Patent Application
20210121863
The present disclosure provides catalyst systems and methods for polymerizing olefins.
Polyolefins are widely used commercially because of their robust physical properties. Polyolefins are typically prepared with a catalyst that polymerizes olefin monomers. Therefore, there is interest in finding new catalysts and catalyst systems that provide polymers having improved properties.
Catalysts for olefin polymerization are often based on metallocenes as catalyst precursors, which are activated either with an alumoxane or an activator containing a non-coordinating anion. A non-coordinating anion, such as tetrakis(pentafluorophenyl)borate, is capable of stabilizing the resulting metal cation of the catalyst. Because such activators are fully ionized and the corresponding anion is highly non-coordinating, such activators can be effective as olefin polymerization catalyst activators. However, because they are ionic salts, such activators are insoluble in aliphatic hydrocarbons and only sparingly soluble in aromatic hydrocarbons. It is desirable to conduct most polymerizations of α-olefins in aliphatic hydrocarbon solvents due to the compatibility of such solvents with the olefin monomer and in order to reduce the aromatic hydrocarbon content of the resulting polymer product. Typically, ionic salt activators are added to such polymerizations in the form of a solution in an aromatic solvent such as toluene. The use of even a small quantity of such an aromatic solvent for this purpose is undesirable since it needs to be removed in a post-polymerization devolatilization step and separated from other volatile components, which is a process that adds significant cost and complexity to any commercial process. In addition, the activators often exist in the form of an oily, intractable material which is not readily handled and metered or precisely incorporated into the reaction mixture.
U.S. Pat. No. 5,919,983 discloses polymerization of ethylene and octene using a catalyst system comprising [(C18)2MeN)]+[B(PhF5)4]− activator having four perfluoro-phenyl groups bound to the boron atom and two linear C18 groups bound to the nitrogen, as well as describing other linear groups at column 3, line 51 et seq.
U.S. Pat. No. 8,642,497 discloses the preparation of N,N-dimethylanilinium tetrakis(heptafluoronaphth-2-yl)borate anion.
US 2003/0013913 (granted as U.S. Pat. No. 7,101,940) discloses various activators such as N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate [0070], and N,N-diethylbenzylammoniumtetrakis(pentafluorophenyl)borate [0124].
US 2002/0062011 discloses phenyl dioctadecylammonium(hydroxyphenyl) tris(pentafluorophenyl) borate at paragraph [0200] and (pentafluorophenyl) dioctadecylammonium tetrakis(pentafluorophenyl) borate at paragraph [0209].
U.S. Pat. Nos. 7,799,879, 7,985,816, 8,580,902, 8,835,587, and WO2010/014344 describe ammonium borate activators that include some that use a tetrakis(heptafluoronaphth-2-yl)borate anion.
Furthermore, it would be expected that altering the activator chemical structure, such as using a different anion, would provide altered polymerization and polymer properties. As an example, using an activator having heptafluoronaphth-2-yl groups instead of perfluoro-phenyl groups as part of the borate anion would reduce activation of the catalyst because of the increased steric bulk of heptafluoronaphth-2-yl groups versus perfluoro-phenyl groups. Accordingly, research into different activator chemical structures has been limited.
Nonetheless, there remains a need for catalyst systems having activators that are soluble in aliphatic hydrocarbons and catalyst systems capable of producing polyolefins having, for example, high comonomer incorporation, high molecular weight, and or a melt temperature of about 95° C. or greater. There is further a need for catalyst systems capable of producing polyolefins having, for example, low comonomer incorporation, low molecular weight, and or a melt temperature of about 110° C. or greater. Likewise, there is a need for catalyst systems having activators that are soluble in aliphatic hydrocarbons and capable of producing polyolefins at the same or improved activity levels, as compared to conventional activators, where the polymers can have (1) high comonomer incorporation, high molecular weight, and or a melt temperature of about 95° C. or greater, (2) low molecular weight and or a melt temperature of about 110° C. or greater, (3) high molecular weight and or a melt temperature of about 110° C. or greater, or (4) low comonomer incorporation, high molecular weight, and or a melt temperature of about 110° C. or greater.
References of interest include: WO 2002/002577; WO 2006/066126; WO 2010/132811; U.S. Pat. Nos. 7,087,602; 8,642,497; 6,121,185; 8,642,497; US2015/0203602; Chemical Abstract Service (CAS) number 909721-53-5; Chemical Abstract Service (CAS) number 943521-08-2; U.S. Ser. No. 16/394,174, filed Apr. 25, 2019, U.S. Ser. No. 16/394,166, filed Apr. 25, 2019; U.S. Ser. No. 16/394,197, filed Apr. 25, 2019; U.S. Ser. No. 16/394,186, filed Apr. 25, 2019; U.S. Ser. No. 16/394,520, filed Apr. 25, 2019; U.S. Ser. No. 16/394,566, filed Apr. 25, 2019; and U.S. Ser. No. 62/882,088, filed Aug. 2, 2019.
The present disclosure relates to catalyst systems comprising:
1) a salan catalyst compound represented by Formula (CI) or (CII):
wherein:
M is a Group 3, 4, 5 or 6 transition metal;
X1 and X2 are independently selected from the group consisting of a C1 to C20 hydrocarbyl, a C1 to C20 substituted hydrocarbyl, a heteroatom, and a heteroatom containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure; wherein if M is trivalent then X2 is not present;
each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 is independently selected from the group consisting of hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom, and a heteroatom containing group, or two or more of R1 to R14 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure;
Y is a divalent C1 to C20 hydrocarbyl or substituted divalent C1 to C20 hydrocarbyl; and
Q is a neutral donor group; and
2) an activator compound represented by Formula (AI):
[R1R2R3EH]d+[Mk+Qn]d− (AI)
wherein:
E is nitrogen or phosphorous;
d is 1, 2 or 3; k is 1, 2, or 3;
n is 1, 2, 3, 4, 5, or 6; n−k=d;
each of R1, R2, and R3 is independently H, an optionally substituted C1-C40 alkyl, or an optionally substituted C5-C50-aryl, wherein R1, R2, and R3 together comprise 15 or more carbon atoms;
M is an element selected from group 13 of the Periodic Table of the Elements; and
each Q is independently a hydrogen, bridged or unbridged dialkylamido, halide, alkoxy, substituted alkoxy, aryloxy, substituted aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical.
In yet another embodiment, the present disclosure provides a catalyst system further comprising a support.
In still another embodiment, the present disclosure provides a polymerization process comprising a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator as described herein, ii) a catalyst compound as described herein, and iii) optional support.
In still another embodiment, the present disclosure provides a polyolefin formed by a catalyst system and or method of the present disclosure.
Unless otherwise noted all melt temperatures (Tm) are DSC second melt and are determined using the following DSC procedure according to ASTM D3418-03. Differential scanning calorimetric (DSC) data are obtained using a TA Instruments model Q200 machine. Samples weighing about 5 to about 10 mg are sealed in an aluminum hermetic sample pan. The DSC data are recorded by first gradually heating the sample to about 200° C. at a rate of about 10° C./minute. The sample is kept at about 200° C. for about 2 minutes, then cooled to about −90° C. at a rate of about 10° C./minute, followed by an isothermal for about 2 minutes and heating to about 200° C. at about 10° C./minute. Both the first and second cycle thermal events are recorded. The melting points reported herein are obtained during the second heating/cooling cycle unless otherwise noted.
All molecular weights are weight average (Mw) unless otherwise noted. All molecular weights are reported in g/mol unless otherwise noted. Melt index (MI), also referred to as I2, reported in g/10 min, is determined according to ASTM D-1238, 190° C., 2.16 kg load. High load melt index (HLMI) also referred to as I21, reported in g/10 min, is determined according to ASTM D-1238, 190° C., 21.6 kg load. Melt index ratio (MIR) is MI divided by HLMI as determined by ASTM D1238.
The specification describes catalysts that can be transition metal complexes. The term complex is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom. The ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization. The ligand may be coordinated to the transition metal by covalent bond and or/and or electron donation coordination or intermediate bonds. The transition metal complexes are generally subjected to activation to perform their polymerization or oligomerization function using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.
For the purposes of the present disclosure, the numbering scheme for the Periodic Table Groups is the “New” notation as described in Chemical and Engineering News, 63(5), pg. 27 (1985). Therefore, a “Group 8 metal” is an element from Group 8 of the Periodic Table, e.g., Fe, and so on.
The following abbreviations are used through this specification: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TNOAL is tri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, Bn is benzyl (i.e., CH2Ph), RT is room temperature (and is 23° C. unless otherwise indicated), tol is toluene, MeCy is methylcyclohexane, and Cy is cyclohexyl.
Unless otherwise indicated (e.g., the definition of “substituted hydrocarbyl”, etc.), the term “substituted” means that at least one hydrogen atom has been replaced with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*, —SiR*3, —GeR*, —GeR*3, —SnR*, —SnR*3, —PbR*3, and the like, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a ring structure.
The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group,” are used interchangeably throughout this disclosure. Likewise, the terms “group”, “radical”, and “substituent” are also used interchangeably in this disclosure. For purposes of this disclosure, “hydrocarbyl radical” is defined to be C1-C100 radicals of carbon and hydrogen, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like.
Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been replaced with a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*, —SiR*3, —GeR*, —GeR*3, —SnR*, —SnR*3, —PbR*3, and the like, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring.
Halocarbyl radicals (also referred to as halocarbyls, halocarbyl groups or halocarbyl substituents) are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen (also referred to as a “halide”) (e.g., F, Cl, Br, I) or halogen-containing group (e.g., CF3). Substituted halocarbyl radicals are radicals in which at least one halocarbyl hydrogen or halogen atom has been substituted with at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like or where at least one non-carbon atom or group has been inserted within the halocarbyl radical such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B, —Si(R*)2—, —Ge(R*)2—, —Sn(R*)2—, —Pb(R*)2— and the like, where R* is independently a hydrocarbyl or halocarbyl radical provided that at least one halogen atom remains on the original halocarbyl radical. Additionally, two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.
Hydrocarbylsilyl groups, also referred to as silylcarbyl groups (also referred to as hydrocarbyl silyl groups), are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one SiR*3 containing group or where at least one —Si(R*)2— has been inserted within the hydrocarbyl radical where R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. Silylcarbyl radicals can be bonded via a silicon atom or a carbon atom.
Substituted silylcarbyl radicals are silylcarbyl radicals in which at least one hydrogen atom has been substituted with at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR3 and the like or where at least one non-hydrocarbon atom or group has been inserted within the silylcarbyl radical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Ge(R*)2—, —Sn(R*)2—, —Pb(R*)2— and the like, where R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.
The terms “alkyl radical,” and “alkyl” are used interchangeably throughout this disclosure. For purposes of this disclosure, “alkyl radicals” are defined to be C1-C100 alkyls that may be linear, branched, or cyclic. Examples of such radicals can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like. Substituted alkyl radicals are radicals in which at least one hydrogen atom of the alkyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*, —SiR*3, —GeR*, —GeR*3, —SnR*, —SnR*3, —PbR*3, and the like, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring.
The term “branched alkyl” means that the alkyl group contains a tertiary or quaternary carbon (a tertiary carbon is a carbon atom bound to three other carbon atoms. A quaternary carbon is a carbon atom bound to four other carbon atoms). For example, 3,5,5 trimethylhexylphenyl is an alkyl group (hexyl) having three methyl branches (hence, one tertiary and one quaternary carbon) and thus is a branched alkyl bound to a phenyl group. Unless otherwise indicated a branched alkyl includes all isomers thereof.
The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. These alkenyl radicals may be substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl, 1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl and the like.
The term “arylalkenyl” means an aryl group where a hydrogen has been replaced with an alkenyl or substituted alkenyl group. For example, styryl indenyl is an indene substituted with an arylalkenyl group (a styrene group).
The term “alkoxy”, “alkoxyl”, or “alkoxide” means an alkyl ether or aryl ether radical wherein the terms “alkyl” and “aryl” are as defined herein. Examples of suitable alkyl ether radicals can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy, and the like.
The term “aryl” or “aryl group” means a carbon-containing aromatic ring such as phenyl. Likewise, heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. As used herein, the term “aromatic” also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic.
Heterocyclic means a cyclic group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring.
Substituted heterocyclic means a heterocyclic group where at least one hydrogen atom of the heterocyclic radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*, —SiR*3, —GeR*, —GeR*3, —SnR*, —SnR*3, —PbR*3, and the like, where each R* is independently a hydrocarbyl or halocarbyl radical.
A substituted aryl is an aryl group where at least one hydrogen atom of the aryl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*, —SiR*3, —GeR*, —GeR*3, —SnR*, —SnR*3, —PbR*3, and the like, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring, for example 3,5-dimethylphenyl is a substituted phenyl group.
The term “substituted phenyl,” or “substituted phenyl group” means a phenyl group having one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*2, —OR*, —SeR*, —TeR*, —PR*2, —AsR*2, —SbR*2, —SR*, —BR*2, —SiR*, —SiR*3, —GeR*, —GeR*3, —SnR*, —SnR*3, —PbR*3, and the like, where each R* is independently a hydrocarbyl, halogen, or halocarbyl radical. Preferably the “substituted phenyl” group is represented by the formula:
where each of R17, R18, R19, R20, and R20 is independently selected from hydrogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl, a heteroatom, such as halogen, or a heteroatom-containing group (provided that at least one of R17, R18, R19, R20, and R20 is not H).
A “fluorophenyl” or “fluorophenyl group” is a phenyl group substituted with one, two, three, four or five fluorine atoms.
A “fluoroaryl” or “fluoroaryl group” is an aryl group substituted with at least one fluorine atom, such as the aryl is perfluorinated. The term “arylalkyl” means an aryl group where a hydrogen has been replaced with an alkyl or substituted alkyl group. For example, 3,5′-di-tert-butyl-phenyl indenyl is an indene substituted with an arylalkyl group. When an arylalkyl group is a substituent on another group, it is bound to that group via the aryl. For example in Formula (AI), the aryl portion is bound to E.
The term “alkylaryl” means an alkyl group where a hydrogen has been replaced with an aryl or substituted aryl group. For example, phenethyl indenyl is an indene substituted with an ethyl group bound to a benzene group. When an alkylaryl group is a substituent on another group, it is bound to that group via the alkyl. For example in Formula (AI), the alkyl portion is bound to E.
Reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), unless otherwise indicated.
