has a polydispersity index of less than or equal to 2.
69. The copolymer of any one of sentences 28-68, wherein the C3-C10 alpha-olefin-derived units comprise propylene-derived units.
70. The copolymer of any one of sentences 28-69, wherein the number average molecular weight of the copolymer is less than 5000 g/mol.
71. The copolymer of any one of sentences 28-70, wherein the number average molecular weight of the copolymer is less than 4000 g/mol.
72. The copolymer of any one of sentences 28-71, wherein the number average molecular weight of the copolymer is less than 3000 g/mol.
73. The copolymer of any one of sentences 28-72, wherein the number average molecular weight of the copolymer is less than 2500 g/mol.
74. The copolymer of any one of sentences 28-73, wherein the number average molecular weight of the copolymer is less than 2000 g/mol.
75. The copolymer of any one of sentences 28-74, wherein the number average molecular weight of the copolymer is less than 1500 g/mol.
76. The copolymer of any one of sentences 28-75, wherein the number average molecular weight of the copolymer is less than 1000 g/mol.
77. The copolymer of any one of sentences 28-76, wherein the number average molecular weight of the copolymer is between 800 and 3000 g/mol as measured by GPC.
78. The copolymer of any one of sentences 28-77, having a total metal or ash content of 25 ppmw or less, based on the total weight of the copolymer.
79. The copolymer of sentence 78, wherein the total metal or ash content is a total content of Zr, Ti, Al and B, derived from a single-site catalyst and an optional co-catalyst.
80. The copolymer of any one of sentences 78 and 79, wherein the total metal or ash content of the copolymer is 10 ppmw or less, or 5 ppmw or less, or 1 ppmw or less, based on the total weight of the copolymer.
81. The copolymer of any one of sentences 28-80, having a fluorine content of less than 10 ppmw, or less than 8 ppmw, or less than 5 ppmw, based on the total weight of the copolymer.
82. A dispersant prepared by functionalizing a copolymer of any one of sentences 28-81.
83. The dispersant of sentence 82, wherein the dispersant has one of the following formulas:
wherein R1 is an hydrocarbyl radical derived from the copolymer, R2 is a divalent C1-C6 alkylene, R3 is a divalent C1-C6 alkylene, each of R4 and R5, independently, is H, C1-C6 alkyl, or, together with the N to which they are attached to, form a 5 or 6-membered ring optionally fused with an aromatic or non-aromatic ring; R6 is H or C1-C6 alkyl, Y is a covalent bond or C(O), and n is 0, 1, 2, 3, 4, 5, 6, 7, or 8.
84. A lubricating oil, comprising: a base oil; and 0.2-20 wt. % a dispersant of any one of sentences 82 or 83.
85. The lubricating oil of sentence 84, wherein the dispersant comprises less than 15 wt. % of the lubricating oil, based on a total weight of the lubricating oil.
86. The lubricating oil of any one of sentences 84 or 85, wherein the dispersant comprises less than 10 wt. % of the lubricating oil, based on a total weight of the lubricating oil.
87. The lubricating oil of any one of sentences 84-86, wherein the dispersant comprises less than 5 wt. % of the lubricating oil, based on a total weight of the lubricating oil.
88. The lubricating oil of any one of sentences 84-87, wherein the lubricating oil has an MRV viscosity value of 60,000 cP or less at −25° C.
89. The lubricating oil of any one of sentences 84-88, wherein the lubricating oil has an MRV viscosity value of 60,000 cP or less at −30° C.
90. The lubricating oil of any one of sentences 84-89, wherein the lubricating oil has an MRV viscosity value of 60,000 cP or less at −35° C.
91. The lubricating oil of any one of sentences 84-90, wherein the lubricating oil has an MRV viscosity value of 60,000 cP or less at −40° C.
92. A fuel or fuel additive composition, comprising a derivatized copolymer of the following formula:
wherein R1 is an hydrocarbyl radical derived from the copolymer of sentence 1, each of R4 and R5, independently, is H, C1-C6 alkyl, or, together with the N to which they are attached to, form a 5 or 6-membered ring optionally fused with an aromatic or non-aromatic ring; and R6 is H or C1-C6 alkyl.
93. The dispersant of sentence 82, wherein the dispersant is prepared by functionalizing the copolymer through one of the following chemical mechanisms: a succinimide-succinimide approach, a Koch-approach, a Mannich-approach, a hydroformylation-reductive-amination approach, or a halogenation-amination approach.
94. A dispersant prepared by a process comprising: functionalizing a copolymer derived from ethylene and one or more C3-10 alpha-olefins, wherein the copolymer has a number average molecular weight of less than 5,000 g/mol as measured by GPC; wherein the ethylene content of the copolymer is less than 80 mol %; wherein 70 mol % or greater of the copolymer has a carbon-carbon double bond in a terminal monomer unit, and at least 70 mol % of the terminal monomer units that have a carbon-carbon double bond have a terminal group selected from a vinylidene group and a tri-substituted isomer of a vinylidene group; and wherein the copolymer has an average ethylene run length nc2, as determined by 13C NMR spectroscopy, of less than 2.6, the average ethylene-derived unit run length nc2 is defined as the total number of ethylene-derived units in the copolymer divided by a number of runs of one or more sequential ethylene-derived units in the copolymer, and the average ethylene-derived unit run length nc2 and also satisfies the relationship shown by the expression below:
95. The dispersant of sentence 94, wherein the vinylidene group and the tri-substituted isomer of a vinylidene group of the copolymer has one or more of the following structural formulas (A)-(C):
wherein R represents a C1-C8 alkyl group and
96. The dispersant of sentence 94 or 95, wherein the copolymer has a crossover temperature of −25° C. or lower.
97. The dispersant of any one of sentences 94-96, wherein the copolymer has a crossover temperature of −35° C. or lower.
98. The dispersant of any one of sentences 94-97, wherein the ethylene content is less than 60 mol %.
99. The dispersant of any one of sentences 94-98, wherein the ethylene content is less than 50 mol %.
100. The dispersant of any one of sentences 94-99, wherein at least 10% and less than 80% of the total number of units in the copolymer are ethylene-derived units.
101. The dispersant of any one of sentences 94-100, wherein at least 85 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
102. The dispersant of any one of sentences 94-101, wherein at least 95 mol % of the terminal monomer units that have the carbon-carbon double bond have a terminal group selected from the vinylidene group and the tri-substituted isomer of the vinylidene group.
103. The dispersant of any one of sentences 94-102, wherein the copolymer has an average ethylene run length of less than 2.4.
104. The dispersant of any one of sentences 94-103, wherein the copolymer has an average ethylene run length of less than 2.2.
105. The dispersant of any one of sentences 94-104, wherein the copolymer has a polydispersity index of less than or equal to 4.
106. The dispersant of any one of sentences 94-105, wherein the copolymer has a polydispersity index of less than or equal to 3.
107. The dispersant of any one of sentences 94-106, wherein the copolymer is an ethylene-propylene copolymer, wherein the ethylene content is 30-80 mol % and the propylene content is 20-70 mol %.
108. The dispersant of any one of sentences 94-107, wherein the copolymer is an ethylene-propylene copolymer, wherein the ethylene content is 40-60 mol % and the propylene content is 40-60 mol %.
109. The dispersant of any one of sentences 94-108, wherein the copolymer is an ethylene-propylene copolymer, wherein the ethylene content is about 40-50 mol % and the propylene content is about 50-60 mol %.
110. The dispersant of any one of sentences 94-109, wherein the number average molecular weight of the copolymer is less than 3,500 g/mol, as measured by GPC.
111. The dispersant of any one of sentences 94-110, wherein the number average molecular weight of the copolymer is less than 1,500 g/mol, as measured by GPC.
112. The dispersant of any one of sentences 94-111, wherein the dispersant is post-treated.
113. The dispersant of any one of sentences 94-112, wherein the dispersant is posted treated with anhydride, a boron compound, or a mixture thereof.
114. The dispersant of any one of sentences 94-113, wherein the dispersant has one of the following formulas:
wherein R1 is an hydrocarbyl radical derived from the copolymer; R2 is a divalent C1-C6 alkylene; R3 is a divalent C1-C6 alkylene; each of R4 and R5, independently, is H, C1-C6 alkyl,
115. The dispersant of any one of sentences 94-113, wherein the copolymer has a total metal or ash content of 25 ppmw or less, based on the total weight of the copolymer.
116. The dispersant of sentence 115, wherein the total metal or ash content is a total content of Zr, Ti, Al and B, derived from a single-site catalyst and an optional co-catalyst.
117. The dispersant of any one of sentences 115 and 116, wherein the total metal or ash content of the copolymer is 10 ppmw or less, or 5 ppmw or less, or 1 ppmw or less, based on the total weight of the copolymer.
118. The dispersant of any one of sentences 94-117, having a fluorine content of less than 10 ppmw, or less than 8 ppmw, or less than 5 ppmw, based on the total weight of the copolymer.
119. A lubricating oil, comprising: at least 50 wt. % of a base oil; 3-20 wt. % of a viscosity index improver; 0-1 wt. % of a pour point depressant; and 0.2-20 wt. % of the dispersant of any one of sentences 94-118.