The term “ring atom” means an atom that is part of a cyclic ring structure. Accordingly, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.
For purposes of the present disclosure, a “catalyst system” is a combination of at least one catalyst compound, an activator, and an optional support material. The catalyst systems may further comprise one or more additional catalyst compounds. For the purposes of the present disclosure, when catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. Catalysts of the present disclosure represented by Formula (CI) or (CII), etc. and activators represented by Formula (I) or (AI), etc. are intended to embrace ionic forms in addition to the neutral forms of the compounds.
“Complex” as used herein, is also often referred to as catalyst precursor, precatalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. These words are used interchangeably.
A scavenger is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments a co-activator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.
In the description herein, a catalyst may be described as a catalyst precursor, a pre-catalyst compound, a catalyst compound or a transition metal compound, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymer. An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
A metallocene catalyst is defined as an organometallic compound with at least one π-bound cyclopentadienyl moiety or substituted cyclopentadienyl moiety (such as substituted or unsubstituted Cp, Ind, or Flu) and more frequently two (or three) π-bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties (such as substituted or unsubstituted Cp, Ind, or Flu). (Cp=cyclopentadienyl, Ind=indenyl, Flu=fluorenyl).
For purposes of the present disclosure, in relation to catalyst compounds, the term “substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.
“Catalyst productivity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T×W) and expressed in units of gPgcat−1hr−1. “Conversion” is the amount of monomer that is converted to polymer product, and is reported as mol % and is calculated based on the polymer yield and the amount of monomer fed into the reactor. “Catalyst activity” is a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mole (or mmol) of catalyst (cat) used (kgP/molCat or gP/mmolCat or kgP/mmolCat), and catalyst activity can also be expressed per unit of time, for example, per hour (hr), e.g., (kg/mmol h).
For purposes herein an “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have a “propylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from propylene in the polymerization reaction and the derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer.
For purposes herein a “polymer” has two or more of the same or different monomer (“mer”) units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. “Different” in reference to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, copolymer, as used herein, can include terpolymers and the like. An oligomer is typically a polymer having a low molecular weight, such an Mn of less than 25,000 g/mol, or less than 2,500 g/mol, or a low number of mer units, such as 75 mer units or less or 50 mer units or less. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mole % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole % propylene derived units, and so on.
As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt % is weight percent, and mol % is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined to be Mw divided by Mn.
The term “continuous” means a system that operates without interruption or cessation for a period of time, such as where reactants are continually fed into a reaction zone and products are continually or regularly withdrawn without stopping the reaction in the reaction zone. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
A “solution polymerization” means a polymerization process in which the polymerization is conducted in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are typically not turbid as described in Oliveira, J. V. et al. (2000) “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v. 39, pp. 4627-4633.
A bulk polymerization means a polymerization process in which the monomers and or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than about 25 wt % of inert solvent or diluent, such as less than about 10 wt %, such as less than about 1 wt %, such as 0 wt %.
Unless otherwise indicated, as used herein, “low comonomer content” is defined as a polyolefin having less than 8 wt % of comonomer based upon the total weight of the polyolefin. As used herein, “high comonomer content” is defined as a polyolefin having greater than or equal to 8 wt % of comonomer based upon the total weight of the polyolefin.
Unless otherwise indicated, as used herein, “high molecular weight” is defined as a number average molecular weight (Mn) value of 100,000 g/mol or more. “Low molecular weight” is defined as an Mn value of less than 100,000 g/mol.
A “salan” catalyst compound is a Group 3 to 6 organometallic compound having the following ligands: (1) two phenols and (2) two nitrogens or one nitrogen and one oxygen, where the nitrogen-nitrogen or nitrogen-oxygen are bridged to one another through a divalent hydrocarbyl group, and for example where additionally the phenol groups and nitrogen-nitrogen or nitrogen-oxygen are bridged together as one ligand with four coordination sites to the metal.
For example, the present disclosure provides activators, catalyst systems comprising catalyst compounds and activators, and methods for polymerizing olefins using said catalyst systems. In the present disclosure, activators are described that feature ammonium or phosphonium groups with long-chain aliphatic hydrocarbyl groups for improved solubility of the activator in aliphatic solvents, as compared to conventional activator compounds.
The present disclosure provides catalyst systems and methods thereof. The catalyst systems include one or more salan catalysts and one or more catalyst activators (having a non-coordinating anion) that are soluble in an aliphatic hydrocarbon solvent. It has been discovered that catalyst systems having a salan catalyst and a catalyst activator having, for example, a cation having 15 or more carbon atoms can provide catalyst systems having activators that are soluble in aliphatic hydrocarbons, and the catalyst systems are capable of producing polyolefins at the same or improved catalyst activities, as compared to conventional activators. In addition, the polymers produced herein can have the same or improved polymer properties, as compared to polymers produced using conventional catalyst systems. For example, polyolefins of the present disclosure can have (1) high comonomer incorporation, high molecular weight, and or a melt temperature of about 95° C. or greater, (2) low molecular weight and or a melt temperature of about 110° C. or greater, (3) high molecular weight and or a melt temperature of about 110° C. or greater, or (4) low comonomer incorporation, high molecular weight, and or a melt temperature of about 110° C. or greater. For example, a salan catalyst having one or more fluorenyl moieties can provide high molecular weight polyolefins, and a salan catalyst having one or more carbazolyl moieties can provide low molecular weight polyolefins. Accordingly, catalyst systems of the present disclosure provide soluble activators in addition to improved or maintained catalyst activities and polymer properties. Catalyst systems therefore provide commercially viable catalyst systems without the use of toluene for preparation of the catalyst systems.
The present disclosure relates to catalyst systems having salan catalyst compound(s) and activator compound(s) that can be used in olefin polymerization processes. For example, the present disclosure provides catalyst systems including salan catalyst compound(s) and ammonium borate activator(s), and methods for polymerizing olefins using such catalyst systems. In the present disclosure, activators are described that feature ammonium groups with long-chain aliphatic hydrocarbyl groups for improved solubility of the activator in aliphatic solvents, as compared to conventional activator compounds. Useful borate groups of the present disclosure include fluoroaryl (such as fluoronaphthyl borates and or fluorophenyl borates). It has been discovered that activators of the present disclosure having borate anions and ammonium cations having, for example, an aliphatic hydrocarbyl moiety can have improved solubility in aliphatic solvents, as compared to conventional activator compounds. Activators having a cation as described herein can provide enhanced activity for polymer production.
In another aspect, the present disclosure relates to polymer compositions obtained from the catalyst systems and processes set forth herein. The components of the catalyst systems according to the present disclosure and used in the polymerization processes of the present disclosure, as well as the resulting polymers, are described in more detail herein below.
The present disclosure relates to catalyst systems including a transition metal compound represented by Formula (CI) or (CII) and an activator compound represented by Formula (AI), to the use of an activator compound represented by Formula (AI) for activating the transition metal compound represented by Formula (CI) or (CII) in catalyst systems for polymerizing olefins, and to processes for polymerizing olefins, the processes including contacting under polymerization conditions one or more olefins with a catalyst system comprising a transition metal compound represented by Formula (CI) or (CII) and an activator compound represented by Formula (AI).
The activator compounds of Formula (AI) and the transition metal compounds represented by Formula (CI) or (CII) are further illustrated below. Any combinations of cations and non-coordinating anions disclosed herein are suitable to be used in the processes of the present disclosure and are thus incorporated herein.
The terms “cocatalyst” and “activator” are used herein interchangeably and are a compound which can activate any one of the catalyst compounds of the present disclosure by converting the neutral catalyst compound to a catalytically active catalyst compound cation. Activators of the present disclosure have one or more non-coordinating anions (NCAs). Non-coordinating anion (NCA) means an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluoronaphthyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non-coordinating anion. Suitable metals can include aluminum, gold, and platinum. Suitable metalloids can include boron, aluminum, phosphorus, and silicon. The term non-coordinating anion activator includes neutral activators, ionic activators, and Lewis acid activators.
“Compatible” non-coordinating anions can be those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.
The present disclosure provides activators, such as ammonium or phosphonium metallate or metalloid activator compounds, the activators comprising (1) ammonium or phosphonium groups and long-chain aliphatic hydrocarbyl groups and (2) metallate or metalloid anions, such as borates or aluminates. When an activator of the present disclosure is used with one or more catalyst compounds described herein in an olefin polymerization, a polymer can be formed having (1) high comonomer incorporation, high molecular weight, and or a melt temperature of about 95° C. or greater, (2) low molecular weight and or a melt temperature of about 110° C. or greater, (3) high molecular weight and or a melt temperature of about 110° C. or greater, or (4) low comonomer incorporation, high molecular weight, and or a melt temperature of about 110° C. or greater. In addition, it has been discovered that activators of the present disclosure are soluble in aliphatic solvent.
In one or more embodiments, a 10 wt % mixture (such as a 20 wt % mixture) of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25° C., preferably a 30 wt % mixture of the compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25° C.
In one or more embodiments, a 10 wt % mixture (such as a 20 wt % mixture) of the catalyst system in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25° C., preferably a 30 wt % mixture of the compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof, forms a clear homogeneous solution at 25° C.
In some embodiments, the activators described herein have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) at 25° C. (stirred 2 hours) in methylcyclohexane (MeCy).
In some embodiments, the activators described herein have a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) at 25° C. (stirred 2 hours) in isohexane.
In some embodiments, the activators described herein have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) at 25° C. (stirred 2 hours) in methylcyclohexane and a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) at 25° C. (stirred 2 hours) in isohexane.
In some embodiments, the catalyst systems described herein have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) at 25° C. (stirred 2 hours) in methylcyclohexane and a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) at 25° C. (stirred 2 hours) in isohexane.
The present disclosure relates to a catalyst system comprising a transition metal compound and an activator compound as described herein, to the use of such activator compounds for activating a transition metal compound in a catalyst system for polymerizing olefins, and to processes for polymerizing olefins, the process comprising contacting under polymerization conditions one or more olefins with a catalyst system comprising a transition metal compound and such activator compounds, where aromatic solvents, such as toluene, are absent (e.g. present at zero mol %, alternately present at less than 1 mol %, preferably the catalyst system, the polymerization reaction and or the polymer produced are free of “detectable aromatic hydrocarbon solvent,” such as toluene. For purposes of the present disclosure, “detectable aromatic hydrocarbon solvent” means 0.1 mg/m2 or more as determined by gas phase chromatography. For purposes of the present disclosure, “detectable toluene” means 0.1 mg/m2 or more as determined by gas phase chromatography.
The polyolefins produced herein preferably contain 0 ppm (alternately less than 1 ppm, alternately less than 1 ppb) of aromatic hydrocarbon. Preferably, the polyolefins produced herein contain 0 ppm (alternately less than 1 ppm, alternately less than 1 ppb) of toluene.
The catalyst systems used herein preferably contain 0 ppm (alternately less than 1 ppm, alternately less than 1 ppb) of aromatic hydrocarbon. Preferably, the catalyst systems used herein contain 0 ppm (alternately less than 1 ppm, alternately less than 1 ppb) of toluene.
The present disclosure provides activator compounds represented by Formula (AI):
[R1R2R3EH]d+[Mk+Qn]d− (AI)
wherein:
E is nitrogen or phosphorous, preferably nitrogen;
d is 1, 2 or 3 (preferably 3); k is 1, 2, or 3 (preferably 3); n is 1, 2, 3, 4, 5, or 6 (preferably 4, 5, or 6); n−k=d (preferably d is 1, 2 or 3; k is 3; n is 4, 5, or 6, preferably when M is B, n is 4);
each of R1, R2, and R3 is independently H, optionally substituted C1-C40 alkyl (such as branched or linear alkyl), or optionally substituted C5-C50-aryl (alternately each of R1, R2, and R3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl); wherein R1, R2, and R3 together comprise 15 or more carbon atoms;
M is an element selected from group 13 of the Periodic Table of the Elements, preferably B or Al, preferably B; and
each Q is independently a hydrogen, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical, preferably a fluorinated aryl group, such fluoro-phenyl or fluoro-naphthyl, more preferably perfluorophenyl or perfluoronaphthyl.
In some embodiments of activator compounds represented by Formula (AI), at least one of R1, R2, and R3 is a linear or branched C3-C40 alkyl group (alternately such as a linear or branched C7 to C40 alkyl group).
The present disclosure also provides activator compounds represented by Formula (AI), described above where R1 is a C1-C30 alkyl group (preferably a C1-C10 alkyl group, preferably C1 to C2 alkyl, preferably methyl), wherein R1 is optionally substituted, and each of R2 and R3 is independently an optionally substituted branched or linear C1-C40 alkyl group or meta and or para-substituted phenyl group, where the meta and para substituents are, independently, an optionally substituted C1 to C40 hydrocarbyl group, an optionally substituted alkoxy group, an optionally substituted silyl group, a halogen, or a halogen containing group, wherein R1, R2, and R3 together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms) and at least one of R1, R2, and R3 is a linear or branched alkyl (such as a C3-C40 branched alkyl, alternately C7-C40 branched alkyl).
The present disclosure further provides catalyst systems including activator compounds represented by Formula (AI), as described above where R1 is methyl; and each of R2 and R3 is independently C1-C40 branched or linear alkyl or C5-C50-aryl, wherein each of R1, R2, and R3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl; wherein R1, R2, and R3 together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms).
The present disclosure also provides catalyst systems having activator compounds represented by Formula (I):
[R1R2R3EH]+[BR4R5R6R7]− (I)
where:
E is nitrogen or phosphorous;
each of R1, R2, and R3 is independently C1-C40 linear or branched alkyl or C5-C50-aryl (such as C5 to C22), where each of R1, R2, and R3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl; where R1, R2, and R3 together comprise 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms); and
each of R4, R5, R6, and R7 is phenyl or naphthyl, wherein at least one of R4, R5, R6, and R7 is substituted with from one to seven fluorine atoms.
In some embodiments, at least one of R1, R2, and R3 is a linear or branched C3-C40 alkyl (such as a linear or branched C7 to C40 alkyl).
The present disclosure further provides catalyst systems including activator compounds represented by Formula (AI) as described above, where each of R1, R2, and R3 is independently C1-C40 linear or branched alkyl, C5-C50-aryl (such as C5 to C22), wherein each of R1, R2, and R3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl; wherein R1, R2, and R3 together comprise 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms. In some embodiments, at least one of R1, R2, and R3 is a linear or branched alkyl (such as a linear or branched C3-C40 alkyl), such as at least two of R1, R2, and R3 are a branched alkyl (such as a C3-C40 branched alkyl), such as each of R1, R2, and R3 is a branched alkyl (such as a C10-C40 branched alkyl).
In at least one embodiment of Formula (AI) or (I) herein, M is an element selected from group 13 of the Periodic Table of the Elements, preferably boron or aluminum, preferably B.
In at least one embodiment of Formula (AI) or (I) herein, each Q is independently selected from a hydrogen, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl (such as phenyl or naphthyl) group, and most preferably each Q is a perfluorinated aryl (such as phenyl or naphthyl) group.
In at least one embodiment of Formula (AI) herein, examples of suitable [Mk+Qn]d− also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.
In at least one embodiment, the activator is represented by Formula (I):
[R1R2R3EH]+[BR4R5R6R7]− (I)
wherein:
E is nitrogen or phosphorous, preferably nitrogen;
each of R1, R2, and R3 is independently C1-C40 linear or branched alkyl, C5-C22-aryl, arylalkyl where the alkyl has from 1 to 30 carbon atoms and the aryl has from 6 to 20 carbon atoms, or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S, wherein each of R1 R2, and R3 is optionally substituted by halogen, wherein R2 optionally bonds with R5 to independently form a five-, six- or seven-membered ring, preferably wherein, R1, R2, and R3 together comprise 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms; each of R4, R5, R6, and R7 is independently is independently a hydrogen, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical, preferably, each of R4, R5, R6, and R7 is independently is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl (such as phenyl or naphthyl) group (substituted with from one to seven fluorine atoms), and most preferably each Q is a perfluorinated aryl (such as phenyl or naphthyl) group.
In some embodiments of the activator represented by Formula (I), at least one of R1, R2, and R3 is a branched alkyl (such as a C7-C40 branched alkyl), alternately at least two of R1, R2, and R3 are a branched alkyl (such as a C7-C40 branched alkyl), alternately all three of R1, R2, and R3 are a branched alkyl (such as a C7-C40 branched alkyl).
In at least one embodiment, an activator is an ionic ammonium or phosphonium borate represented by Formula (I):
[R1R2R3EH]+[BR4R5R6R7]− (I)
where:
E is nitrogen or phosphorous;
R1 is a C1-C40 linear alkyl, preferably methyl;
each of R2, and R3 is independently C1-C40 linear or branched alkyl, C5-C22-aryl, C5 to C50 arylalkyl where the alkyl has from 1 to 30 carbon atoms and the aryl has from 6 to 20 carbon atoms, or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S, wherein each of R1 R2, and R3 is optionally substituted by halogen, wherein R2 optionally bonds with R5 to independently form a five-, six- or seven-membered ring, preferably wherein, R1, R2, and R3 together comprise 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms; and
each of R4, R5, R6, and R7 is independently each a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each of R4, R5, R6, and R7 is independently is a fluorinated aryl (such as phenyl or naphthyl) group, and most preferably each of R4, R5, R6, and R7 is independently is a perflourinated aryl (such as phenyl or naphthyl) group, wherein at least one of R4, R5, R6, and R7 is substituted with from one to seven fluorine atoms.
The present disclosure also provides catalyst systems including activator compounds represented by Formula (I):
[R1R2R3EH]+[BR4R5R6R7]− (I)
where:
E is nitrogen or phosphorous, preferably nitrogen;
each of R1, R2, and R3 is independently C1-C40 linear or branched alkyl, C5-C50-aryl, wherein each of R1, R2, and R3 is independently unsubstituted or substituted with at least one of halide, C1-C50 alkyl, C5-C50 aryl, C6-C35 arylalkyl, or C6-C35 alkylaryl, wherein R1, R2, and R3 together comprise 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms, provided that at least one of R1, R2, and R3 is a C3-C40 branched alkyl, alternately at least two of R1, R2, and R3 are a C3-C40 branched alkyl; and each of R4, R5, R6, and R7 is naphthyl, wherein at least one of R4, R5, R6, and R7 is substituted with from one to seven fluorine atoms, preferably seven fluorine atoms.
In a preferred aspect, the activator is an ionic ammonium borate represented by Formula (I):
[R1R2R3EH]+[BR4R5R6R7]− (I)
where:
E is nitrogen or phosphorous;
R1 is a methyl group;
R2 is C6-C50 aryl which is optionally substituted with at least one of halide, C1-C35 alkyl, C5-C15 aryl, C6-C35 arylalkyl, and C6-C35 alkylaryl;
R3 is C1-C40 branched alkyl which is optionally substituted with at least one of halide, C1-C35 alkyl, C5-C15 aryl, C6-C35 arylalkyl, and C6-C35 alkylaryl, wherein R2 optionally bonds with R3 to independently form a five-, six- or seven-membered ring, and R2 and R3 together comprise 20 or more carbon atoms, such as 21 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms, and
each of R4, R5, R6, and R7 is independently each a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, wherein at least one of R4, R5, R6, and R7 is independently substituted with from one, two, three, four, five, six, or seven fluorine atoms, more preferably each of R4, R5, R6, and R7 is independently a fluorinated aryl (such as phenyl or naphthyl) group, and most preferably each of R4, R5, R6, and R7 is independently is a perfluorinated aryl (such as phenyl or naphthyl) group.
Catalyst systems of the present disclosure may be formed by combining the catalysts with activators in any suitable manner, including by supporting them for use in slurry or gas phase polymerization. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer, i.e., little or no solvent).
Both the cation part of Formulas (AI) and (I) as well as the anion part thereof, which is an NCA, will be further illustrated below. Any combinations of cations and NCAs disclosed herein are suitable to be used in the processes of the present disclosure and are thus incorporated herein.
The cation component of the activators described herein (such as those of Formulas (AI) and (I) above), is a protonated Lewis base that can be capable of protonating a moiety, such as an alkyl or aryl, from the transition metal compound. Thus, upon release of a neutral leaving group (e.g. an alkane resulting from the combination of a proton donated from the cationic component of the activator and an alkyl substituent of the transition metal compound) transition metal cation results, which is the catalytically active species.
In at least one embodiment of Formula (I) or (AI), where the cation is [R1R2R3EH]+, E is nitrogen or phosphorous, preferably nitrogen; each of R1, R2, and R3 is independently hydrogen, C1-C40 branched or linear alkyl or C5-C50-aryl, wherein each of R1, R2, and R3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl; where R1, R2, and R3 together comprise 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as 45 or more carbon atoms. In some embodiments, at least one (alternately one, two or three) of R1, R2, and R3 is a linear or branched alkyl, (such as a linear or branched C3-C40 alkyl, alternately such as a linear or branched C7 to C40 alkyl).
In at least one embodiment of Formula (I) or (AI), where the cation is [R1R2R3EH]+, E is nitrogen or phosphorous, and each of R1, R2, and R3 is independently C1-C40 linear or branched alkyl, C5-C50-aryl (such as C5-C22-aryl, preferably an arylalkyl (where the alkyl has from 1 to 10 carbon atoms and the aryl has from 6 to 20 carbon atoms), or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S, where each of R1 R2, and R3 is optionally substituted by halogen, —NR′2, —OR′ or —SiR′3 (where R is independently hydrogen or C1-C20 hydrocarbyl), where R2 optionally bonds with R5 to independently form a five-, six- or seven-membered ring. R1, R2, and R3 together comprise 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as 45 or more carbon atoms. In some embodiments, at least one of R1, R2, and R3 is a linear or branched C3-C40 alkyl, alternately at least two of R1, R2, and R3 are a linear or branched C3-C40 alkyl.
In at least one embodiment of Formula (I) or (AI) described herein one, two or three of R1, R2 and R3 may independently be represented by the Formula (AIII):
where each of RA and RE are independently H, a C1-C40 linear or branched alkyl or C5-C50-aryl, where each of RA and RE is optionally substituted with one or more of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl, provided that in at least one (RA—C— RE) group, one or both of RA and RE is not H; and
RC, RB and RD are hydrogen; and Q is an integer from 5 to 40.
In at least one embodiment of Formula (I) or (AI) herein, one, two or three of R1, R2 and R3 may independently be represented by the Formula (IV) where:
where each of R17, R18, R19, R20, and R21 is independently selected from hydrogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl, a heteroatom, such as halogen, a heteroatom-containing group, or is represented by Formula (BIII), for example at least one of R17, R18, R19, R20, and R21 is not hydrogen.
In at least one embodiment of Formula (I) or (AI) one, two or three of R1, R2 and R3 may independently be represented by the Formula (AIII) or (IV):
where each of RA and RE are independently selected from H, a C1-C40 linear or branched alkyl or C5-C50-aryl, where each of RA and RE is optionally substituted with one or more of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl, provided that in at least one (RA—C—RE) group, one or both of RA and RE is not H;
RC, RB and RD are hydrogen; and
Q is an integer from 5 to 40,
each of R17, R18, R19, R20, and R21 is independently selected from hydrogen, C1-C40 hydrocarbyl or C1-C40 substituted hydrocarbyl, a heteroatom, such as halogen, a heteroatom-containing group, or is represented by Formula (AIII). In some embodiments, at least one of R17, R18, R19, R20, and R21 is a branched alkyl, preferably one, two, three, four, or five of R17, R19, R20, and R21 are represented by Formula (AIII)).
In at least one embodiment, the branched alkyl may have 1 to 30 tertiary or quaternary carbons, alternately 2 to 10 tertiary or quaternary carbons, alternately 2 to 4 tertiary or quaternary carbons, alternately the branched alkyl has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 tertiary or quaternary carbons.
In at least one embodiment of Formula (I) or (AI), each of R1, R2 and R3 may independently be selected from:
1) optionally substituted linear alkyls (such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, or n-tricontyl);
2) optionally substituted branched alkyls (such as alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-icosyl (including multi-alkyl analogs, i.e, dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, and trialkyl-icosyl, etc.), and isomers thereof where each alkyl group is independently a C1 to C40, (alternately C2 to C30, alternately C3 to C20) linear, branched or cyclic alkyl group), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl);
3) optionally substituted arylalkyls, such as (methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, icosylphenyl, henicosylphenyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, pentacosylphenyl, hexacosylphenyl, heptacosylphenyl, octacosylphenyl, nonacosylphenyl, tricontylphenyl, 3,5,5-trimethylhexylphenyl, dioctylphenyl, 3,3,5-trimethylhexylphenyl, 2,2,3,3,4 pentamethypentylylphenyl, and the like);
4) optionally substituted silyl groups, such as a trialkylsilyl group, where each alkyl is independently an optionally substituted C1 to C20 alkyl (such as trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl, tri-nonadecylsilyl, tri-icosylsilyl);
5) optionally substituted alkoxy groups (such as —OR*, where R* is an optionally substituted C1 to C20 alkyl or aryl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, phenyl, alkylphenyl (such as methyl phenyl, propyl phenyl, etc.), naphthyl, or anthracenyl);
6) halogens (such as Br or Cl); and
7) halogen containing groups (such as bromomethyl, bromophenyl, and the like).
In at least one embodiment of Formula (I) or (AI), R1 is methyl.
In at least one embodiment of Formula (I) or (AI), R2 is unsubstituted phenyl or substituted phenyl. In at least one embodiment, R2 is phenyl, methyl phenyl, n-butyl phenyl, n-octadecyl-phenyl, or an isomer thereof, preferably R2 is meta or para substituted phenyl, such as meta- or para-substituted alkyl substituted phenyl.
In at least one embodiment of Formula (I) or (AI), R3 is linear or branched alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-tricontyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoicosyl, isohenicosyl, isodocosyl, isotricosyl, isotetracosyl, isopentacosyl, isohexacosyl, isoheptacosyl, isooctacosyl, isononacosyl, or isotricontyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-icosyl (including multi-alkyl analogs, i.e, dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, and trialkyl-icosyl), and isomers thereof where each alkyl group is independently a C1 to C40, (alternately C2 to C30, alternately C3 to C20) linear, branched or cyclic alkyl group, preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl).
In at least one embodiment of Formula (I) or (AI), R1 is methyl, and R2 is phenyl, methyl phenyl, n-butyl phenyl, n-octadecyl-phenyl, or an isomer thereof, preferably R2 is meta or para substituted phenyl, such as meta- or para-substituted alkyl substituted phenyl, and R3 is linear or branched alkyl.
In at least one embodiment of Formula (I) or (AI), R1 is methyl, and R2 is branched alkyl, and R3 is linear or branched alkyl.
In a preferred embodiment, R1 is methyl, R2 is substituted phenyl, R3 is C10 to C30 linear or branched alkyl.
In some embodiments, R2 is not meta substituted phenyl. In some embodiments, R2 is not ortho substituted phenyl.
In at least one embodiment, R1 is methyl, R2 is C1 to C35 alkyl substituted phenyl (preferably ortho- or meta-substituted), R3 is C8 to C30 branched alkyl.
In at least one embodiment, R1 is C1 to C10 alkyl, R2 is C1 to C35 alkyl substituted phenyl (preferably para substituted phenyl), R3 is C8 to C30 linear or branched alkyl.
In at least one embodiment, R1 is methyl; R2 is C1 to C35 alkyl substituted phenyl, such as methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecyl, phenyl n-dodecylphenyl, n-tridecylphenyl, n-butadecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl; and R3 is C8 to C30 linear or branched alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-tricontyl, i-propyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, and alkyl-icosyl (such as 2-alkyl-pentyl, 2-alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl, 2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl, 2-alkyl-tridecyl, 2-alkyl-butadecyl, 2-alkyl-pentadecyl, 2-alkyl-hexadecyl, 2-alkyl-heptadecyl, 2-alkyl-octadecyl, 2-alkyl-nonadecyl, 2-alkyl-icosyl or a multi-alkyl analogs, i.e, dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, and trialkyl-icosyl, etc.), or an isomer thereof where each alkyl group is independently a C1 to C40, (alternately C2 to C30, alternately C3 to C20) linear, branched or cyclic alkyl group), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl).
In some embodiments, R2 is C1 to C35 alkyl substituted phenyl, such as methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecyl, phenyl n-dodecylphenyl, n-tridecylphenyl, n-butadecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl; and R3 is C8 to C30 linear or branched alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-tricontyl, i-propyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, and alkyl-icosyl (such as 2-alkyl-pentyl, 2-alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl, 2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl, 2-alkyl-tridecyl, 2-alkyl-butadecyl, 2-alkyl-pentadecyl, 2-alkyl-hexadecyl, 2-alkyl-heptadecyl, 2-alkyl-octadecyl, 2-alkyl-nonadecyl, 2-alkyl-icosyl or a multi-alkyl analog, i.e, dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, and trialkyl-icosyl, etc.), or an isomer thereof where each alkyl group is independently a C1 to C40, (alternately C2 to C30, alternately C3 to C20) linear, branched or cyclic alkyl group), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl).