120. The lubricating oil of sentence 119, wherein the lubricating oil has a mini-rotary viscometer (MRV) value of 60,000 cP or less at −30° C. as determined by the ASTM D4684 test.
121. The lubricating oil of any one of sentences 119 or 120, wherein the lubricating oil has a mini-rotary viscometer (MRV) value of 60,000 cP or less at −40° C. as determined by the ASTM D4684 test.
122. The lubricating oil of any one of sentences 119-121, wherein the dispersant comprises less than 10 wt. % of the lubricating oil.
123. A lubricating additive package comprising 30-80 wt. % of the dispersant of any one of sentences 94-118.
124. A fuel composition or fuel additive composition, comprising the dispersant of sentence 94-118.
125. The fuel composition or fuel additive composition of sentence 124, the dispersant having one of the following formulas:
wherein R1 is an hydrocarbyl radical derived from the copolymer; R2 is a divalent C1-C6 alkylene; R3 is a divalent C1-C6 alkylene; each of R4 and R3, independently, is H, C1-C6 alkyl,
or, together with the N to which they are attached to, form a 5 or 6-membered ring optionally fused with an aromatic or non-aromatic ring; R6 is H or C1-C6 alkyl, or —CH2—(NH—R2)n—NR4R5; Y is a covalent bond or C(O); and n is 0, 1, 2, 3, 4, 5, 6, 7, or 8.
The functionalized copolymer may also be post-treated by conventional methods by a reaction with any of a variety of agents, which are known in the art. Among these are boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, anhydrides, nitriles, epoxides, cyclic carbonates, and phosphorus compounds. See U.S. Pat. No. 5,241,003.
The boron compound used as a post-treating reagent can be selected from the group consisting of boron oxide, boron halides, boron acids and esters of boron acids in an amount to provide from about 0.1 atomic proportion of boron for each mole of the nitrogen composition to about 20 atomic proportions of boron for each atomic proportion of nitrogen used. The borated derivatized copolymer can contain from about 0.05 to 2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron based on the total weight of said borated nitrogen-containing dispersant compound.
Carboxylic acid used as a post-treating reagent can be saturated or unsaturated mono-, di-, or poly-carboxylic acid. Examples of carboxylic acid include, but are not limited to, maleic acid, fumaric acid, succinic acid, naphthalic diacid (e.g., 1,8-naphthalic diacid).
Anhydride used as a post-treating reagent can be selected from the group consisting of mono-unsaturated anhydride (e.g., maieic anhydride), alkyl or alkylene-substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), aromatic carboxylic anhydrides (including naphthalic anhydride, e.g., 1,8-naphthalic anhydride).
According to one or more embodiments, the dispersants described herein comprising a functionalized copolymer may be introduced to a major amount of a base oil to produce a lubricating oil that is configured to pass the MRV test. The lubricating oil may also contain a viscosity index improver, it may further contain a pour point depressant. The TBN of a suitable dispersant may be from about 10 to about 65 on an oil-free basis, which is comparable to about 5 to about 30 TBN if measured on a dispersant sample containing about 50% diluent oil.
According to some embodiments, the lubricating oil comprises a certain weight percentage of the dispersant. In one or more embodiments, the dispersant comprises about 0.1 wt. % to about 15 wt. %, or about 0.1 wt. % to about 10 wt. %, or about 3 wt. % to about 10 wt. %, or about 1 wt. % to about 6 wt. %, or about 7 wt. % to about 12 wt. %, based upon the total final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.
In some other embodiments, the lubricating oil composition is prepared from a lubricating additive package which comprises 30-80 wt. % of a dispersant as described above.
According to some embodiments, the lubricating oil comprises a certain weight percentage of the viscosity index improver. According to one or more embodiments, the viscosity index improver comprises less than 1-20 wt. %, 3-10 wt. %, or 5-9 wt. %, based on the total weight of the lubricating oil. Other values are also possible. Other potential components of the lubricating oil are described below.
The base oil used in the lubricating oil compositions herein may be selected from any suitable bale oil. Examples include the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. These five base oil groups are as follows:
Groups I, II, and III are mineral oil process stocks. Group IV base oils contain true synthetic molecular species, which are produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and/or polyphenyl ethers, and the like, but may also be naturally occurring oils, such as vegetable oils. It should be noted that although Group III base oils are derived from mineral oil, the rigorous processing that these fluids undergo causes their physical properties to be very similar to some true synthetics, such as PAOs. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in the industry.
The base oil used in the disclosed lubricating oil composition may be a mineral oil, animal oil, vegetable oil, synthetic oil, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and re-refined oils, and mixtures thereof.
Unrefined oils are those derived from a natural, mineral, or synthetic source without or with little further purification treatment. Refined oils are similar to the unrefined oils except that they have been treated in one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. Oils refined to the quality of an edible may or may not be useful. Edible oils may also be called white oils. In some embodiments, lubricating oil compositions are free of edible or white oils.
Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
Mineral oils may include oils obtained by drilling or from plants and animals or any mixtures thereof. For example such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.
Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), trimers or oligomers of 1-decene, e.g., poly(1-decenes), such materials being often referred to as alpha-olefins, and mixtures thereof; alkyl-benzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkalies, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.
Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
The major amount of base oil included in a lubricating composition may be selected from the group consisting of Group I, Group II, a Group III, a Group IV, a Group V, and a combination of two or more of the foregoing, and wherein the major amount of base oil is other than base oils that arise from provision of additive components or viscosity index improvers in the composition. In another embodiment, the major amount of base oil included in a lubricating composition may be selected from the group consisting of Group II, a Group III, a Group IV, a Group V, and a combination of two or more of the foregoing, and wherein the major amount of base oil is other than base oils that arise from provision of additive components or viscosity index improvers in the composition.
The amount of the oil of lubricating viscosity present may be the balance remaining after subtracting from 100 wt. % the sum of the amount of the performance additives inclusive of viscosity index improver(s) and/or pour point depressant(s) and/or other top treat additives. For example, the oil of lubricating viscosity that may be present in a finished fluid may be a “major amount,” such as greater than about 50 wt. %, greater than about 60 wt. %, greater than about 70 wt. %, greater than about 80 wt. %, greater than about 85 wt,%, greater than about 90 wt. %, or greater than 95 wt. %.
The lubricating oil compositions herein also may optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins (e.g., polyisobutenes), olefin copolymers (e.g., ethylene/propylene copolymers), hydrogenated styrene-isoprene polymers, styrene/maleic ester copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers and suitable examples are described in US Pat, Apl. Pub. No. 20120101017A1.
The lubricating oil compositions herein also may optionally contain one or more dispersant viscosity index improvers in addition to a viscosity index improver or in lieu of a viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine.
The total amount of viscosity index improver and/or dispersant viscosity index improver may be about 0.1 wt. % to about 20 wt. %, about 0.1 wt. % to about 15 wt. %, about 0.1 wt. % to about 12 wt. %, about 0.5 wt. % to about 10 wt. %, about 3 wt. % to about 20 wt. %, about 3 wt. % to about 15 wt. %, about 5 wt. % to about 15 wt. %, or about 5 wt. % to about 10 wt. %, of the lubricating oil composition. In some embodiments, the viscosity index improver is a polyolefin or olefin copolymer having a number average molecular weight of 10,000-500,000, 50,000-200,000, or 50,000-150,000. In some embodiments, the viscosity index improver is a hydrogenated styrene/butadiene copolymer having a number average molecular weight of 40,000-500,000, 50,000-200,000, or 50,000-150,000. In some embodiments, the viscosity index improver is a polymethacrylate having a number average molecular weight of 10,000-500,000, 50,000-200,000, or 50,000-150,000,
The lubricating oil compositions herein also may optionally contain one or more antioxidants. Antioxidant compounds are known and include for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.
The hindered phenol antioxidant may contain a secondary butyl and/or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered phenol antioxidant may be an ester and may include, e.g., Irganox™ L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox™ 4716 available from Albemarle Corporation.
Useful antioxidants may include diarylamines and high molecular weight phenols. In an embodiment, the lubricating o il composition may contain a mixture of a diarylamine and a high molecular weight phenol, such that each antioxidant may be present in an amount sufficient to provide up to about 5%, by weight, based upon the final weight of the lubricating oil composition. In an embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5% diarylamine and about 0.4 to about 2.5% high molecular weight phenol, by weight, based upon the final weight of the lubricating oil composition.
Examples of suitable olefins that may be sulfurized to form a sulfurized olefin include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful 1 olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butylacrylate.
Another class of sulfurized olefin includes sulfurized fatty acids and their esters. The fatty acids are often obtained from vegetable oil or animal oil and typically contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Often, the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. Fatty acids and/or ester may be mixed with olefins, such as alpha-olefins.
The one or more antioxidant(s) may be present in ranges about 0 wt. % to about 20 wt. %, or about 0.1 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt. %, of the lubricating oil composition.