In at least one embodiment of Formula (I), R1 is methyl, R2 is substituted phenyl, R3 is C8 to C30 linear or branched alkyl, and R4, R5, R6, R7 are perfluoronaphthyl.
In at least one embodiment of Formula (AI), R1 is methyl, R2 is substituted phenyl, R3 is C8 to C30 linear or branched alkyl, E is nitrogen, and each Q is perfluoronaphthyl.
In a preferred embodiment, R1 is methyl; R2 is C1 to C35 alkyl substituted phenyl, such as methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecyl, phenyl n-dodecylphenyl, n-tridecylphenyl, n-butadecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl; R3 is a linear or branched alkyl (such as C10 to C30 branched alkyl) or alternately is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-tricontyl, i-propyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, and alkyl-icosyl (such as 2-alkyl-pentyl, 2-alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl, 2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl, 2-alkyl-tridecyl, 2-alkyl-butadecyl, 2-alkyl-pentadecyl, 2-alkyl-hexadecyl, 2-alkyl-heptadecyl, 2-alkyl-octadecyl, 2-alkyl-nonadecyl, and 2-alkyl-icosyl or a multi-alkyl analog, i.e, dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, trialkyl-icosyl, etc.), or an isomer thereof where each alkyl group is independently a C1 to C40, (alternately C2 to C30, alternately C3 to C20) linear, branched or cyclic alkyl group), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl); and each Q is or each of R4, R5, R6, R7 are perfluoronaphthyl.
In at least one embodiment herein the branched alkyl can be isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoicosyl, isohenicosyl, isodocosyl, isotricosyl, isotetracosyl, isopentacosyl, isohexacosyl, isoheptacosyl, isooctacosyl, isononacosyl, or isotricontyl.
In at least one embodiment, R1 is o-MePh, R2 and R3 are iso-octadecyl.
In at least one embodiment, R1, R2 and R3 together comprise 20 or more carbon atoms, such as 21 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as 45 or more carbon atoms.
The anion component of the activators described herein includes those represented by the formula [Mk+Qn] where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydrogen, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group, optionally having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a perfluorinated aryl group. Preferably at least one Q is not substituted phenyl, such as perfluorophenyl, preferably all Q are not substituted phenyl, such as perfluorophenyl.
Alternately, in at least one embodiment described herein, at least one Q is not substituted phenyl, alternately all Q are not substituted phenyl. Alternately, at least one Q is not fluoro-substituted phenyl, alternately all Q are not fluoro-substituted phenyl. Alternately, at least one Q is not perfluorophenyl, alternately, all Q are not perfluorophenyl.
In at least one embodiment of Formula (AI), when R1 is methyl, R2 is C18 and R3 is C18, then each Q is not perfluorophenyl.
In at least one embodiment, for the borate moiety ([BR4R5R6R7]−) of the activator represented by Formula (I), each of R4, R5, R6, and R7 is independently aryl (such as naphthyl), where at least one of R4, R5, R6, and R7 is substituted with from one to seven fluorine atoms. In at least one embodiment, each of R4, R5, R6, and R7 is naphthyl, where at least one of R4, R5, R6, and R7 is substituted with from one to seven fluorine atoms.
In at least one embodiment, each of R4, R5, R6, and R7 is independently naphthyl comprising one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms.
In at least one embodiment of Formula (I), when R1 is methyl, R2 is C18 and R3 is C18, then each of R4, R5, R6, and R7 is not perfluorophenyl.
In at least one embodiment, R4 is independently naphthyl comprising one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms, and each of R5, R6, and R7 is independently phenyl comprising one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, or five fluorine atoms or naphthyl comprising one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms.
In at least one embodiment of Formula (I) or (AI), each of R4, R5, R6, and R7 is independently naphthyl, where at least one of R4, R5, R6, and R7 is naphthyl substituted with one, two, three, four, five, six or seven fluorine atoms.
In at least one embodiment of Formula (I) or (AI), each of R4, R5, R6, and R7 is independently phenyl, where at least one of R4, R5, R6, and R7 is phenyl substituted with one, two, three, four, or five fluorine atoms.
Alternately, in at least one embodiment of Formula (I) or (AI), preferably at least one R4, R5, R6, and R7 is not substituted phenyl, preferably all of R4, R5, R6, and R7 are not substituted phenyl. In a preferred embodiment, R1 is not methyl, R2 is not C18 and R3 is not C18.
In at least one embodiment of Formula (I) or (AI), preferably all Q or all of R4, R5, R6, and R7 are not perfluoroaryl, such as perfluorophenyl.
In at least one embodiment of Formula (I) or (AI), all of R4, R5, R6, and R7 are naphthyl, where at least one, two, three, or four of R4, R5, R6, and R7 is/are substituted with one, two, three, four, five, six or seven fluorine atoms.
In at least one embodiment, preferably each of R4, R5, R6, and R7 is independently a naphthyl comprising one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms, preferably seven fluorine atoms.
In at least one embodiment, R4 is independently naphthyl comprising one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms.
In at least one embodiment, each of R4, R5, R6, and R7 is independently each a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each of R4, R5, R6, and R7 is independently a fluorinated aryl (such as phenyl, biphenyl, [(C6H3(C6H5)2)4B], or naphthyl) group, and most preferably each of R4, R5, R6, and R7 is independently is a perfluorinated aryl (such as bi-phenyl, [(C6H3(C6H5)2)4B], or naphthyl) group, preferably at least one R4, R5, R6, and R7 is not perfluorophenyl.
In at least one embodiment, the borate activator comprises tetrakis(heptafluoronaphth-2-yl)borate.
Preferred anions for use in the non-coordinating anion activators described herein include those represented by Formula 1 below:
where:
M* is a group 13 atom, preferably B or Al, preferably B;
each R11 is, independently, a halide, preferably a fluoride;
each R12 is, independently, a halide, a C6 to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—Ra, where Ra is a C1 to C20 hydrocarbyl or hydrocarbylsilyl group, preferably R12 is a fluoride or a perfluorinated phenyl group;
each R13 is a halide, a C6 to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—Ra, where Ra is a C1 to C20 hydrocarbyl or hydrocarbylsilyl group, preferably R13 is a fluoride or a C6 perfluorinated aromatic hydrocarbyl group;
where an R12 and R13 can form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably an R12 and R13 form a perfluorinated phenyl ring. Preferably the anion has a molecular weight of greater than 700 g/mol, and, preferably, at least three of the substituents on the M* atom each have a molecular volume of greater than 180 cubic A.
“Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.
Molecular volume may be calculated as reported in Girolami, G. S. (1994) “A Simple “Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, v. 71(11), pp. 962-964. Molecular volume (MV), in units of cubic Å, is calculated using the formula: MV=8.3VS, where VS is the scaled volume. VS is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using Table 1 below of relative volumes. For fused rings, the VS is decreased by 7.5% per fused ring. The Calculated Total MV of the anion is the sum of the MV per substituent, for example, the MV of perfluorophenyl is 183 Å3, and the Calculated Total MV for tetrakis(perfluorophenyl)borate is four times 183 Å3, or 732 Å3.
Exemplary anions useful herein and their respective scaled volumes and molecular volumes are shown in Table 2 below. The dashed bonds indicate bonding to boron.
The activators may be added to a polymerization in the form of an ion pair using, for example, [DEBAH]+ [NCA]− in which the 4-butyl-N,N-bis(isotridecyl)benzenaminium-(“DEBAH)”) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]−. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(C10F7)3, which abstracts an anionic group from the complex to form an activated species.
In at least one embodiment, the activators obtained in their salt form used for a borate activator compound are: Lithium tetrakis(heptafluoronaphthalen-2-yl)borate etherate (Li—BF28), N,N-Dimethylanilinium tetrakis(heptafluoronaphthalen-2-yl)borate (DMAH-BF28), Sodium tetrakis(heptafluoronaphthalen-2-yl)borate (Na—BF28) and N,N-dimethylanilinium tetrakis(heptafluoronaphthalen-2-yl)borate (DMAH-BF28).
In at least one embodiment of the activator represented by Formula (AI), when Q is a fluorophenyl group, then R2 is not a C1-C40 linear alkyl group, preferably R2 is not an optionally substituted C1-C40 linear alkyl group (alternately when Q is a substituted phenyl group, then R2 is not a C1-C40 linear alkyl group, preferably R2 is not an optionally substituted C1-C40 linear alkyl group). Optionally, when Q is a fluorophenyl group (alternately when Q is a substituted phenyl group), then R2 is a meta- and or para-substituted phenyl group, where the meta and para substituents are, independently, an optionally substituted C1 to C40 hydrocarbyl group (such as a C6 to C40 aryl group or linear alkyl group, a C12 to C30 aryl group or linear alkyl group, or a C10 to C20 aryl group or linear alkyl group), an optionally substituted alkoxy group, or an optionally substituted silyl group. Optionally, each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl (such as phenyl or naphthyl) group, and most preferably each Q is a perfluorinated aryl (such as phenyl or naphthyl) group. Optionally, at least one Q is not substituted phenyl. Optionally all Q are not substituted phenyl. Optionally at least one Q is not perfluorophenyl. Optionally all Q are not perfluorophenyl.
In some embodiments, R1 is not methyl, R2 is not C18 alkyl and R3 is not C18 alkyl, alternately R1 is not methyl, R2 is not C18 alkyl and R3 is not C18 alkyl and at least one Q is not substituted phenyl, optionally all Q are not substituted phenyl.
Useful cation components in Formulas (AI) or (I) include those represented by the formula:
Useful cation components in Formulas (AI) or (I) include those represented by the formula:
The activators may be added to a polymerization in the form of an ion pair using, for example, [M2HTH]+ [NCA]− in which the di(hydrogenated tallow)methylamine (“M2HTH”) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]−. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(C6F5)3, which abstracts an anionic group from the complex to form an activated species. Useful activators include di(hydrogenated tallow)methylammonium[tetrakis(pentafluorophenyl)borate] (i.e., [M2HTH]B(C6F5)4) and di(octadecyl)tolylammonium [tetrakis(pentafluorophenyeborate] (i.e., [DOdTH]B(C6F5)4).
Activator compounds can include one or more of: N,N-di(hydrogenated tallow)methylammonium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-tetradecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-dodecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-butyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octadecyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-ethyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didodecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctylammonium [tetrakis(perfluorophenyl)borate], N-ethyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N,N-di(octadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(hexadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(tetradecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(dodecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and N-methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate].
Additional useful activators and the synthesis thereof, are described in U.S. Ser. No. 16/394,166 filed Apr. 25, 2019, U.S. Ser. No. 16/394,186, filed Apr. 25, 2019, and U.S. Ser. No. 16/394,197, filed Apr. 25, 2019, which are incorporated by reference herein.
In at least one embodiment, the activator is not:
In at least one embodiment, an activator of the present disclosure, when combined with a catalyst compound to form an active olefin polymerization catalyst, produces a higher molecular weight polymer (e.g., Mw) than comparative activators that use other borate anions.
In at least one embodiment, an activator of the present disclosure where R1 is methyl, when combined with a catalyst compound to form an active olefin polymerization catalyst, produces a higher molecular weight polymer (e.g., Mw) than comparative activators that use other borate anions.
The typical activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio is about a 1:1 molar ratio. Alternate preferred ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. A particularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.
It is also within the scope of the present disclosure that the catalyst compounds can be combined with combinations of alumoxanes and the activators described herein.
In at least one embodiment, the general synthesis of the activators can be performed using a two-step process. In the first step, an amine or phosphine is dissolved in a solvent (e.g. hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form a chloride salt. This salt is typically isolated by filtration from the reaction medium and dried under reduced pressure. The isolated chloride is then heated to reflux with about one molar equivalent of an alkali metal metallate or metalloid (such as a borate or aluminate) in a solvent (e.g. cyclohexane, dichloromethane, methylcyclohexane) to form the desired borate or aluminate along with byproduct alkali metal chloride, the latter of which can typically be removed by filtration.
In at least one embodiment, the general synthesis of the ammonium borate activators can be performed using a two-step process. In the first step, an amine is dissolved in a solvent (e.g. hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form an ammonium chloride salt. This salt is typically isolated by filtration from the reaction medium and dried under reduced pressure. The isolated ammonium chloride is then heated to reflux with about one molar equivalent of an alkali metal borate in a solvent (e.g. cyclohexane, dichloromethane, methylcyclohexane) to form the ammonium borate along with byproduct alkali metal chloride, the latter of which can typically be removed by filtration.
In at least one embodiment, an activator of the present disclosure is soluble in an aliphatic solvent at a concentration of about 10 mM or greater, such as about 20 mM or greater, such as about 30 mM or greater, such as about 50 mM or greater, such as about 75 mM or greater, such as about 100 mM or greater, such as about 200 mM or greater, such as about 300 mM or greater. In at least one embodiment, an activator of the present disclosure dissolves in isohexane or methylcyclohexane at 25° C. to form a homogeneous solution of at least 10 mM concentration.
In at least one embodiment, the solubility of the borate or aluminate activators of the present disclosure in aliphatic hydrocarbon solvents increases with the number of aliphatic carbons in the cation group (i.e., the ammonium or the phosphonium). In at least one embodiment, a solubility of at least 10 mM is achieved with an activator having an ammonium or phosphonium group of about 21 aliphatic carbon atoms or more, such as about 25 aliphatic carbons atoms or more, such as about 35 carbon atoms or more.
In at least one embodiment, the solubility of the ammonium borate activators of the present disclosure in aliphatic hydrocarbon solvents increases with the number of aliphatic carbons in the ammonium group. In at least one embodiment, a solubility of at least 10 mM is achieved with an activator having an ammonium group of about 21 aliphatic carbon atoms or more, such as about 25 aliphatic carbons atoms or more, such as about 35 carbon atoms or more.
Useful aliphatic hydrocarbon solvent can be isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In at least one embodiment, aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as at 0 wt % based upon the weight of the solvents.
The activators of the present disclosure can be dissolved in one or more additional solvents. Additional solvent includes ethereal, halogenated and N,N-dimethylformamide solvents.
In at least one embodiment, the aliphatic solvent is isohexane and or and or methylcyclohexane.
In addition to these activator compounds, scavengers or co-activators may be used. Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.
In at least one embodiment, little or no scavenger is used in the process to produce the ethylene polymer. Scavenger (such as trialkyl aluminum) can be present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.
Transition metal compounds capable of catalyzing a reaction, such as a polymerization reaction, upon activation with an activator as described above are suitable for use in polymerization processes of the present disclosure.
Catalyst compounds for producing polyolefins include various catalyst compounds. Catalyst compounds of the present disclosure can provide polyolefins having (1) high comonomer incorporation, high molecular weight, and or a melt temperature of about 95° C. or greater, (2) low molecular weight and or a melt temperature of about 110° C. or greater, (3) high molecular weight and or a melt temperature of about 110° C. or greater, or (4) low comonomer incorporation, high molecular weight, and or a melt temperature of about 110° C. or greater. For example, a salan catalyst having one or more fluorenyl moieties can provide high molecular weight polyolefins, and a salan catalyst having one or more carbazolyl moieties can provide low molecular weight polyolefins.
A salan catalyst of the present disclosure can be represented by Formula (CI) or (CII):
wherein:
M is a Group 3, 4, 5 or 6 transition metal (such as a Group 4 transition metal, such as Hf, Zr, or Ti);
X1 and X2 are, independently, a C1 to C20 hydrocarbyl, a C1 to C20 substituted hydrocarbyl, a heteroatom or a heteroatom containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure (e.g., benzyl, methyl, ethyl, chloro, or bromo); wherein if M is trivalent then X2 is not present;
each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 is independently hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom, a heteroatom containing group, or two or more of R1 to R14 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure (e.g., H, methyl, ethyl, propyl, butyl, pentyl, or isomers thereof);
Y is a divalent C1 to C20 hydrocarbyl or substituted divalent C1 to C20 hydrocarbyl; and
Q is a neutral donor group, for example, a neutral donor group containing at least one atom from Group 15 (e.g., N or P) or Group 16 (e.g., O, S, or Se).
In some embodiments, R6 is a C7 to C60 fused polycyclic (e.g., having at least 2 ring structures) group, which optionally contains up to 20 atoms from Groups 15 and 16, where at least one ring is aromatic, or may independently form a C4 to C60 cyclic or polycyclic ring structure with R3, R4, or R5 or a combination thereof; R7 is, independently, as defined for R6, a hydrogen, a C1-C60 hydrocarbyl, a substituted C1-C60 hydrocarbyl, a heteroatom, or a heteroatom containing group, or may independently form a C4 to C60 cyclic or polycyclic ring structure with R8, R9, or R10 or a combination thereof.
In some embodiments, M is a Group 4 metal, or M is Hf, Ti and or Zr, or M is Hf or Zr. In some embodiments, each of X1 and X2 is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides having from 1 to 20 carbon atoms, sulfides, phosphides, halides, amines, phosphines, and ethers.
For purposes herein, any hydrocarbyl (and any alkyl) may be independently selected from methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl.
In at least one embodiment, for the catalyst compound of Formula (CII), Y is a divalent C1-C40 hydrocarbyl or divalent substituted hydrocarbyl containing a portion that has a linker backbone having from 1 to 18 carbon atoms linking or bridging between Q and N. In an embodiment, Y is a divalent C1-C40 hydrocarbyl or substituted hydrocarbyl containing a portion that has a linker backbone containing from 1 to 18 carbon atoms linking Q and N wherein the hydrocarbyl contains O, S, S(O), S(O)2, Si(R′)2, P(R′), N or N(R′), wherein each R′ is independently a C1-C18 hydrocarbyl. In an embodiment, Y is ethylene (—CH2CH2—) or 1,2-cyclohexylene. In an embodiment, Y is —CH2CH2CH2— derived from propylene. In an embodiment, Y is a C1 to C20 alkyl group, such as divalent methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl.
In at least one embodiment, for the catalyst compound of Formula (CI) or (CII), Y is a divalent C1-C40 hydrocarbyl radical having a portion that has a linker backbone including from 1 to 18 carbon atoms linking or bridging between nitrogen atoms N. In some embodiments, Y is a C1-C40 hydrocarbyl radical comprising a portion that includes a linker backbone having from 1 to 18 carbon atoms linking the nitrogen atoms N where the hydrocarbyl further includes O, S, S(O), S(O)2, Si(R*)2, P(R*), N or N(R*), where each R* is independently a C1-C18 hydrocarbyl. In at least one embodiment, Y is selected from ethylene (—CH2CH2—) 1,2-cyclohexylene, or —CH2CH2CH2—. In at least one embodiment, Y is ethylene (—CH2CH2—).
In some embodiments, X1 and X2 together form a part of a fused ring or a ring system having from 4 to 62 carbon atoms.
In at least one embodiment, each of X1 and X2 is independently selected from the group consisting of halides, alkyl radicals having from 1 to 7 carbon atoms, or benzyl.
In at least one embodiment, for the catalyst compound of Formula (CI) or (CII), each of X1 and X2 is independently a halogen or a C1 to C7 hydrocarbyl radical. In some embodiments, each of X1 and X2 is benzyl.
In some embodiments, for the catalyst compound of Formula (CI) or (CII), methyl, each of R4 and R9 is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
In some embodiments, for the catalyst compound of Formula (CI) or (CII), each R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 is, independently, hydrogen, a halogen, or a C1 to C30 hydrocarbyl, such as methyl or fluoro.
In at least one embodiment, for the catalyst compound of Formula (CI), R13 and R14 are methyl; and R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 are hydrogen.
In at least one embodiment, for the catalyst compound of Formula (CI), R4, R9, R13 and R14 are methyl; and R1, R2, R3, R5, R6, R7, R8, R10, R11, and R12 are hydrogen.
In embodiments, for the catalyst compound of Formula (CI) or (CII), R6 and or R7 are represented by the formula:
Each of R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, and R26 is, independently, a hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom containing group, or two or more of R15, R16, R17, R18, R19, R20, R21 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or two or more of R22, R23, R24, R25, and R26 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
In at least one embodiment, one or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, and R26 is independently selected from:
1) methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, or n-tricontyl;
2) alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-icosyl (including multi-alkyl analogs, i.e, dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, and trialkyl-icosyl, wherein each alkyl group is independently a C1 to C40, linear, branched or cyclic alkyl group;
3) methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, icosylphenyl, henicosylphenyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, pentacosylphenyl, hexacosylphenyl, heptacosylphenyl, octacosylphenyl, nonacosylphenyl, tricontylphenyl, 3,5,5-trimethylhexylphenyl, dioctylphenyl, 3,3,5-trimethylhexylphenyl, or 2,2,3,3,4 pentamethypentylylphenyl;
4) trialkylsilyl group, wherein each alkyl is independently an optionally substituted trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl, tri-nonadecylsilyl, or tri-icosylsilyl;
5) an alkoxy group represented by the formula —OR*, wherein R* is an optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, phenyl, alkylphenyl, naphthyl, or anthracenyl;
6) a halogen; and
7) a halogen containing group.
In some embodiments, the catalyst compound represented by Formula (CI) is represented by the Formula (IV) or (V):
where:
M is a Group 3, 4, 5 or 6 transition metal (such as a Group 4 transition metal, such as Hf, Zr, or Ti);
X1 and X2 are, independently, C1 to C20 hydrocarbyl, a C1 to C20 substituted hydrocarbyl, a heteroatom or a heteroatom containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure (e.g., benzyl, methyl, ethyl, chloro, or bromo); wherein if M is trivalent then X2 is not present;
Y is a divalent C1 to C20 hydrocarbyl or substituted divalent C1 to C20 hydrocarbyl;
Q* is a group 15 or 16 atom (e.g., N, O, S or P);
z is 0 or 1;
J* is CR′″ or N;
G* is CR′″ or N; and
each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R′″, and R″ is independently hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom, a heteroatom containing group, or two or more of R1 to R28, R′″, and R″ may independently join together to form a C4 to C62 cyclic or polycyclic ring structure (e.g., H, methyl, ethyl, propyl, butyl, pentyl, or isomers thereof).
In some embodiments, for the catalyst compound of Formula (IV) or (V), each R1, R2, R3, R4, R5, R10, R14, R15, R16, R17, and R18 is, independently, a hydrogen, a C1-C20 hydrocarbyl, a substituted C1 to C20 hydrocarbyl, or two or more of R1, R2, R3, R4, R5, R10, R14, R15, R16, R17, and R18 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
In some embodiments, for the catalyst compound of Formula (IV) or (V), each R″, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, R27, and R28 is, independently, hydrogen, a halogen, a C1 to C30 hydrocarbyl, a C1 to C20 hydrocarbyl, or a C1 to C10 hydrocarbyl (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl).
In some embodiments, for the catalyst compound of Formula (IV) or (V), one or more of R″, R′″, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, R27, and R28 is, independently, a substituted C1 to C30 hydrocarbyl, a substituted C1 to C20 hydrocarbyl, or a substituted C1 to C10 hydrocarbyl (such as 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4-dimethylaminophenyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, trifluoromethyl, fluoromethyl, trichloromethyl, chloromethyl, mesityl, methylthio, phenylthio, (trimethylsilyl)methyl, and (triphenylsilyl)methyl.
In at least one embodiment, for the catalyst compound of Formula (IV) or (V), one or more of R″, R′″, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, R27, and R28 is a methyl, a fluoride, chloride, bromide, iodide, methoxy, ethoxy, isopropoxy, trifluoromethyl, dimethylamino, diphenylamino, adamantyl, phenyl, pentafluorphenyl, naphthyl, anthracenyl, dimethylphosphanyl, diisopropylphosphanyl, diphenylphosphanyl, methylthio, and phenylthio.
In at least one embodiment, for the catalyst compound of Formula (IV) or (V), G* and J* are the same, such as G* and J* are N, alternately G* and J* are CR′″, where each R′″ is H or a C1 to C12 hydrocarbyl or substituted hydrocarbyl (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, trifluoromethylphenyl, tolyl, phenyl, methoxyphenyl, tertbutylphenyl, fluorophenyl, diphenyl, dimethylaminophenyl, chlorophenyl, bromophenyl, iodophenyl, (trimethylsilyl)phenyl, (triethylsilyl)phenyl, (triethylsilyl)methyl, (triethylsilyl)methyl. In some embodiments, G* and J* are different than each other (e.g., G* is CR′″ and J* is N, alternatively J* is CR′″ and G* is N).
In at least one embodiment, for the catalyst compound of Formula (IV) or (V), G* and J* are the same or different. For example, each G* and J* is independently carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, substituted fluorenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, or substituted phenanthryl. In some embodiments, G* and J* are different than each other (e.g., G* is CR′″ and J* is N, alternatively J* is CR′″ and G* is N).
In at least one embodiment, for the catalyst compound of Formula (IV) or (V), R1 and R28 are methyl; R2 through R27 are hydrogen; Y is ethylene (—CH2CH2—), and G* and J* are N.
In at least one embodiment, for the catalyst compound of Formula (IV) or (V), R4 and R7 are methyl; R3, R5 and R15 through R17 are hydrogen; Y is ethylene (—CH2CH2—), and G* and J* are carbazolyl or fluorenyl. In some examples, G* and J* are carbazolyl; or G* and J* are substituted fluorenyl.
In at least one embodiment, a catalyst compound of Formula (CI) is selected from:
In at least one embodiment, a catalyst compound of Formula (CI) is selected from:
Additional examples of catalysts represented by Formula (CI) include those described in U.S. Pat. Nos. 8,907,032; 9,193,813, 9,290,589; 7,544,749; 6,686,490; 6,632,899; and 9,493,587; US Publication No. 2014/0039137; and PCT Published Applications: WO 2012/098521; WO 2011/158241; WO 2014/022008; WO 2014/022010; WO 2014/022011; WO 2014/022012; WO 2014/022013; WO 2014/022746; WO 2014/070502; WO 2014/143202; WO 2014/204624; WO 2014/204681; and WO 2014/204625.
In some embodiments, the catalyst compound represented by Formula (CII) is represented by the Formula (VI) or (VII):
where:
M is a Group 3, 4, 5 or 6 transition metal (such as a Group 4 transition metal, such as Hf, Zr, or Ti);
X1 and X2 are, independently, a C1 to C20 hydrocarbyl, a C1 to C20 substituted hydrocarbyl, a heteroatom or a heteroatom containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure (e.g., benzyl, methyl, ethyl, chloro, or bromo); wherein if M is trivalent then X2 is not present;
Y is a divalent C1 to C20 hydrocarbyl or substituted divalent C1 to C20 hydrocarbyl;
Q* is a group 15 or 16 atom (e.g., N, O, S or P);
z is 0 or 1;
J* is CR′″ or N;
G* is CR′″ or N; and
each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R′″, R*, and R″ is independently hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom, a heteroatom containing group, or two or more of R1 to R27, R′″, R*, and R″ may independently join together to form a C4 to C62 cyclic or polycyclic ring structure (e.g., H, methyl, ethyl, propyl, butyl, pentyl, or isomers thereof).
In some embodiments, for the catalyst compound of Formula (VI) or (VII), each R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 is, independently, a hydrogen, a C1-C20 hydrocarbyl, a substituted C1 to C20 hydrocarbyl, or two or more of R1 to R10 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
In some embodiments, for the catalyst compound of Formula (VI) or (VII), each R*, R″, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, and R27 is, independently, hydrogen, a halogen, a C1 to C30 hydrocarbyl, a C1 to C20 hydrocarbyl, or a C1 to C10 hydrocarbyl (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl).
In some embodiments, for the catalyst compound of Formula (VI) or (VII), one or more of R*, R″, R′″, R1R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, and R27 is, independently, a substituted C1 to C30 hydrocarbyl, a substituted C1 to C20 hydrocarbyl, or a substituted C1 to C10 hydrocarbyl (such as 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4-dimethylaminophenyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, trifluoromethyl, fluoromethyl, trichloromethyl, chloromethyl, mesityl, methylthio, phenylthio, (trimethylsilyl)methyl, and (triphenylsilyl)methyl).