The lubricating oil compositions herein also may optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, a metal thiophosphate; a metal dialkyldithiophosphate; a phosphoric acid ester or salt thereof; a phosphate ester(s); a phosphite; a phosphorus-containing carboxylic ester, ether, or amide; a sulfurized olefin; thiocarbamate-containing compounds including, thiocarbamate esters, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl)disulfides; and mixtures thereof. A suitable antiwear agent may be a molybdenum dithiocarbamate. The phosphorus containing antiwear agents are more fully described in European Patent 0612839. The metal in the dialkyl dithio phosphate salts may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkylthiophosphate.
Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbaniate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups may be at least 8. The antiwear agent may in one embodiment include a citrate.
The antiwear agent may be present in ranges including about 0 wt. % to about 15 wt. %, or about 0.01 wt. % to about 10 wt. %, or about 0.05 wt. % to about 5 wt. %, or about 0.1 wt. % to about 3 wt. % of the lubricating oil composition.
The lubricating oil compositions herein may optionally contain one or more boron-containing compounds.
Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057.
The boron-containing compound, if present, can be used in an amount sufficient to provide up to about 8 wt. %, about 0.01 wt. % to about 7 wt. %, about 0.05 wt. % to about 5 wt. %, or about 0.1 wt. % to about 3 wt. % of the lubricating oil composition.
The lubricating oil composition may optionally further comprise one or more neutral, low based, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids, mono- and/or di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or methylene bridged phenols. Statable detergents and their methods of preparation are described in greater detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein. The detergent substrate may be salted with an alkali or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is free of barium. A suitable detergent may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylarylsulfonic acids with the atyl group being benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, calcium sulfur containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphorus acids, calcium mono- and/or di-thiophosphoric acids, calcium alkyl phenols, calcium sulfur coupled alkyl phenol compounds, calcium methylene bridged phenols, magnesium phenates, magnesium sulfur containing phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium phosphorus acids, magnesium mono- and/or di-thiophosphoric acids, magnesium alkyl phenols, magnesium sulfur coupled alkyl phenol compounds, magnesium methylene bridged phenols, sodium phenates, sodium sulfur containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphorus acids, sodium mono- and/or di-thiophosphoric acids, sodium alkyl phenols, sodium sulfur coupled alkyl phenol compounds, or sodium methylene bridged phenols.
Overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, for example, an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.
The terminology “overbased” relates to metal salts, such as metal salts of sulfonates, carboxylases, and phenates, wherein the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its “normal,” “neutral” salt). The expression “metal ratio,” often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is one and in an overbased salt, MR, is greater than one. They are commonly referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.
An overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH/gram or greater, or as further examples, about 250 mg KOH/gram or greater, or about 350 mg KOH/gram or greater, or about 375 mg KOH/gram or greater, or about 400 mg KOH/gram or greater.
Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphorus acids, overbased calcium mono- and/or di-thiophosphoric acids, overbased calcium alkyl phenols, overbased calcium sulfur coupled alkyl phenol compounds, overbased calcium methylene bridged phenols, overbased magnesium phenates, overbased magnesium sulfur containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylie acids, overbased magnesium phosphorus acids, overbased magnesium mono- and/or di-thiophosphoric acids, overbased magnesium alkyl phenols, overbased magnesium sulfur coupled alkyl phenol compounds, or overbased magnesium methylene bridged phenols.
The overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.
The low-based/neutral detergent has a TBN of up to 175 mg KOH/g, or up to 150 mg KOH/g. The low-based/neutral detergent may include a calcium-containing detergent. The low-based neutral calcium-containing detergent may be selected from a calcium sulfonate detergent, a calcium phenate detergent and a calcium salicylate detergent. In some embodiments, the low-based/neutral detergent is a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low-based/neutral detergent is a calcium sulfonate detergent or a calcium phenate detergent.
The low-based/neutral detergent may comprise at least 2.5 wt. % of the total detergent in the lubricating oil composition. In some embodiments, at least 4 wt. %, or at least 6 wt. %, or at least 8 wt. %, or at least 10 wt. % or at least 12 wt. % or at least 20 wt. % of the total detergent in the lubricating oil composition is a low-based/neutral detergent which may optionally be a low-based/neutral calcium-containing detergent.
In certain embodiments, the one or more low-based/neutral detergents provide from about 50 to about 1000 ppm calcium by weight to the lubricating oil composition based on a total weight of the lubricating oil composition. In some embodiments, the one or more low-based/neutral calcium-containing detergents provide from 75 to less than 800 ppm, or from 100 to 600 ppm, or from 125 to 500 ppm by weight calcium to the lubricating oil composition based on a total weight of the lubricating oil composition.
In some embodiments, a detergent is effective at reducing or preventing rust in an engine.
The detergent may be present at about 0 wt. % to about 10 wt. %, or about 0.1 wt. % to about 8 wt. %, or about 1 wt. % to about 4 wt. %, or greater than about 4 wt. % to about 8 wt. %.
Additional dispersants contained in the lubricant composition may include, but are not limited to, an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed. Typically, the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group. Dispersants may be selected from Manntch dispersants as described in U.S. Pat. Nos. 3,634,535, 3,697,574 and 3,736,357; ashless succinimide dispersants as described in U.S. Pat. Nos. 4,234,435 and 4,636,322; amine dispersants as described in U.S. Pat. Nos. 3,219,666, 3,565,804, and 5,633,326; Koch dispersants as described in U.S. Pat. Nos. 5,936,041, 5,643,859, and 5,627,259, and polyalkylene suecinimide dispersants as described in U.S. Pat. Nos. 5,851,96.5; 5,853,434; and 5,792,729.
In various embodiments, the additional dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride, an olefin maleic anhydride copolymer. As an example, the additional dispersant may be described as a poly-PIBSA. In another embodiment, the additional dispersant may be derived from an anhydride which is grafted to an ethylene-propylene copolymer. Another additional dispersant may be a high molecular weight ester or half ester amide.
The additional dispersant, if present, can be used in an amount sufficient to provide up to about 10 wt. %, based upon the final weight of the lubricating oil composition. Another amount of the dispersant that can be used may be about 0.1 wt. % to about 10 wt. %, or about 0.1 wt. % to about 10 wt. %, or about 3 wt. % to about 8 wt. %, or about 1 wt. % to about 6 wt. %, based upon the final weight of the lubricating oil composition.
The lubricating oil compositions herein also may optionally contain one or more friction modifiers. Suitable friction modifiers may comprise metal containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, amino guanadine, alkanolatnides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of a polyol and one or more aliphatic or aromatic carboxylic acids, and the like.
Suitable friction modifiers may contain hydrocarbyl groups that are selected from straight chain, branched chain, or aromatic hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or hetero atoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments the friction modifier may be a long chain fatty acid ester. In another embodiment the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (triglyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.
Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols and generally include a polar terminal group (e.g. carboxyl or hydroxyl ) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is known generally as glycerol monooleate (GMO) which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, herein incorporated by reference in its entirety.
Aminic friction modifiers may include amines or polyamines. Such compounds can have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, either saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.
The amines and amides may be used as such or in the form of an adduct or reaction product with a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, herein incorporated by reference in its entirety.
A friction modifier may optionally be present in ranges such as about 0 wt. % to about 10 wt. %, or about 0.01 wt. % to about 8 wt. %, or about 0.1 wt. % to about 4 wt. %.
The lubricating oil compositions herein also may optionally contain one or more molybdenum-containing compounds. An oil-soluble molybdenum compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof. An oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-molybdenum compound, and/or mixtures thereof. The molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion, in one embodiment the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.
Suitable examples of molybdenum compounds which may be used include commercial materials sold under the trade names such as Molyvan 822™, Molyvan™ A, Molvvan 2000™ and Molyvan 855™ from R. T. Vanderbilt Co., Ltd., and Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381; U.S. Pat. No.RE 37,363 E1; U.S. Pat. No.RE 38,929 E1; and U.S. Pat. No.RE 40,595 E1, incorporated herein by reference in their entireties.
Additionally, the molybdenum compound may be an acidic molybdenum compound. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the compositions can be provided with molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds as described, for example, in U.S. Pat. Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94/06897, each incorporated herein by reference in their entireties.
Another class of suitable organo-molybdenum compounds are trinuclear molybdenum compounds, such as those of the formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms may be present among ail the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, herein incorporated by reference in its entirety.
The oil-soluble molybdenum compound may be present in an amount sufficient to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm of molybdenum.
In another embodiment, the oil-soluble compound may be a transition metal containing compound or a metalloid. The transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, and the like.
In an embodiment, an oil-soluble transition metal-containing compound may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. In an embodiment the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as a titanium (IV) alkoxide. Among the titanium containing compounds that may be used in, or which may be used for preparation of the oils-soluble materials of, the disclosed technology are various Ti (TV) compounds such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes including but not limited to titanium phenates; titanium carboxylates such as titanium (IV) 2-ethyl-1-3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed within the disclosed technology include titanium phosphates such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzenesulfonates), or, generally, the reaction product of titanium compounds with various acid materials to form salts, such as oil-soluble salts. Titanium compounds can thus be derived from, among others, organic acids, alcohols, and glycols, Ti compounds may also exist in dimeric or oligomeric form, containing Ti—O—Ti structures. Such titanium materials are commercially available or can be readily prepared by appropriate synthesis techniques which will be apparent to the person skilled in the art. They may exist at room temperature as a solid or a liquid, depending on the particular compound. They may also be provided in a solution form in an appropriate inert solvent.