In at least one embodiment, for the catalyst compound of Formula (VI) or (VII), one or more of R*, R″, R′″, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, and R27 is a methyl, a fluoride, chloride, bromide, iodide, methoxy, ethoxy, isopropoxy, trifluoromethyl, dimethylamino, diphenylamino, adamantyl, phenyl, pentafluorphenyl, naphthyl, anthracenyl, dimethylphosphanyl, diisopropylphosphanyl, diphenylphosphanyl, methylthio, and phenylthio.
In at least one embodiment, for the catalyst compound of Formula (VI) or (VII), Q* is N, O, S or P. When Q* is a Group 15 atom, z is 1, and when Q* is a group 16 atom, z is 0.
In at least one embodiment, for the catalyst compound of Formula (VI) or (VII), Q* is a neutral donor group containing at least one atom from Group 15 or Group 16. In one or more examples, Q* is NR′2, OR, SR, PR′2, where R′ is methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl or two R groups are linked together to form a 5-membered ring such as pyrrolidinyl or a six-membered ring such as piperidinyl. In other examples, the -(-Q*-Y—)-fragment can form a substituted or unsubstituted heterocycle which may or may not be aromatic and may have multiple fused rings. In at least one embodiment of the transition metal complexes described herein Q* can be or include an amine, ether, or pyridine.
In at least one embodiment, for the catalyst compound of Formula (VI) or (VII), G* and J* are the same, such as G* and J* are N, alternately G* and J* are CR′″, where each R′″ is H or a C1 to C12 hydrocarbyl or substituted hydrocarbyl (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, trifluoromethylphenyl, tolyl, phenyl, methoxyphenyl, tertbutylphenyl, fluorophenyl, diphenyl, dimethylaminophenyl, chlorophenyl, bromophenyl, iodophenyl, (trimethylsilyl)phenyl, (triethylsilyl)phenyl, (triethylsilyl)methyl, (triethylsilyl)methyl). In some embodiments, G* and J* are different than each other (e.g., G* is CR′″ and J* is N, alternatively J* is CR′″ and G* is N).
In at least one embodiment, for the catalyst compound of Formula (VI) or (VII), G* and J* are the same or different. For example, each G* and J* is independently carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, substituted fluorenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, or substituted phenanthryl. In a useful embodiment of the transition metal complexes described herein G* and J* are different than each other (e.g., G* is CR′″ and J* is N, alternatively J* is CR′″ and G* is N).
In at least one embodiment, for the catalyst compound of Formula (VI) or (VII), R1 is methyl; R2 through R27 are hydrogen; Y is ethylene (—CH2CH2—), Q*, G* and J* are N, and R*z is methyl.
In at least one embodiment, for the catalyst compound of Formula (VI) or (VII), R4 and R7 are methyl; R1 through R3, R5 through R6, and R8 through R10 are hydrogen; Y is ethylene (—CH2CH2—), Q* is an N-containing or O-containing group, G* and J* are carbazolyl or fluorenyl. In some examples, G* and J* are carbazolyl and Q* is an amine group; or G* and J* are substituted fluorenyl and Q* is an ether group.
In at least one embodiment, a catalyst compound of Formula (CII) is selected from:
In at least one embodiment, a catalyst compound of Formula (CII) is selected from:
Additional examples of catalysts represented by Formula (CII) include those described in WO 2016/153682.
All air sensitive syntheses are carried out in nitrogen or argon purged dry boxes.
All solvents are available from commercial sources. Methylmagnesium bromide solution (Grignard reagent), 9H-fluoren-9-one, ammonium chloride, tetrahydrofuran, p-cresol, dichloromethane, concentrated sulfuric acid, paraformaldehyde, 2-methoxyethanamine, methanol, ethyl acetate, hexane, toluene, tetrabenzyl hafnium, tetrabenzyl zirconium, and other precursors, reagents, and solvents are available from commercial sources.
For example, a catalyst compound may be prepared by two general synthetic routes. The salan ligands can be prepared by a one-step Mannich reaction from a phenol (representative Reaction A) or by a two-step imine-condensation/alkylation procedure if the salicylaldehyde is used (representative Reaction B). The ligand is then converted into the metal dibenzyl catalyst precursor by reaction with the metal tetra-aryl starting material, e.g., tetrabenzyl, to yield the finished complex (representative Reaction C).
Alternatively, ligands can be synthesized according to the representative schematic reaction procedure described in Schemes 1-3 and transition metal catalysts can be synthesized according to the schematic reaction procedure described in Scheme 4.
As shown in Scheme 1: 9H-fluoren-9-one is treated with the methyl Grignard reagent MeMgBr to produce 9-methyl-9H-fluoren-9-ol (S1).
As shown in Scheme 2: 9-methyl-9H-fluoren-9-ol (S1) is treated with p-cresol and sulfuric acid to produce 4-methyl-2-(9-methyl-9H-fluoren-9-yl)phenol (S2).
As shown in Scheme 3: 4-methyl-2-(9-methyl-9H-fluoren-9-yl)phenol (S2), paraformaldehyde, 2-methoxyethanamine, water, and methanol are combined and heated to produce the ligand of Formula (IV), also referred to as 2-(((2-hydroxy-3-(9-methyl-9H-fluoren-9-yl)benzyl)(2-methoxyethyl)amino)methyl)-4-methyl-6-(9-methyl-9H-fluoren-9-yl)phenol.
As shown in Scheme 4: the ligand of Formula (L4) is treated with tetrabenzyl zirconium (ZrBn4) in toluene to produce the transition metal complex or catalysts.
In general, once the desired ligand is formed, it can be combined with a metal atom, ion, compound or other metal precursor compound, and in some embodiments, compositions can include ligands in combination with an appropriate metal precursor and an optional activator. For example, in some embodiments, the metal precursor can be an activated metal precursor, which refers to a metal precursor (described below) that has been combined or reacted with an activator prior to combination or reaction with the ancillary ligand. As noted above, in one aspect the invention provides compositions that include such combinations of ligand and metal atom, ion, compound or precursor. In some applications, the ligands are combined with a metal compound or precursor and the product of such combination is not determined, if a product forms. For example, the ligand may be added to a reaction vessel at the same time as the metal or metal precursor compound along with the reactants, activators, scavengers, etc. Additionally, the ligand can be modified prior to addition to or after the addition of the metal precursor, e.g. through a deprotonation reaction or some other modification.
In general, the metal precursor compounds can be characterized by the general formula M(L)m where M is a metal selected from, for example, the group consisting of Ti, Hf, and Zr. Each L is a ligand independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof. Optionally, two or more L groups are joined into a ring structure. One or more of the ligands L may be ionically bonded to the metal M and, for example, L may be a non-coordinated or loosely coordinated or weakly coordinated anion (e.g., L may be selected from the group consisting of those anions described below in the conjunction with the activators). (See Marks et al., Chem. Rev. (2000) v. 100, pp. 1391-1434, for a detailed discussion of these weak interactions.) The metal precursors may be monomeric, dimeric or higher orders thereof. In more specific embodiments, the metal precursor includes a metal selected from Zr and Hf. Examples of suitable titanium, hafnium and zirconium precursors include TiCl4, Ti(CH2Ph)4, Ti(CH2CMe3)4, Ti(CH2SiMe3)4, Ti(CH2Ph)3Cl, Ti(CH2CMe3)3Cl, Ti(CH2SiMe3)3Cl, Ti(CH2Ph)2Cl2, Ti(CH2CMe3)2Cl2, Ti(CH2SiMe3)2Cl2, Ti(NMe2)4, Ti(NEt2)4, Ti(O-iPr)4, and Ti(N(SiMe3)2)2Cl2; HfCl4, Hf(CH2Ph)4, Hf(CH2CMe3)4, Hf(CH2SiMe3)4, Hf(CH2Ph)3Cl, Hf(CH2CMe3)3Cl, Hf(CH2SiMe3)3α Hf(CH2Ph)2Cl2, Hf(CH2CMe3)2Cl2, Hf(CH2SiMe3)2Cl2, Hf(NMe2)4, Hf(NEt2)4, Hf(N(SiMe3)2)2Cl2, Hf(N(SiMe3)CH2CH2CH2N(SiMe3))Cl2, and Hf(N(Ph)CH2CH2CH2N(Ph))Cl2; ZrCl4, Zr(CH2Ph)4, Zr(CH2CMe3)4, Zr(CH2SiMe3)4, Zr(CH2Ph)3Cl, Zr(CH2CMe3)3Cl, Zr(CH2SiMe3)3Cl, Zr(CH2Ph)2Cl2, Zr(CH2CMe3)2Cl2, Zr(CH2SiMe3)2Cl2, Zr(NMe2)4, Zr(NEt2)4, Zr(NMe2)2Cl2, Zr(NEt2)2Cl2, Zr(N(SiMe3)2)2Cl2) Zr(N(SiMe3)CH2 CH2CH2N(SiMe3))Cl2, and Zr(N(Ph)CH2CH2CH2N(Ph))Cl2.
The ligand to metal precursor compound ratio is typically from about 0.01:1 to about 100:1, such as from about 0.1:1 to about 10:1 such as from about 1:1, 2:1 or 3:1.
In some embodiments, a co-activator is combined with the catalyst compound (such as halogenated catalyst compounds described above) to form an alkylated catalyst compound. Organoaluminum compounds which may be utilized as co-activators include, for example, trialkyl aluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like, or alumoxanes.
In some embodiments, two or more different catalyst compounds are present in the catalyst system used herein (e.g., a dual catalyst system). In some embodiments, two or more different catalyst compounds are present in the reaction zone where the process(es) described herein occur. When two transition metal compound based catalysts are used in one reactor as a mixed catalyst system, the two transition metal compounds are preferably chosen such that the two are compatible. A simple screening method such as by 1H or 13C NMR, known to those of ordinary skill in the art, can be used to determine which transition metal compounds are compatible. It is preferable to use the same activator for the transition metal compounds, however, two different activators can be used in combination. If one or more transition metal compounds contain an anionic ligand as a leaving group which is not a hydrogen, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane or other alkyl aluminum is typically contacted with the transition metal compounds prior to addition of the non-coordinating anion activator.
The two transition metal compounds (pre-catalysts) may be used in any ratio. Preferred molar ratios of (A) transition metal compound to (B) transition metal compound fall within the range of (A:B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The particular ratio chosen will depend on the exact pre-catalysts chosen, the method of activation, and the end product desired. In a particular embodiment, when using the two pre-catalysts, where both are activated with the same activator, useful mole percents, based upon the molecular weight of the pre-catalysts, are 10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to 10% B.
In embodiments herein, the catalyst system may comprise a support material. In at least one embodiment, the support material is a porous support material, for example, talc, or inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other suitable organic or inorganic support material and the like, or mixtures thereof.
In at least one embodiment, the support material is an inorganic oxide. Suitable inorganic oxide materials for use in catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be used, for example, functionalized polyolefins, such as polypropylene. Supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. Support materials include Al2O3, ZrO2, SiO2, SiO2/Al2O3, SiO2/TiO2, silica clay, silicon oxide/clay, or mixtures thereof.
The support material, such as an inorganic oxide, can have a surface area of from 10 m2/g to 700 m2/g, pore volume in the range of from 0.1 cc/g to 4.0 cc/g and average particle size in the range of from 5 μm to 500 μm. In at least one embodiment, the surface area of the support material is in the range of from 50 m2/g to 500 m2/g, pore volume of from 0.5 cc/g to 3.5 cc/g and average particle size of from 10 μm to 200 μm. In at least one embodiment, the surface area of the support material is in the range is from 100 m2/g to 400 m2/g, pore volume from 0.8 cc/g to 3.0 cc/g and average particle size is from 5 μm to 100 μm. The average pore size of the support material useful in the present disclosure is in the range of from 10 Å to 1000 Å, such as 50 Å to 500 Å, such as 75 Å to 350 Å. In some embodiments, the support material is a high surface area, amorphous silica (surface area=300 m2/gm; pore volume of 1.65 cm3/gm). Exemplary silicas are marketed under the tradenames of DAVISON 952 or DAVISON 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments DAVISON 948 is used.
The support material should be dry, that is, substantially free of absorbed water. Drying of the support material can be effected by heating or calcining at 100° C. to 1,000° C., such as at least about 600° C. When the support material is silica, it is heated to at least 200° C., such as 200° C. to 850° C., such as at about 600° C.; and for a time of 1 minute to about 100 hours, from 12 hours to 72 hours, or from 24 hours to 60 hours. The calcined support material should have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.
The support material, having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In some embodiments, the slurry of the support material is first contacted with the activator for a period of time in the range of from 0.5 hours to 24 hours, from 2 hours to 16 hours, or from 4 hours to 8 hours. The solution of the catalyst compound is then contacted with the isolated support/activator. In some embodiments, the supported catalyst system is generated in situ. In at least one embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time in the range of from 0.5 hours to 24 hours, from 2 hours to 16 hours, or from 4 hours to 8 hours. The slurry of the supported catalyst compound is then contacted with the activator solution.
The mixture of the catalyst, activator and support is heated to 0° C. to 70° C., such as to 23° C. to 60° C., such as at room temperature. Contact times typically range from 0.5 hours to 24 hours, from 2 hours to 16 hours, or from 4 hours to 8 hours.
Suitable non-polar solvents are materials in which all of the reactants used herein, e.g., the activator, and the catalyst compound, are at least partially soluble and which are liquid at room temperature. Non-limiting example non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene.
In at least one embodiment, the support material comprises a support material treated with an electron-withdrawing anion. The support material can be silica, alumina, silica-alumina, silica-zirconia, alumina-zirconia, aluminum phosphate, heteropolytungstates, titania, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and the electron-withdrawing anion is selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof.
The electron-withdrawing component used to treat the support material can be any component that increases the Lewis or Brønsted acidity of the support material upon treatment (as compared to the support material that is not treated with at least one electron-withdrawing anion). In at least one embodiment, the electron-withdrawing component is an electron-withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion. Electron-withdrawing anions can be sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or mixtures thereof, or combinations thereof. An electron-withdrawing anion can be fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, or any combination thereof, at least one embodiment of this disclosure. In at least one embodiment, the electron-withdrawing anion is sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or combinations thereof.
Thus, for example, the support material suitable for use in the catalyst systems of the present disclosure can be one or more of fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof. In at least one embodiment, the activator-support can be, or can comprise, fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof. In another embodiment, the support material includes alumina treated with hexafluorotitanic acid, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, fluorided boria-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, or combinations thereof. Further, any of these activator-supports optionally can be treated with a metal ion.
Nonlimiting examples of cations suitable for use in the present disclosure in the salt of the electron-withdrawing anion include ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H+, [H(OEt2)2]+, or combinations thereof.
Further, combinations of one or more different electron-withdrawing anions, in varying proportions, can be used to tailor the specific acidity of the support material to a desired level. Combinations of electron-withdrawing components can be contacted with the support material simultaneously or individually, and in any order that provides a desired chemically-treated support material acidity. For example, in at least one embodiment, two or more electron-withdrawing anion source compounds in two or more separate contacting steps.
In at least one embodiment of the present disclosure, one example of a process by which a chemically-treated support material is prepared is as follows: a selected support material, or combination of support materials, can be contacted with a first electron-withdrawing anion source compound to form a first mixture; such first mixture can be calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture can then be calcined to form a treated support material. In such a process, the first and second electron-withdrawing anion source compounds can be either the same or different compounds.
The method by which the oxide is contacted with the electron-withdrawing component, typically a salt or an acid of an electron-withdrawing anion, can include gelling, co-gelling, impregnation of one compound onto another, or combinations thereof. Following a contacting method, the contacted mixture of the support material, electron-withdrawing anion, and optional metal ion, can be calcined.
According to another embodiment of the present disclosure, the support material can be treated by a process comprising: (i) contacting a support material with a first electron-withdrawing anion source compound to form a first mixture; (ii) calcining the first mixture to produce a calcined first mixture; (iii) contacting the calcined first mixture with a second electron-withdrawing anion source compound to form a second mixture; and (iv) calcining the second mixture to form the treated support material.
In embodiments herein, the present disclosure provides polymerization processes where monomer (such as propylene or ethylene), and optionally comonomer, are contacted with a catalyst system comprising an activator and at least one catalyst compound, as described above. The catalyst compound and activator may be combined in any order, and are combined typically prior to contacting with the monomer.
In at least one embodiment, a polymerization process includes a) contacting one or more olefin monomers with a catalyst system comprising: i) an activator and ii) a catalyst compound of the present disclosure. The activator is a non-coordination anion activator. The one or more olefin monomers may be propylene and or ethylene and the polymerization process further comprises heating the one or more olefin monomers and the catalyst system to 70° C. or more to form propylene polymers or ethylene polymers, such as propylene polymers.
Monomers useful herein include substituted or unsubstituted C2 to C40 alpha olefins, such as C2 to C20 alpha olefins, such as C2 to C12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In at least one embodiment, the monomer comprises propylene and an optional comonomers comprising one or more propylene or C4 to C40 olefins, such as C4 to C20 olefins, such as C6 to C12 olefins. The C4 to C40 olefin monomers may be linear, branched, or cyclic. The C4 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups. In at least one embodiment, the monomer comprises propylene and an optional comonomers comprising one or more C3 to C40 olefins, such as C4 to C20 olefins, such as C6 to C12 olefins. The C3 to C40 olefin monomers may be linear, branched, or cyclic. The C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups.
Exemplary C2 to C40 olefin monomers and optional comonomers include propylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.
In at least one embodiment, one or more dienes are present in the polymer produced herein at up to 10 wt %, such as at 0.00001 to 1.0 wt %, such as 0.002 to 0.5 wt %, such as 0.003 to 0.2 wt %, based upon the total weight of the composition. In some embodiments, 500 ppm or less of diene is added to the polymerization, such as 400 ppm or less, such as 300 ppm or less. In other embodiments at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
Diene monomers include any hydrocarbon structure, such as C4 to C30, having at least two unsaturated bonds, where at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). The diene monomers can be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers). The diolefin monomers are linear di-vinyl monomers, such as those containing from 4 to 30 carbon atoms. Examples of dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g/mol). Cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
Polymerization processes of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be performed. (A useful homogeneous polymerization process is one where at least 90 wt % of the product is soluble in the reaction media.) A bulk homogeneous process can be used. (An example bulk process is one where monomer concentration in all feeds to the reactor is 70 volume % or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene). In at least one embodiment, the process is a slurry polymerization process. As used herein the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt % of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
Suitable diluents/solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C4-C10 alkanes, chlorobenzene, and aromatic and alkyl substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, the solvent is not aromatic, such that aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as 0 wt % based upon the weight of the solvents.
In at least one embodiment, the feed concentration of the monomers and comonomers for the polymerization is 60 vol % solvent or less, such as 40 vol % or less, such as 20 vol % or less, based on the total volume of the feedstream. The polymerization can be performed in a bulk process.
Polymerizations can be performed at any temperature and or pressure suitable to obtain the desired polymers, such as ethylene and or propylene polymers. Typical temperatures and or pressures include a temperature in the range of from 0° C. to 300° C., such as 20° C. to 200° C., such as 35° C. to 150° C., such as 40° C. to 120° C., such as 45° C. to 80° C., for example about 74° C., and at a pressure in the range of from 0.35 MPa to 10 MPa, such as 0.45 MPa to 6 MPa, such as 0.5 MPa to 4 MPa.
In a typical polymerization, the run time of the reaction is up to 300 minutes, such as in the range of from 5 to 250 minutes, such as 10 to 120 minutes.
In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), such as from 0.01 to 25 psig (0.07 to 172 kPa), such as 0.1 to 10 psig (0.7 to 70 kPa).
In at least one embodiment, the activity of the catalyst is from 30 kgP/mmolCat/hour to 20,000 kgP/mmolCat/hr, such as from 30 kgP/mmolCat/hr to 100 kgP/mmolCat/hr, alternatively from 150 kgP/mmolCat/hr to 900 kgP/mmolCat/hr, as alternatively from 900 kgP/mmolCat/hr to 4,000 kgP/mmolCat/hr, such as 1,000 kgP/mmolCat/hr or more.
In at least one embodiment, the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, such as 20% or more, such as 30% or more, such as 50% or more, such as 80% or more.
In at least one embodiment, a catalyst system of the present disclosure is capable of producing a polyolefin. In at least one embodiment, the polyolefin is a homopolymer of ethylene or propylene or a copolymer of ethylene such as a copolymer of ethylene having from 0.1 to 25 wt % (such as from 0.5 to 20 wt %, such as from 1 to 15 wt %, such as from 5 to 17 wt %) of ethylene with the remainder balance being one or more C3 to C20 olefin comonomers (such as C3 to C12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene). The polyolefin can be a copolymer of propylene such as a copolymer of propylene having from 0.1 to 25 wt % (such as from 0.5 to 20 wt %, such as from 1 to 15 wt %, such as from 3 to 10 wt %) of propylene and from 99.9 to 75 wt % of one or more of C2 or C4 to C20 olefin comonomer (such as ethylene or C4 to C12 alpha-olefin, such as butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene).
In at least one embodiment, a catalyst system of the present disclosure is capable of producing a polyolefin that is a copolymer of ethylene and a comonomer, where the copolymer has a comonomer content of from 0.1 to 25 wt % (such as from 1 to 15 wt %, such as from 5 to 15 wt %, such as from 8 to 15 wt %, alternatively from 1 wt % to 7 wt %, such as from 2 wt % to 6 wt %, such as from 2 wt % to 4 wt %). Comonomers can be one or more of a C3 to C20 olefin comonomer (such as C3 to C12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene). For example, a comonomer can be octene.
In at least one embodiment, a catalyst system of the present disclosure is capable of producing polyolefins, such as polypropylene or ethylene-alpha olefin copolymer, having an Mw from 10,000 to 1,500,000 g/mol, such as from 100,000 to 500,000 g/mol, such as from 150,000 to 400,000 g/mol, alternatively from 450,000 to 1,200,000 g/mol, such as from 800,000 to 1,200,000 g/mol, such as from 1,000,000 to 1,200,000 g/mol, alternatively from 10,000 to 100,000, such as from 50,000 to 100,000.
In at least one embodiment, a catalyst system of the present disclosure is capable of producing polyolefins, such as polypropylene or ethylene-alpha olefin copolymer, having an Mn from 1,000 to 2,000,000 g/mol, such as from 100,000 to 500,000 g/mol, such as from 300,000 to 500,000 g/mol, alternatively from 1,000,000 to 2,000,000 g/mol, such as from 1,500,000 to 2,000,000 g/mol, alternatively from 6,000 to 100,000, such as from 30,000 to 50,000.
In at least one embodiment, a catalyst system of the present disclosure is capable of producing polypropylene or ethylene-alpha olefin copolymer having an Mw/Mn value from 1 to 10, such as from 1.5 to 9, such as from 1.5 to 7, such as from 2 to 4, such as from 2 to 3, for example about 2.
In at least one embodiment, little or no scavenger is used in the process to produce polymer, such as propylene polymer. Scavenger (such as trialkyl aluminum) can be present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.
In at least one embodiment, the polymerization: 1) is conducted at temperatures of 0 to 300° C. (such as 25 to 150° C., such as 40 to 120° C., such as 70 to 110° C., such as 85 to 100° C.); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (such as 0.35 to 10 MPa, such as from 0.45 to 6 MPa, such as from 0.5 to 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, where aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as at 0 wt % based upon the weight of the solvents); and 4) the activity of the catalyst compound is at least 200 kgP/mmolCat/hr (such as at least 250 kgP/mmolCat/hr, such as at least 300 kgP/mmolCat/hr).
In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A “reaction zone” also referred to as a “polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone.
Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), hydrogen, or aluminum alkyls. Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AlR3, ZnR2 (where each R is, independently, a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, phenyl, hexyl, octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.
Generally, in a fluidized gas bed process used for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See, for example, U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are fully incorporated herein by reference.)
A slurry polymerization process generally operates between 1 to about 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5,068 kPa) or even greater and temperatures in the range of 0° C. to about 120° C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers, along with catalysts, are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent used in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, such as a branched alkane. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used, the process must be operated above the reaction diluent critical temperature and pressure. For example, a hexane or an isobutane medium is employed.
In at least one embodiment, a polymerization process is a particle form polymerization, or a slurry process, where the temperature is kept below the temperature at which the polymer goes into solution. Such technique is well known in the art, and described in for instance U.S. Pat. No. 3,248,179 which is fully incorporated herein by reference. The temperature in the particle form process can be from about 85° C. to about 110° C. Two example polymerization methods for the slurry process are those using a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Also, other examples of slurry processes are described in U.S. Pat. No. 4,613,484, which is herein fully incorporated by reference.
In another embodiment, the slurry process is carried out continuously in a loop reactor. The catalyst, as a slurry in isohexane or as a dry free flowing powder, is injected regularly to the reactor loop, which is itself filled with circulating slurry of growing polymer particles in a diluent of isohexane containing monomer and optional comonomer. Hydrogen, optionally, may be added as a molecular weight control. (In one embodiment hydrogen is added from 50 ppm to 500 ppm, such as from 100 ppm to 400 ppm, such as 150 ppm to 300 ppm.)
The reactor may be maintained at a pressure of 2,000 kPa to 5,000 kPa, such as from 3,620 kPa to 4,309 kPa, and at a temperature of from about 60° C. to about 120° C. depending on the desired polymer melting characteristics. Reaction heat is removed through the loop wall since much of the reactor is in the form of a double-jacketed pipe. The slurry is allowed to exit the reactor at regular intervals or continuously to a heated low pressure flash vessel, rotary dryer and a nitrogen purge column in sequence for removal of the isohexane diluent and all unreacted monomer and comonomer. The resulting hydrocarbon free powder is then compounded for use in various applications.
Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.
Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AlR3, ZnR2 (where each R is, independently, a C1-C8 hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof). Examples can include diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.
A solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are typically not turbid as described in in Oliveira, J. V. et al. (2000) “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v. 39, pp. 4627-4633. Generally solution polymerization involves polymerization in a continuous reactor in which the polymer formed and the starting monomer and catalyst materials supplied, are agitated to reduce or avoid concentration gradients and in which the monomer acts as a diluent or solvent or in which a hydrocarbon is used as a diluent or solvent. Suitable processes typically operate at temperatures from about 0° C. to about 250° C., such as about 10° C. to about 150° C., such as about 40° C. to about 140° C., such as about 50° C. to about 120° C., and at pressures of about 0.1 MPa or more, such as 2 MPa or more. The upper pressure limit is not critically constrained but typically can be about 200 MPa or less, such as 120 MPa or less. Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used. The purity, type, and amount of solvent can be optimized for the maximum catalyst productivity for a particular type of polymerization. The solvent can be also introduced as a catalyst carrier. The solvent can be introduced as a gas phase or as a liquid phase depending on the pressure and temperature. Advantageously, the solvent can be kept in the liquid phase and introduced as a liquid. Solvent can be introduced in the feed to the polymerization reactors.
The present disclosure also provides compositions of matter, such as polyolefins, which can be produced by the methods described herein.
In at least one embodiment, the polyolefin is a propylene homopolymer, a propylene copolymer, an ethylene homopolymer or an ethylene copolymer, such as propylene-ethylene and or ethylene-alphaolefin (such as C4 to C20) copolymer (such as an ethylene-hexene copolymer or an ethylene-octene copolymer). The polyolefin can have an Mw/Mn of greater than 1 to 4 (such as greater than 1 to 3).
In at least one embodiment, the polyolefin is a homopolymer of ethylene or propylene or a copolymer of ethylene such as a copolymer of ethylene having from 0.1 to 25 wt % (such as from 0.5 to 20 wt %, such as from 1 to 15 wt %, such as from 5 to 17 wt %) of ethylene with the remaining balance being one or more C3 to C20 olefin comonomers (such as C3 to C12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene). The polyolefin can be a copolymer of propylene such as a copolymer of propylene having from 0.1 to 25 wt % (such as from 0.5 to 20 wt %, such as from 1 to 15 wt %, such as from 3 to 10 wt %) of propylene and from 99.9 to 75 wt % of one or more of C2 or C4 to C20 olefin comonomer (such as ethylene or C4 to C12 alpha-olefin, such as butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene).
In at least one embodiment, a polyolefin is a copolymer of ethylene and a comonomer, where the copolymer has a comonomer content of from 0.1 to 25 wt % (such as from 1 to 15 wt %, such as from 5 to 15 wt %, such as from 8 to 15 wt %, alternatively from 1 wt % to 7 wt %, such as from 2 wt % to 6 wt %, such as from 2 wt % to 4 wt %). Comonomers can be one or more of a C3 to C20 olefin comonomer (such as C3 to C12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene). For example, a comonomer can be octene.