In one embodiment, the titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyi- (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or it may be reacted with any of a lumber of materials, such as (a) a polyamine-based succinimide/amide dispersant having free, condensable —NH functionality; (b) the components of a polyamine-based succinimide/amide dispersant, i.e., an alkenyi- (or alkyl-) succinic anhydride and a polyamine, (c) a hydroxy-containing polyester dispersant prepared by the reaction of a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product thereof either used directly to impart Ti to a lubricant, or else further reacted with the succinic dispersants as described above. As an example, 1 part (by mole) of tetraisopropyl titanate may be reacted with about 2 parts (by mole) of a polyisobutene-substituted succinic anhydride at 140-150° C. for 5 to 6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30 g) may be further reacted with a succinimide dispersant from polyisobutene-substituted succinic anhydride and a polyethylenepolyamine mixture (127 grams+diluent oil) at 150° C. for 1.5 hours, to produce a titanium-modified succinimide dispersant.
Another titanium containing compound may be a reaction product of titanium alkoxide and C6 to C25 carboxylic acid. The reaction product may be represented by the following formula:
wherein m+n=4; n ranges from 1 to 3; R4 is an alkyl moiety with carbon atoms ranging from 1-8; R1 is selected from a hydrocarbyl group containing from about 6 to 25 carbon atoms; R2, and R3 are the same or different and are selected from a hydrocarbyl group containing from about 1 to 6 carbon atoms; or by the formula:
wherein x ranges from 0 to 3; R1 is selected from a hydrocarbyl group containing from about 6 to 25 carbon atoms. R2, and R3 are the same or different and are selected from a hydrocarbyl group containing from about 1 to 6 carbon atoms; and/or R4 is selected from a group consisting of either H, or C6 to C25 carboxylic acid moiety. Suitable carboxylic acids may include, but are not limited to caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic aicd, neodecanoic acid, and the like.
In an embodiment the oil soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 to 3000 ppm titanium by weight or 25 to about 1500 ppm titanium by weight or about 35 ppm to 500 ppm titanium by weight or about 50 ppm to about 300 ppm.
Other additives may be selected to perform one or more functions required of a lubricating fluid. Further, one or more of the mentioned additives may be multi-functional and provide functions in addition to or other than the function prescribed herein.
A lubricating oil composition according to the present disclosure may optionally comprise other performance additives. The other performance additives may be in addition to specified additives of the present disclosure and/or may comprise one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents and mixtures thereof. Typically, fully-formulated lubricating oil will contain one or more of these performance additives.
Suitable metal deactivators may include derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethaerylates, polyacrylates or polyacrylamides.
Suitable foam inhibitors include silicon-based compounds, such as siloxane.
Suitable pour point depressants may include a polymethylmethacrylates or mixtures thereof. Pour point depressants may be present in an amount sufficient to provide from about 0 wt. % to about 1 wt. %, about 0.01 wt. % to about 0.5 wt. %, or about 0.02 wt. % to about 0.04 wt. %, based upon the final weight of the lubricating oil composition.
Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000 and alkenylsuccinic acids in which the alkenyl group contains about 10 or more carbon atoms such as, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, and hexadecenylsuccinic acid. Another useful type of acidic corrosion inhibitors are the half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful. A useful rust inhibitor is a high molecular weight organic acid. In some embodiments, an engine oil is devoid of a rust inhibitor.
The rust inhibitor, if present, can be used in an amount sufficient to provide about 0 wt. % to about 5 wt. %, about 0.01 wt. % to about 3 wt. %, about 0.1 wt. % to about 2 wt. %, based upon the final weight of the lubricating oil composition.
In general terms, as an example, a suitable lubricant composition may include additive components in the ranges listed in the following Table 5.
The percentages of each component above represent the weight percent of each component, based upon the weight of the total final lubricating oil composition. The balance of the lubricating oil composition consists of one or more base oils.
Additives used in formulating the compositions described herein may be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).
Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant/inhibitor package or DI package, that will supply the characteristics that are required in the formulations. Suitable DI packages are described for example in U.S. Pat. Nos. 5,204,012 and 6,034,040 for example. Among the types of additives included in the additive package may be dispersants, seal swell agents, antioxidants, foam inhibitors, lubricity agents, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, and the like. Several of these components are well known to those skilled in the art and are generally used in conventional amounts with the additives and compositions described herein.
In all of the embodiments described herein, the lubri cant or additive composition may further comprise one or more of detergents, dispersants, friction modifiers, antioxidants, rust inhibitors, viscosity index improvers, emulsifiers, demulsifiers, corrosion inhibitors, antiwear agents, metal dihydrocarbyl dithiophosphates, ash-free amine phosphate salts, antifoam agents, and pour point depressants and any combination thereof.
According to one or more embodiments, the functionalized copolymer described herein may be introduced as a functionalized dispersant (also known as a fuel detergent) along with other additives in gasoline, biodiesel or diesel to produce a fuel composition or a fuel additive composition. According to one or more embodiments, the fuel composition comprises less than 0.5%, or less than 0.1% of a fuel additive composition comprising the functionalized dispersant. Other values are also possible. Embodiments of a fuel composition or a fuel additive composition may contain more than 500 part per million (ppm) of the functionalized fuel dispersant, or less than 300 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm. Examples of other additives which may be used include, but are not limited to, a corrosion inhibitors or antirust additives, antistatic dispersants, dehazers, demulsifiers, anti-icers, biocides, antifoamants, drag reducers, friction modifiers, antivalve-seat recession additives, phenolic antioxidants, cold flow improvers, combustion improvers, metal deactivators, friction modifiers, conductivity improvers, and pour point depressants. See, e.g., U.S. Pat. No. 5,405,417.
In selecting a functionalized fuel dispersant, it may be important to ensure that the selected dispersant is soluble or stably dispersible in an additive package and finished fuel composition, is compatible with the other components of the composition, and does not interfere significantly with the performance properties of the composition, such as rust inhibition, corrosion inhibition, improved lubricity, and improved lead compatibility, needed or desired, as applicable, in the overall finished fuel composition.
For the sake of convenience, the functionalized fuel dispersant may be provided as a concentrate for dilution. Such a concentrate forms part of the present disclosure and typically comprises from about 99 to about 1% by weight additive and from about 1 to about 99% by weight of solvent or diluent for the additive, which solvent or diluent may be miscible and/or capable of dissolving in gasoline or diesel, in which the concentrate may be used. The solvent or diluent may be gasoline, diesel, mineral oil (either paraffinic or naphthenic oils), aromatic oils, synthetic oils, or derivatives thereof. In general, the functionalized fuel dispersant additive may be employed in minor amounts sufficient to improve the performance characteristics and properties of the base fluid.
It will be appreciated that the individual components employed can be separately blended into the base fluid or can be blended therein in various subcombinations, if desired. Ordinarily, the particular sequence of such blending steps may not be crucial. Moreover, such components can be blended in the form of separate solutions in a diluent. According to various embodiments, however, the additive components may be blended in the form of a concentrate, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
In further embodiments, the invention relates to a method for lubricating an engine by lubricating an engine with a lubricant composition of any of the forgoing embodiments.
In yet a further embodiment, the invention relates to the use of a lubricating composition according to any of the forgoing embodiments to lubricate an engine.
Lubricants, combinations of components, or individual components of the present description may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to heavy duty diesel, passenger car, light duty diesel, medium speed diesel, or marine engines. An internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine, a bio-fueled engine, a mixed diesel/biofuel fueled engine, a mixed gasoline/biofuel fueled engine, an alcohol fueled engine, a mixed gasoline/alcohol fueled engine, a compressed natural gas (CNG) fueled engine, or mixtures thereof. A diesel engine may be a compression ignited engine. A gasoline engine may be a spark-ignited engine. An internal combustion engine may also be used in combination with an electrical or battery source of power. An engine so configured is commonly known as a hybrid engine. The internal combustion engine may be a 2-stroke, 4-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, low-load diesel engines, and motorcycle, automobile, locomotive, and truck engines. Particularly preferred types of engines for which the lubricant compositions of the present invention may be used are heavy duty diesel (HDD) engines. HDD engines are commonly known to produce soot levels in lubricants in the range of about 2% to about 3%. Additionally, in older model HDD engines the soot level could reach levels of up to about 8%. Additionally, gasoline direct injection (GDi) engines also suffer from soot in their lubricating fluids. A test of a GDi engine using the Ford Chain Wear Test run for 312 hours produced a soot level of 2.387% in the lubricant. Depending on the manufacturer and operating conditions the soot levels in direct fuel injection gasoline engines can be in the range of about 1.5% to about 3%. For comparison a non-direct injection gasoline engine was also tested to determine the soot amounts produced in the lubricant. The results of this test showed only about 1.152% soot in the lubricant.
Based on the higher levels of soot produced by HDD and GDi engines, the present synergistic dispersants are preferred for use with these types of engines. For use in HDD engines and direct fuel injected gasoline engines the soot present in the oil can range from about 0.05% to about 8% depending on the age, manufacturer, and operating conditions of the engine. In some embodiments, the soot level in the lubricating composition is greater than about 1.5%, or preferably the soot level is from about 1.5% to about 8%, and most preferably the soot level in the lubricating fluid is from about 2% to about 3%.
The internal combustion engine may contain components of one or more of an aluminum-alloy, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and/or mixtures thereof. The components may be coated, for example, with a diamond-like carbon coating, a lubricated coating, a phosphorus-containing coating, molybdenum-containing coating, a graphite coating, a nano-particle-containing coating, and/or mixtures thereof. The aluminum-alloy may include aluminum silicates, aluminum oxides, or other ceramic materials. In one embodiment the aluminum-alloy is an aluminum-silicate surface. As used herein, the term “aluminum alloy” is intended to be synonymous with “aluminum composite” and to describe a component or surface comprising aluminum and another component intermixed or reacted on a microscopic or nearly microscopic level, regardless of the detailed structure thereof. This would include any conventional alloys with metals other than aluminum as well as composite or alloy-like structures with non-metallic elements or compounds such with ceramic-like materials.
The lubricating oil composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt. % or less, or about 0.8 wt. % or less, or about 0.5 wt. % or less, or about 0.3 wt. % or less, or about 0.2 wt. % or less. In one embodiment the sulfur content may be in the range of about 0.001 wt. % to about 0.5 wt. %, or about 0.01 wt. % to about 0.3 wt. %. The phosphorus content may be about 0.2 wt. % or less, or about 0.1 wt. % or less, or about 0.085 wt. % or less, or about 0.08 wt. % or less, or even about 0.06 wt. % or less, about 0.055 wt. % or less, or about 0.05 wt. % or less. In one embodiment the phosphorus content may be about 50 ppm to about 1000 ppm, or about 325 ppm to about 850 ppm. The total sulfated ash content may be about 2 wt. % or less, or about 1.5 wt. % or less, or about 1.1 wt. % or less, or about 1 wt. % or less, or about 0.8 wt. % or less, or about 0.5 wt. % or less. In one embodiment the sulfated ash content may be about 0.05 wt. % to about 0.9 wt. %, or about 0.1 wt. % or about 0.2 wt. % to about 0.45 wt. %. In another embodiment, the sulfur content may be about 0.4 wt. % or less, the phosphorus content may be about 0.08 wt. % or less, and the sulfated ash is about 1 wt. % or less. In yet another embodiment the sulfur content may be about 0.3 wt. % or less, the phosphorus content is about 0.05 wt. % or less, and the sulfated ash may be about 0.8 wt. % or less.
In one embodiment the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt. % or less, (ii) a phosphorus content of about 0.1 wt. % or less, and (iii) a sulfated ash content of about 1.5 wt. % or less.
In one embodiment the lubricating oil composition is suitable for a 2-stroke or a 4-stroke marine diesel internal combustion engine. In one embodiment the marine diesel combustion engine is a 2-stroke engine. In some embodiments, the lubricating oil composition is not suitable for a 2-stroke or a 4-stroke marine diesel internal combustion engine for one or more reasons, including but not limited to, the high sulfur content of fuel used in powering a marine engine and the high TBN required for a marine-suitable engine oil (e.g., above about 40 TBN in a marine-suitable engine oil).
In some embodiments, the lubricating oil composition is suitable for use with engines powered by low sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Highway vehicle fuels contain about 15 ppm sulfur (or about 0.0015% sulfur).
Low speed diesel typically refers to marine engines, medium speed diesel typically refers to locomotives, and high speed diesel typically refers to highway vehicles. The lubricating oil composition may be suitable for only one of these types or all.
Further, lubricants of the present description may be statable to meet one or more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-6, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, ACEA A1/B1, A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6,JASO DL-1, Low SAPS, Mid SAPS, or original equipment manufacturer specifications such as Dexos™ 1, Dexos™ 2, MB-Approval 229.51/229.31, VW 502.00, 503.00/503.01, 504.00, 505.00, 506.00/506.01, 507.00, 508.00, 509.00, BMW Longlife-04, Porsche C30, Peugeot Citroën Automobiles B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM 6094-M, Chrysler MS-6395, or any past or future PCMO or HDD specifications not mentioned herein. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppm or less or 900 ppm or less or 800 ppm or less.
Other hardware may not be suitable for use with the disclosed lubricant. A “functional fluid” is a term which encompasses a variety of fluids including but not limited to tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids, including tractor hydraulic fluids, some gear oils, power steering fluids, fluids used in wind turbines, compressors, some industrial fluids, and fluids related to power train components. It should be noted that within each of these fluids such as, for example, automatic transmission fluids, there are a variety of different types of fluids due to the various transmissions having different designs which have led to the need for fluids of markedly different functional characteristics. This is contrasted by the term “lubricating fluid” which is not used to generate or transfer power.
With respect to tractor hydraulic fluids, for example, these fluids are all-purpose products used for all lubricant applications in a tractor except for lubricating the engine. These lubricating applications may include lubrication of gearboxes, power take-off and clutch(es), rear axles, reduction gears, wet brakes, and hydraulic accessories.
When the functional fluid is an automatic transmission fluid, the automatic transmission fluids must have enough friction for the clutch plates to transfer power. However, the friction coefficient of fluids has a tendency to decline due to the temperature effects as the fluid heats up during operation. It is important that the tractor hydraulic fluid or automatic transmission fluid maintain its high friction coefficient at elevated temperatures, otherwise brake systems or automatic transmissions may fail. This is not a function of an engine oil.
Tractor fluids, and for example Super Tractor Universal Oils (STUOs) or Universal Tractor Transmission Oils (UTTOs), may combine the performance of engine oils with transmissions, differentials, final-drive planetary gears, wet-brakes, and hydraulic performance. While many of the additives used to formulate a UTTO or a STUO fluid are similar in functionality, they may have deleterious effect if not incorporated properly. For example, some anti-wear and extreme pressure additives used in engine oils can be extremely corrosive to the copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance may be detrimental to wet brake performance. Friction modifiers specific to quiet wet brake noise, may lack the thermal stability required for engine oil performance. Each of these fluids, whether functional, tractor, or lubricating, are designed to meet specific and stringent manufacturer requirements.
Engine oils as discussed herein may be formulated by the addition of one or more additives, as described in detail below, to an appropriate base oil formulation. The additives may be combined with a base oil in the form of an additive package (or concentrate) or, alternatively, may be combined individually with a base oil (or a mixture of both). The fully formulated engine oil may exhibit improved performance properties, based on the additives added and their respective proportions.
The details and advantages of the disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that the descriptions herein are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.
All patents and publications cited herein are fully incorporated by reference herein in their entirety.
The following examples are illustrative, but not limiting, of the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which are obvious to those skilled in the art, are within the spirit and scope of the disclosure.
The following examples are illustrative, but not limiting, of the methods and compositions of the present disclosure. Examples 1-16 exemplify different copolymers comprising ethylene units and propylene units and processes for producing them. As shown, changes in the conditions and parameters of the process, such as the feed rate of various reactants, may be employed to achieve different characteristics of the resulting copolymer such as changing the crossover temperature of the copolymer.
Examples F1-F12 exemplify different functionalized copolymers and processes for producing the same.
Table 5 below summarizes the characteri stics of the copolymer from select examples from below.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reaction was operated continuously; with continuous feed of catalyst (0.127 wt. % Cp2ZrCl2 in toluene), co-catalyst (5.0 wt. % MMAO in toluene), solvent (toluene), and ethylene and propylene monomers. The reactor was operated liquid-full at 70 psig and agitated with a four-blade pitched-turbine impeller operating at 220 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 0.90 g/min and 0.90 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 2.71 g/min, 15.22 g/min and 11.71 g/min, respectively. The reactor temperature was maintained at 65° C. as measured by a ⅛″ thermocouple located in the reactor. The production rate of polymer was measured gravimetrically as 2.78 g/min.
The copolymer was found to contain 49 mol % of ethylene units using 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer were measured by GPC and found to be 1159 g/mol and 3.73, respectively. The weight average molecular weight (Mw) of the copolymer was measured by 1H-NMR and found to be 1038 g/mol and the olefin distribution in the copolymer as measured by 1H-NMR was 96.5% methyl-vinylidene, 1.6% beta-vinylidene, 1.3% di-substituted (i.e. 2 olefins in a single copolymer molecule) and 0.6% vinyl/ally. The average ethylene unit run length as measured by 13C-NMR was 1.68. The crossover temperature measured by oscillatory rheometry was determined to be −73.5 ° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reactor was operated continuously; with a continuous feed of catalyst (0.127 wt. % Cp2ZrCl2 in toluene), co-catalyst (5.0 wt. % MMAO in toluene), solvent (toluene), ethylene and propylene. The reactor was operated liquid-full at 70 psig and agitated with a four-blade pitched-turbine impeller operating at 220 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 0.87 g/min and 0.87 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 2.78 g/min, 15.51 g/min and 10.65 g/min, respectively. The reactor temperature was maintained at 68° C. as measured by a ⅛″ thermocouple located in the reactor. The production rate of polymer was measured gravimetrically as 3.22 g/min.
The copolymer was found to contain 46 mol % ethylene units as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 1466 g/mol and 2.22, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 780 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 96.0% methyl-vinylidene, 1.8% beta-vinylidene, 1.3% di-substituted and 0.9% vinyl/ally. The average ethylene unit run length measured by 13C-NMR was 1.54. The crossover temperature measured by oscillatory rheometry was determined to be −77.6° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reaction was operated continuously; with continuous feed of catalyst (0.077 wt. % Cp2ZrCl2 in toluene), co-catalyst (1.248 wt. % MMAO in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 763 psig and agitated with a four-blade pitched-turbine impeller operating at 900 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 1.02 g/min and 0.82 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 2.23 g/min, 3.30 g/min and 9.31 g/min, respectively. The reactor temperature was maintained at 76° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 3.57 g/min.
The copolymer was found to contain 65 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2085 g/mol and 3.42, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1645 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 95.1% methyl-vinylidene, 1.8% beta-vinylidene, 1.3% di-substituted and 1.8% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.60. The crossover temperature measured by oscillatory rheometry was −24.5 ° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst The reaction was operated continuously; with continuous feed of catalyst (0.075 wt. % Cp2ZrCl2 in toluene), co-catalyst (1.0 wt. % MMAO in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 708 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 0.89 g/min and 0.91 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 2.23 g/min, 3.59 g/min and 9.36 g/min, respectively. The reactor temperature was maintained at 75° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 3.47 g/min.
The copolymer was found to contain 65 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2326 g/mol and 3.35, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1824 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 95.6% methyl-vinylidene, 1.7% beta-vinylidene, 1.1% di-substituted and 1.6% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.52. The crossover temperature measured by oscillatory rheometry was −27.0° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reaction was operated continuously; with continuous feed of catalyst (0.150 wt. % Cp2ZrCl2 in toluene), co-catalyst (2.0 wt. % MMAO in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 715 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 1.28 g/min and 1.26 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 2.23 g/min, 2.60 g/min and 9.38 g/min, respectively. The reactor temperature was maintained at 75° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 3.4 g/min.
The copolymer was found to contain 64 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 1241 g/mol and 3.00, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1114 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 95.5% methyl-vinylidene, 1.9% beta-vinylidene, 1.3% di-substituted and 1.4% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.39. The crossover temperature measured by oscillatory rheometry was −35.8° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reaction was operated continuously; with continuous feed of catalyst (0.167 wt. % Cp2ZrCl2 in toluene), co-catalyst (2.222 wt. % MMAO in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 696 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 0.66 g/min and 0.65 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 3.09 g/min, 8.11 g/min and 3.10 g/min, respectively. The reactor temperature was maintained at 80° C as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 6.63 g/min.
The copolymer was found to contain 58 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 3202 g/mol and 2.03, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1310 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 95.7% methyl-vinylidene, 1.5% beta-vinylidene, 1.6% di-substituted and 1.2% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.02. The crossover temperature measured by oscillatory rheometry was approximately −72.7° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reaction was operated continuously; with continuous feed of catalyst (0.165 wt. % Cp2ZrCl2 in toluene), co-catalyst (2.2 wt. % MMAO in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 703 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 1.21 g/min and 1.20 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 2.23 g/min, 2.51 g/min and 8.50 g/min, respectively. The reactor temperature was maintained at 75° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 3.48 g/min.
The copolymer was found to contain 68 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2838 g/mol and 1.87, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1203 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 94.6% methyl-vinylidene, 2.1% beta-vinylidene, 1.3% di-substituted and 2.0% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.72. The crossover temperature measured by oscillatory rheometry was approximately −13.7° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reaction was operated continuously; with continuous feed of catalyst (0.182 wt. % Cp2ZrCl2 in toluene), co-catalyst (2.42 wt. % MMAO in toluene), solvent (toluene), ethylene, and propylene. The reactor wras operated liquid-full at 704 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 1.15 g/min and 1.14 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 2.20 g/min, 2.40 g/min and 7.97 g/min, respectively. The reactor temperature was maintained at 75° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 3.53 g/min.
The copolymer was found to contain 67 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2269 g/mol and 2.17, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1167 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 94.6% methyl-vinylidene, 2.2% beta-vinylidene, 1.3% di-substituted and 1.9% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.65. The crossover temperature measured by oscillatory rheometry was approximately −18.5° C.
A 300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst and co-catalyst. The reaction was operated continuously; with continuous feed of catalyst (0.167 wt. % Cp2ZrCl2 in toluene), co-catalyst (2.222 wt. % MMAO in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 701 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst and co-catalyst solutions were mixed immediately before introduction to the reactor at feed rates of 0.78 g/min and 0.89 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and co-catalyst solutions at feed rates of 3.34 g/min, 7.77 g/min and 3.20 g/min, respectively. The reactor temperature was maintained at 89° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 7.98 g/min.
The copolymer was found to contain 56 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 3173 g/mol and 6948, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1281 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 94.9% methyl-vinylidene, 2.0% beta-vinylidene, 1.8% di-substituted and 1.3% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.05. The crossover temperature measured by oscillatory rheometry was lower than −37° C.
A 100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst, co-catalyst and scavenger. The reaction was operated continuously; with continuous feed of catalyst (0.011 wt. % Cp2ZrMe2 in toluene), co-catalyst (0.023 wt. % FAB in toluene), scavenger (0.0080 wt. % TEAL in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 1520 psig and agitated with a four-blade pitched-turbine impeller operating at 1041 rpm. The catalyst, co-catalyst and scavenger solutions were mixed immediately before introduction to the reactor at feed rates of 0.31, 0.32 and 0.52 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, co-catalyst and scavenger solutions at feed rates of 0.60, 2.98 and 6.31 g/min, respectively. The reactor temperature was maintained at 134° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 0.96 g/min.
The copolymer was found to contain 55 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2883 g/mol and 2.05, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1411 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 76.6% methyl-vinylidene, 14.1% beta-vinylidene, 7.2% di-substituted and 2.1% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.60. The crossover temperature measured by oscillatory rheometry was approximately −22.4° C.
A 100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst, co-catalyst and scavenger. The reaction was operated continuously; with continuous feed of catalyst (0.141 wt. % Cp2ZrMe2 in toluene), co-catalyst (0.144 wt. % FAB in toluene), scavenger (0.032 wt. % TEAL in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 1553 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst, co-catalyst and scavenger solutions were mixed immediately before introduction to the reactor at feed rates of 0.22 g/min, 0.49 g/min and 0.25 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, co-catalyst and scavenger solutions at feed rates of 1.75 g/min, 2.55 g/min and 7.04 g/min, respectively. The reactor temperature was maintained at 120° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 2.53 g/min.
The copolymer was found to contain 62 mol % ethylene as measured by 1H-NMR. The relative num ber average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2318 g/mol and 1.98, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1199 g/mol and the olefin distribution in the copolymer measur ed by 1H-NMR was 75.% methyl-vinylidene, 16.8% beta-vinylidene, 6.3% di-substituted and 1.4% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.22. The crossover temperature measured by oscillatory rheometry was lower than −37° C.
A 100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst, co-catalyst and scavenger. The reaction was operated continuously; with continuous feed of catalyst (0.04 wt. % Cp2ZrMe2 in toluene), co-catalyst (0.083 wt. % FAB in toluene), scavenger (0.005 wt. % TEAL in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 1533 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst, co-catalyst and scavenger solutions were mixed immediately before introduction to the reactor at feed rates of 0.32 g/min, 0.34 g/min and 0.33 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, co-catalyst and scavenger solutions at feed rates of 1.60 g/min, 3.05 g/min and 3.68 g/min, respectively. The reactor temperature was maintained at 98° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 3.69 g/min.
The copolymer was found to contain 45 mol % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2628 g/mol and 2.00, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1410 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 81.2% methyl-vinylidene, 13.0% beta-vinylidene, 5.2% di-substituted and 0.6% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 1.62. The crossover temperature measured by oscillatory rheometry was lower than −37° C.
A 100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged recei ver for pressure control, a metered feed of ethy lene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst, co-catalyst and scavenger. The reaction was operated continuously; with continuous feed of catalyst (0.04 wt. % Cp2ZrMe2 in toluene), co-catalyst (0.082 wt. % FAB in toluene), scavenger (0.01 wt. % TEAL in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 1533 psig and agitated with a four-blade pitched-turbine impeller operating at 1019 rpm. The catalyst, co-catalyst and scavenger solutions were mixed immediately before introduction to the reactor at feed rates of 0.52 g/min, 0.52 g/min and 0.37 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, co-catalyst and scavenger solutions at feed rates of 1.78 g/min, 2.76 g/min and 3.98 g/min, respectively. The reactor temperature was maintained at 119° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 3.5 g/min. The copolymer was found to contain 54 mol. % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 1673 g/mol and 1.97, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 913 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 79.2% methyl-vinylidene, 14.7% beta-vinylidene, 5.0% di-substituted and 1.1% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 1.99. The crossover temperature measured by oscillatory rheometry was lower than −37° C.
A 100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst, co-catalyst and scavenger. The reaction was operated continuously; with continuous feed of catalyst (0.093 wt. % Cp2ZrMe2 in toluene), co-catalyst (0.191 wt. % FAB in toluene), scavenger (0.011 wt. % TEAL in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 1462 psig and agitated with a four-blade pitched-turbine impeller operating at 1,000 rpm. The catalyst, co-catalyst and scavenger solutions were mixed immediately before introduction to the reactor at feed rates of 0.65 g/min, 0.68 g/min and 0.63 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, co-catalyst and scavenger solutions at feed rates of 1.70 g/min, 2.20 g/min and 6.85 g/min, respectively. The reactor temperature was maintained at 105° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 2.63 g/min.
The copolymer was found to contain 67 mol. % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 3004 g/mol and 2.04, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1504 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 83.0% methyl-vinylidene, 11.0% beta-vinylidene, 5.0% di-substituted and 2.0% vinyl/allyl. The average ethylene unit run length measured by 13C-NMR was 2.64. The crossover temperature measured by oscillatory rheometry was approximately −20.0° C.
A 100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged receiver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst, co-catalyst and scavenger. The reaction was operated continuously; with continuous feed of catalyst (0.008 wt. % Cp2ZrMe2 in toluene), co-catalyst (0.015 wt. % FAB in toluene), scavenger (0.011 wt. % TEAL in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 1549 psig and agitated with a four-blade pitched-turbine impeller operating at 1008 rpm. The catalyst, co-catalyst and scavenger solutions were mixed immediately before introduction to the reactor at feed rates of 0.37 g/min, 0.40 g/min and 0.27 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, co-catalyst and scavenger solutions at feed rates of 0.48 g/min, 3.0 g/min and 6.98 g/min, respectively. The reactor temperature was maintained at 140° C. as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 0.61 g/min.
The copolymer was found to contain 57 mol. % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 3,000 g/mol and 2.23, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1505 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 76.6 % methyl-vinylidene, 13.7% beta-vinylidene, 7.6% di-substituted and 2.1% vinyl/allyl . The average ethylene unit run length measured by 13C-NMR was 2.59. The crossover temperature measured by oscillatory rheometry was approximately 0.7° C.
A 100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen-purged recei ver for pressure control, a metered feed of ethylene gas and high-pressure metering pumps for separate feeds of propylene, toluene, catalyst, co-catalyst and scavenger. The reaction was operated continuously; with continuous feed of catalyst (0.015 wt,% Cp2ZrMe2 in toluene), co-catalyst (0.031 wt. % FAB in toluene), scavenger (0.009 wt. % TEAL in toluene), solvent (toluene), ethylene, and propylene. The reactor was operated liquid-full at 1539 psig and agitated with a four-blade pitched-turbine impeller operating at 1001 rpm. The catalyst, co-catalyst and scavenger solutions were mixed immediately before introduction to the reactor at feed rates of 0.26 g/min, 0.26 g/min and 0.46 g/min, respectively. The ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, co-catalyst and scavenger solutions at feed rates of 0.52 g/min, 3.04 g/min and 6.62 g/min, respectively. The reactor temperature was maintained at 140° C as measured by a ⅛″ thermocouple in the reactor. The production rate of copolymer was measured gravimetrically as 0.64 g/min.
The copolymer was found to contain 57 mol. % ethylene as measured by 1H-NMR. The relative number average molecular weight (Mn) and PDI of the copolymer, as measured by GPC were 2331 g/mol and 2.38, respectively. The weight average molecular weight (Mw) of the copolymer as measured by 1H-NMR was 1197 g/mol and the olefin distribution in the copolymer measured by 1H-NMR was 76.9% methyl-vinylidene, 14.4% beta-vinylidene, 6.9% di-substituted and 1.8% vinyl/ally. The average ethylene unit run length measured by 13C-NMR was 2.57. The crossover temperature measured by oscillatory rheometry was approximately −17.8° C.
Examples and Comparative Examples for Ethylene Alpha olefin Copolymer Functionalization
Ethylene propylene copolymer (Example 1) 168.5 g (0.16 mol) and maleic anhydride 23.5 g (0.24 mol) were charged to a 350 mL PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 500 mL round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo. Analytical analysis: acid number: 0.966 and 91.0% functionalized copolymer.
Ethylene propylene copolymer (Example 2) 150 g (0.19 mol) and maleic anhydride 28.3 g (0.29 mol) were charged to a 350 mL PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 500 mL round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo. Analytical analysis: acid number: 1.24 and 91.6% functionalized copolymer.
Ethylene propylene copolymer (Example 3) 822.5 g (0.5 mol) and maleic anhydride 73.55 g (0.75 mol) were charged to a 2 L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 2 L round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 827.5 g of product. Analytical analysis: acid number: 0.577 and 85.4% functionalized copolymer.
Ethylene propylene copolymer (Example 4) 900 g (0.49 mol) and maleic anhydride 72.65 g (0.74 mol) were charged to a 2 L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 2 L round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 901.4 g of product. Analytical analysis: acid number: 0.571 and 84.8% functionalized copolymer.
Ethylene propylene copolymer (Example 5) 781 g (0.7 mol) and maleic anhydride 103.1 g (1.05 mol) were charged to a 2 L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 1 L round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 846.5 g of product. Analytical analysis: acid number: 0.986, and 88.6% functionalized copolymer.
Ethylene propylene copolymer (Example 6 1,000 g (0.76 mol) and maleic anhydride 112.3 g (1.15 mol) were charged to a 2 L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 2 L round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 1076.8 g of product. Analytical analysis: acid number: 0.76, and 78% functionalized copolymer.
Ethylene propylene copolymer (Example 7) 450 g (0.374 mol), ethylene propylene copolymer (Example 8) 450 g (0.386 mol) and maleic anhydride 111.79 g (1.14 mol) were charged to a 2 L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 2 L round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 960.2 g of product. Analytical analysis: acid number: 0.923, and 87.0% functionalized copolymer.
Ethylene propylene copolymer (Example 9) 845.2 g (0.66 mol) and maieic anhydride 97.0 g (0.99 mol) were charged to a 2 L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 2 L 3N-round bottom flask. The reaction mixture was then heated and the unreacted maieic anhydride was removed in vacuo affording 904.2 g of product. Analytical analysis: acid number: 0.858, and 82.2% functionalized copolymer.
Ethylene propylene copolymer (Example 10) 150.0 g (0.11 mol) and maieic anhydride 15.7 g(0.159 mol) were charged to a 35 0 mL PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 500 mL 3N-round bottom flask. The reaction mixture was then heated and the unreacted maieic anhydride was removed in vacuo affording 155.3 g of product. Analytical analysis: acid number: 0.72, and 85.6% functionalized copolymer.
Ethylene propylene copolymer (Example 11) 150.0 g (0.125 mol) and maieic anhydride 18.4 g (0.19 mol) were charged to a 350 mL PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 500 mL 3N-round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 159.5 g of product. Analytical analysis: acid number: 0.78, and 81.3% functionalized copolymer
Ethylene propylene copolymer (Example 12) 150.0 g (0.11 mol) and maleic anhydride 15.7 g (0.160 mol) were charged to a 350 mL PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 500 mL 3N-round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 155.6 g of product. Analytical analysis: acid number: 0.685, and 85.3% functionalized copolymer.
Ethylene propylene copolymer (Example 13) 1,000 g (1.1 mol) and maleic anhydride 161.2 g (1.64 mol) were charged to a 2 L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50° C., purged with nitrogen for 15 min with stirring. The reactor temperature was raised to 235° C. and maintained at that temperature for 6 h while stirring. The reaction mixture was then cooled to 90° C. and transferred to a 500 mL 3N-round bottom flask. The reaction mixture was then heated and the unreacted maleic anhydride was removed in vacuo affording 1108.5 g of product. Analytical analysis: acid number: 1.057, and 83.8% functionalized copolymer
A 300 mL stirred autoclave was used to prepare a sample which comprised at least 1 kg of ethylene-propylene copolymer. The number average weight of the copolymer was 2085 g/mol, and an ethylene content of 65%. The reaction conditions for preparing the copolymer are shown in Table 6 below:
“Slpm” is standard liters per minute at 25° C. and 101.325 kPa. The test was ran for 50 minutes and the initial sample was discarded. The reaction was then operated continuously for 6 ½ hours and the reactor effluent was collected and sampled every 30 to 45 minutes. A total often samples were collected, water-washed and rotavaped as discussed below. The samples were each weighed and the polymer content was determined.
The polymer samples were washed in a 4-liter glass separation kettle, which was equipped with an overhead stirrer and an electric heating mantle. Toluene was used to strip the samples in a 2-liter Buchi RR III Rotavap, and the temperature was maintained using a temperature-controlled oil bath.
The separation kettle was charged with one liter of distilled water, and then samples 1-4 were charged to the kettle. The kettle was heated to 50° C. and stirred for 25 minutes. After, the stirring was stopped and the phases were allowed to separate, a total of 1664 grams of toluene-polymer phase was removed without disrupting the aqueous layer.
Following this step, a total of 1479 grams of polymer from samples 5-6 were charged to the kettle. Once again the composition was stirred for 25 minutes at 50° C. and then allowed to separate. An additional 1286 grams of toluene layer was then decanted off the aqueous layer.
Next, samples 7-8 were treated as above and a total of 1341 grams were decanted from the aqueous layer.
Sample 9 was then charged to the kettle, stirred for 25 minutes at 50° C. and allowed to separate overnight. The next morning 615 grams were removed from the aqueous layer and the last sample 10 was added. After charging, stirring the composition at 50° C., and separation of the phases, 746 grams of toluene-polymer composition was decanted off. Then, an additional 214 grams of toluene was added to the kettle to dilute the polymer/toluene layer near the aqueous interface. 172 grams of toluene was then removed and a total of 1134 grams of the aqueous layer was drained from the kettle. The layer contained a visible amount of aluminum oxide along with toluene.
A Rotavap was heated to 120° C. and 10 mm Hg vacuum. The toluene-polymer solution recovered from the kettle was charged in a semi-batch manner to the rotavap over the span of nine hour while the toluene was recovered overhead. The polymer remained in the rotavap during operation and the vacuum was incrementally increased to 24 mm Hg as the polymer concentration increased in order to main the necessary boil-up rate. After all the charge was fed, the rotavap temperature was increased to 140° C. and the vacuum was increased to 29 mm Hg. The rotavap was maintained at these conditions for approximately 90 minutes.
Lastly, the rotavap was cooled and then drained and a total of 1310 grams of polymer was recovered.
EPSA (ASA Example 1) 62.3 g (0.06 mol) was charged to a 250 mL three-necked flask equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 6.3 g (0.033 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h.At that time 56.3 g of process oil was added and the reaction product was filtered using a pressure filter to afford 102 g of succinimide product.
EPSA (ASA Example 2) 64.4 g (0.08 mol) was charged to a 250 mL three-necked flask equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 8.4 g (0.044 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 60.5 g of process oil was added and the reaction product was filtered using a pressure filter to afford 110 g of succimmide product.
EPSA (ASA Example 3) 769.8 g (0.44 mol) was charged to a 2 L resin kettle equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 46.7 g (0.247 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 584.1 g of process oil was added and the reaction product was filtered using a pressure filter to afford 1363 g of succinimide product.
EPSA (ASA Example 5) 770.8 g (0.76 mol) was charged to a 2 L resin kettle equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 79.8 g (0.42 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 660.9 g of process oil was added and the reaction product was filtered using a pressure filter to afford 1431.7 g of succinimide product.
EPSA (ASA Example 6) 1032.8 g (0.786 mol) was charged to a 2 L resin kettle equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 82.5 g (0.44 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 645.8 g of process oil was added and the reaction product was filtered using a pressure filter to afford 1647.5 g of succinimide product.
EPSA (ASA Example 7) 872.1 g (0.525 mol) was charged to a 2 L resin kettle equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 55.2 g (0.29 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 593.8 g of process oil was added and the reaction product was filtered using in a pressure filter to afford 1394 g of succinimide product.
EPSA (ASA Example 8) 886.8 g (0.80 mol) was charged to a 2 L resin kettle equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 84 g (0.44 mol) wras added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 711.6 g of process oil was added and the reaction product was filtered using in a pressure filter to afford 1572.2 g of succinimide product.
EPSA (ASA Example 9) 120.0 g (0.087 mol) was charged to a 500 mL 3-necked round bottom flask equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 9.14 g (0.048 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 93.3 g of process oil was added and the reaction product was filtered using a pressure filter to afford 196.9 g of succinimide reaction product.
EPSA (ASA Example 10) 120.0 g (0.094 mol) was charged to a 500 mL 3-necked round bottom flask equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 9.87 g (0.052 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 83.3 g of process oil was added and the reaction product was filtered using a pressure filter to afford 191.5 g of succinimide reaction product.
EPSA. (ASA Example 11) 120.0 g (0.082 mol) was charged to a 500 mL 3-necked round bottom flask equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Tetraethylene pentamine 8.64 g (0.046 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 91.9 g of process oil was added and the reaction product was filtered using a pressure filter to afford 200.7 g of succinimide reaction product.
EPSA (ASA Example 12) 1000 g (1.06 mol) was charged to a 2 L resin kettle equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160° C. under nitrogen. Polyethylene amine 111 g (0.59 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 767.7 g of process oil was added and the reaction product was filtered using a pressure filter to afford 1544.4 g of succinimide reaction product.
EPSA (ASA Example 1) 70.1 g (0.068 mol) was charged to a 250 mL round bottom 3-Neck flask equipped with an overhead stirrer, Dean-Stark trap and condenser. The ASA was stirred and heated to 160° C. under nitrogen, Tetrathylene pentamine 8.48 g (0.024 mol) was added drop wise via an addition funnel. The reaction mixture was stirred with heating under a vacuum for 3 h. At that time 19.3 g Aromatic 150 was added and filtered in a pressure filter to afford of a succinimide product.
An EP-copolymer substituted Mannich product was prepared from an EP copolymer-substituted hydroxyphenol, aldehyde, and dibutylamine under a Mannich reaction condition similar to that used to make a polyisobutene-substituted Mannich product. The EP copolymer-substituted hydroxylphenol was made by alkylation of a hydroxybenzene with copolymer Example 2.
Ethylene propylene copolymer containing 62% ethylene content was prepared under similar conditions used in preparing other inventive copolymers described above.
The above copolymer (100 g, 0.11 mol) and 250 mL heptane were charged to a 1 L 3-necked round bottom flask equipped with overhead stirrer and thermocouple. To the stirred solution at room temperature under nitrogen was added 51.9 g (0.212 mol) of a hydrogen bromide acetic acid solution over 1 h period. The reaction mixture was heated at 45° C. for 2 h. 200 mL of water was added stirred and allowed to stand overnight. Aqueous work up remove aqueous layer, add 200 mL heptane to the organic layer. Wash with 24 g of a 25% w/w sodium carbonate solution. Remove aqueous layer and filter organic layer through sodium sulfate. Concentrate in vacuo to remove organic solvent afforded 100 g of the desired bromine-containing product.
The above bromine-containing product, 75 g (0.073 mol) and 35 g xylene were charged to a 500 mL 3-necked round bottom flask equipped with overhead stirrer, condenser and thermocouple. To the stirred solution at room temperature under nitrogen was added dimethyl amino propylamine (72.8 g (0.7 mol) via an addition funnel. The reaction mixture was heated at 145° C. for 3 h and then cooled to 60 C. 50 mL of a 47% sodium hydroxide solution was added to the reaction mixture and stirred for 2 h. The resulting organic layer was isolated and washed three times with water in a separator funnel and dried over magnesium sulfate. Concentration in vacuo afforded 66.8g of the desired product (Found 2.42 wt. % N, calculated 2.68 wt. %)
In these examples, the inventive and comparative dispersants were blended into SAE 5W-30 quality finished oils. Olefin copolymer HiTEC® 5751, commercially available from Afton Chem. Corp. (VA USA), was included as a viscosity index improver (VII). Base oils used in the examples were RHT120 commercially available from Safety Kleen Corp. (TX USA) or a mixture of Phillips 66 PP100N, 225N and Ultra-S-4 commercially available from ConocoPhillips (TX USA). Viscoplex® 1500 from Evonik Industries (Germany) or HiTEC®5714 was used as a pour point depressant at 0.2 wt. %. The low temperature properties of these formulations were evaluated in the Mini Rotary Viscometer (MRV) Test at −35° C. (ASTM D4684). The results are shown in the table below:
As shown in the above table, Dispersant Examples 2, 4, 7, and 9-11, which were prepared from copolymer having low crossover temperature and low ethylene run length, facilitated the passing of the MRV test.
While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art wrill readily appreciate that ail parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that the invention may be practiced otherwise than as specifically described. The present invention is directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the scope of the present invention.
The patentees do not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equi valents.
It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each and every other component, compound, substituent or parameter disclosed herein.
It is also to be understood that each amount/value or range of amounts/Values for each component, compound, substituent or parameter disclosed herein is to be interpreted as also being disclosed in combination with each amount/value or range of amounts/values disclosed for any other component), compounds(s), substituent(s) or parameters) disclosed herein and that any combination of amounts/values or ranges of amounts/values for two or more component(s), compounds(s), substituent(s) or parameters disclosed herein are thus also disclosed in combination with each other for the purposes of this description.
It is further understood that each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits. Thus, a range of from 1-4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4.
It is further understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter. Thus, this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range.
Furthermore, specific amounts/values of a component, compound, substituent or parameter disclosed in the description or an example is to be interpreted as a disclosure of either a lower or an upper limit of a range and thus can be combined with any other lower or upper limit of a range or specific amount/value for the same component, compound, substituent or parameter disclosed elsewhere in the application to form a range for that component, compound, substituent or parameter.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2017/065767 | Dec 2017 | US |
| Child | 15904324 | US | |
| Parent | PCT/US2017/065773 | Dec 2017 | US |
| Child | PCT/US2017/065767 | US |