In at least one embodiment, a polyolefin, such as polypropylene or ethylene-alpha olefin copolymer, has an Mw from 10,000 to 1,500,000 g/mol, such as from 100,000 to 500,000 g/mol, such as from 150,000 to 400,000 g/mol, alternatively from 450,000 to 1,200,000 g/mol, such as from 800,000 to 1,200,000 g/mol, such as from 1,000,000 to 1,200,000 g/mol, alternatively from 10,000 to 100,000, such as from 50,000 to 100,000.
In at least one embodiment, a polyolefin, such as polypropylene or ethylene-alpha olefin copolymer, has an Mn from 1,000 to 2,000,000 g/mol, such as from 100,000 to 500,000 g/mol, such as from 300,000 to 500,000 g/mol, alternatively from 1,000,000 to 2,000,000 g/mol, such as from 1,500,000 to 2,000,000 g/mol, alternatively from 6,000 to 100,000, such as from 30,000 to 50,000.
In at least one embodiment, the polyolefin can be a polypropylene or ethylene-alpha olefin copolymer having an Mw/Mn value from 1 to 10, such as from 1.5 to 9, such as from 1.5 to 7, such as from 2 to 4, such as from 2 to 3, for example about 2.
In at least one embodiment, the polyolefin, such as a polypropylene or ethylene-alpha olefin copolymer, has a melt temperature (Tm) of from 100° C. to 150° C., such as 110° C. to 140° C., such as 110° C. to 130° C., such as 120° C. to 130° C., alternatively from 115° C. to 120° C., alternatively from 100° C. to 105° C.
In at least one embodiment, the polyolefin is an ethylene copolymer, and the comonomer is octene, at a comonomer content of from 0.1 to 25 wt % (such as from 1 to 15 wt %, such as from 5 to 15 wt %, such as from 8 to 15 wt %, alternatively from 1 wt % to 7 wt %, such as from 2 wt % to 6 wt %, such as from 2 wt % to 4 wt %).
Molecular Weight, Comonomer Composition and Long Chain Branching Determination by Polymer Char GPC-IR Hyphenated with Multiple Detectors (GPC-4D)
In the event of conflict between this GPC-4D procedure and the Rapid GPC procedure below, this GPC-4D procedure shall be used.
For purposes of the claims, and unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content (C2, C3, C6, etc.) and the branching index (g′) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10 μm Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 μm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate is 1.0 mL/min and the nominal injection volume is 200 μL. The whole system including transfer lines, columns, detectors are contained in an oven maintained at 145° C. Given amount of polymer sample is weighed and sealed in a standard vial with 80 μL flow marker (heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 mL added TCB solvent. The polymer is dissolved at 160° C. with continuous shaking for about 1 hour for most PE samples or 2 hour for PP samples. The TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145° C. The sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
The concentration (c), at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal intensity (I), using the following equation:
c=βI
where β is the mass constant determined with PE or PP standards. The mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.
The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M. The MW at each elution volume is calculated with following equation.
where the variables with subscript “PS” stands for polystyrene while those without a subscript are for the test samples. In this method, aPS=0.67 and KPS=0.000175 while a and K are calculated as described in the published in literature (Sun, T. et al. (2001) “Effect of Short Chain Branching on the Coil Dimensions of Polyolefins in Dilute Solutions,” Macromolecules, v. 34(19), pp. 6812-6820), except that for purposes of this invention and claims thereto, α=0.695 and K=0.000579 for polyethylene, α=0.705 and K=0.0002288 for polypropylene, α=0.695+(0.01*(wt. fraction propylene)) and K=0.000579−(0.0003502*(wt. fraction propylene)) for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.695 and K=0.000181 for linear butene polymers, α is 0.695 and K is 0.000579*(1−0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, α is 0.695 and K is 0.000579*(1−0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and α is 0.695 and K is 0.000579*(1−0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm3, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted.
The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR.
The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M. B. Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971):
Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient. P(θ) is the form factor for a monodisperse random coil, and Ko is the optical constant for the system:
where NA is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145° C. and λ=665 nm.
A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ηS, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation:
[η]=ηS/c
where c is concentration and was determined from the IR5 broadband channel output. The viscosity MW at each point is calculated from the below equation:
M=K
PS
M
α
+1/[η].
The branching index (g′vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]avg, of the sample is calculated by:
where the summations are over the chromatographic slices, i, between the integration limits. The branching index g′vis is defined as:
Mv is the viscosity-average molecular weight based on molecular weights determined by LS analysis. The K/a are for the reference linear polymers are as described above.
All the concentration is expressed in g/cm3, molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g unless otherwise noted.
All molecular weights are reported in g/mol unless otherwise noted.
Differential Scanning calorimetry (DSC-Procedure-2). Melt Temperature, Tm, is measured by differential scanning calorimetry (“DSC”) using a DSCQ200 unit. The sample is first equilibrated at 25° C. and subsequently heated to 220° C. using a heating rate of 10° C./min (first heat). The sample is held at 220° C. for 3 minutes. The sample is subsequently cooled down to −100° C. with a constant cooling rate of 10° C./min (first cool). The sample is equilibrated at −100° C. before being heated to 220° C. at a constant heating rate of 10° C./min (second heat). The exothermic peak of crystallization (first cool) is analyzed using the TA Universal Analysis software and the corresponding to 10° C./min cooling rate is determined. The endothermic peak of melting (second heat) is also analyzed using the TA Universal Analysis software and the peak melt temperature (Tm) corresponding to 10° C./min heating rate is determined. In the event of conflict between the DSC Procedure-1 and DSC procedure-2, DSC procedure-2 is used.
In another embodiment, the polymer (such as the polyethylene or polypropylene) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and or butene, and or hexene, polybutene, ethylene vinyl acetate, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and or polyisobutylene.
In at least one embodiment, the polymer (such as polyethylene or polypropylene) is present in the above blends, at from 10 to 99 wt %, based upon the weight of the polymers in the blend, such as 20 to 95 wt %, such as at least 30 to 90 wt %, such as at least 40 to 90 wt %, such as at least 50 to 90 wt %, such as at least 60 to 90 wt %, such as at least 70 to 90 wt %.
The blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
The blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; and talc.
One or more of the foregoing polymers, such as the foregoing polyethylenes, polypropylenes, or blends thereof, may be used in a variety of end-use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, where the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented in the transverse and or longitudinal directions to the same or different extents. The uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. Typically the films are oriented in the Machine Direction (MD) at a ratio of up to 15, such as between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as 7 to 9. However, in at least one embodiment the film is oriented to the same extent in both the MD and TD directions.
The films may vary in thickness depending on the intended application; however, films of a thickness from 1 μm to 50 μm are usually suitable. Films intended for packaging are usually from 10 μm to 50 μm thick. The thickness of the sealing layer is typically 0.2 μm to 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.
In at least one embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In at least one embodiment, one or both of the surface layers is modified by corona treatment.
The present disclosure provides, among others, the following aspects, each of which may be considered as optionally including any alternate aspects.
Clause 1. A catalyst system comprising:
a catalyst compound represented by Formula (CI) or (CII):
wherein:
M is a Group 3, 4, 5 or 6 transition metal;
X1 and X2 are independently selected from the group consisting of a C1 to C20 hydrocarbyl, a C1 to C20 substituted hydrocarbyl, a heteroatom, and a heteroatom containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure; wherein if M is trivalent then X2 is not present;
each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 is independently selected from the group consisting of hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom, and a heteroatom containing group, or two or more of R1 to R14 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure;
Y is a divalent C1 to C20 hydrocarbyl or substituted divalent C1 to C20 hydrocarbyl; and
Q is a neutral donor group; and
an activator represented by Formula (AI):
[R1R2R3EH]d+[Mk+Qn]d− (AI)
wherein:
E is nitrogen or phosphorous;
d is 1, 2 or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n−k=d;
each of R1, R2, and R3 is independently hydrogen, a C1-C40 alkyl, or a C5-C50-aryl, wherein each of R1, R2, and R3 is independently unsubstituted or substituted; wherein R1, R2, and R3 together comprise 15 or more carbon atoms;
M is an element selected from group 13 of the Periodic Table of the Elements; and
each Q is independently selected from the group consisting of a hydrogen, bridged or unbridged dialkylamido, halide, alkoxy, substituted alkoxy, aryloxy, substituted aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl.
Clause 2. The catalyst system of Clause 1, wherein the activator compound of Formula (AI) is represented by Formula (I):
[R1R2R3EH]+[BR4R5R6R7]− (I)
wherein:
E is nitrogen or phosphorous;
each of R1, R2, and R3 is independently C1-C40 branched or linear alkyl or C5-C50-aryl, wherein each of R1, R2, and R3 is independently unsubstituted or substituted with at least one of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl or, in the case of the C5-C50-aryl, C1-C50 alkyl; wherein R1, R2, and R3 together comprise 15 or more carbon atoms; and
each of R4, R5, R6, and R7 is naphthyl, wherein at least one of R4, R5, R6, and R7 is substituted with from one to seven fluorine atoms.
Clause 3. The catalyst system of Clauses 1 or 2, wherein: at least one of R1, R2, and R3 of Formula (AI) or (I) is independently a C3-C40 alkyl which is unsubstituted or substituted with at least one of halide, C5-C15 aryl, C6-C25 arylalkyl, and C6-C25 alkylaryl.
Clause 4. The catalyst system of Clauses 1 or 2, wherein, for the activator of Formula (AI) or (I): R1 is methyl; R2 is C10-C42 aryl; R3 is C1-C40 branched alkyl; wherein each of R2 and R3 is independently unsubstituted or substituted with at least one of halide, C5-C15 aryl, C6-C25 arylalkyl, C6-C25 alkylaryl, and in the case of the C10 to C42 aryl, C1-C10 alkyl; and R2 and R3 together comprise 20 or more carbon atoms.
Clause 5. The catalyst system of Clauses 1, 2, 3, or 4 wherein, for the activator of Formula (AI) or (I), E is nitrogen.
Clause 6. The catalyst system of any of Clauses 1, 2, 3, 4 or 5, wherein, for the activator of Formula (I), R4, R5, R6, and R7 are perfluoroaryl.
Clause 7. The catalyst system of any of Clauses 1, 2, 3, 4, or 5, wherein, for the activator of Formula (I), each of R4, R5, R6, and R7 is substituted with from one to seven fluorine atoms, preferably seven fluorine atoms.
Clause 8. The catalyst system of any of Clauses 1, 2, 3, 4, 5, 6, or 7, wherein R1, R2, and R3 together comprise 21 or more carbon atoms.
Clause 9. The catalyst system of any of Clauses 1 to 7, wherein all Q in Formula (AI) are not perfluorophenyl, and each of R4, R5, R6, and R7 in Formula (I) are not perfluorophenyl.
Clause 10. The catalyst system of Clause 2, wherein at least one of R1, R2, and R3 of Formula (AI) or (I) is an alkyl group represented by the Formula:
wherein each of RA and RE are independently selected from the group consisting of H, a C1-C40 linear or branched alkyl, and C5-C50-aryl, wherein each of RA and RE is optionally substituted with one or more of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl and, in the case of the C5-C50-aryl, C1-C50 alkyl, provided that in at least one (RA—C—RE) group, one or both of RA and RE is not H; and
RC, RB and RD are hydrogen; and Q is an integer from 5 to 40.
Clause 11. The catalyst system of any of the above Clauses wherein one, two or three of R1, R2 and R3 are independently represented by the Formula (IV):
wherein each of R17, R18, R19, R20, and R21 is independently selected from the group consisting of hydrogen, C1-C40 hydrocarbyl, C1-C40 substituted hydrocarbyl, a heteroatom, a heteroatom-containing group, or is represented by Formula (BIII), provided that at least one of R17, R18, R19, R20, and R21 is not hydrogen, wherein Formula (BIII) is:
wherein each of RA and RE is independently selected from the group consisting of H, a C1-C40 linear or branched alkyl, and C5-C50-aryl, wherein each of RA and RE is optionally substituted with one or more groups selected from the group consisting of halide, C5-C50 aryl, C6-C35 arylalkyl, C6-C35 alkylaryl, and, in the case of the C5-C50-aryl, C1-C50 alkyl, provided that in at least one (RA—C—RE) group, one or both of RA and RE is not H;
RC, RB and RD are hydrogen; and
Q is an integer from 5 to 40.
Clause 12. The catalyst system of Clauses 1 or 2, wherein R1 is C1-C10 alkyl and each of R2 and R3 is independently a linear or branched C10-C40 alkyl.
Clause 13. The catalyst system of Clauses 1 or 2, wherein R1 is C5-C22-aryl and each of R2 and R3 is independently a linear or branched C1-C40 alkyl, wherein R1 is unsubstituted or substituted with at least one C1-C10 alkyl.
Clause 14. The catalyst system of Clause 13, wherein R1 is phenyl, R2 is methyl, and R3 is a C10-C40 branched alkyl.
Clause 15. The catalyst system of any of Clauses 1 to 14, wherein the activator compound has a solubility of more than 10 mM at 25° C. (stirred 2 hours) in methylcyclohexane and or a solubility of more than 1 mM at 25° C. (stirred 2 hours) in isohexane.
Clause 16. The catalyst system of any of Clauses 1 to 15, wherein the catalyst system has a solubility of more than 20 mM at 25° C. (stirred 2 hours) in methylcyclohexane and or a solubility of more than 10 mM at 25° C. (stirred 2 hours) in isohexane.
Clause 17. The catalyst system of any of Clauses 1 to 16, wherein the catalyst compound is the catalyst compound represented by Formula (CI) and is further represented by the Formula (IV) or (V):
wherein:
M is a Group 3, 4, 5 or 6 transition metal;
X1 and X2 are independently selected from the group consisting of a C1 to C20 hydrocarbyl, a C1 to C20 substituted hydrocarbyl, a heteroatom, and a heteroatom containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure; wherein if M is trivalent then X2 is not present;
Y is a divalent C1 to C20 hydrocarbyl or substituted divalent C1 to C20 hydrocarbyl;
Q* is a group 15 or 16 atom;
z is 0 or 1;
J* is CR′″ or N;
G* is CR′″ or N; and
each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R′″, and R″ is independently selected from the group consisting of hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom, and a heteroatom containing group, or two or more of R1 to R28, R′″, and R″ may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
Clause 18. The catalyst system of Clause 17, wherein, for the catalyst compound of Formula (IV) or (V), each of R″, R′″, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, R27, and R28 is selected from the group consisting of hydrogen, halide, a C1-C20 hydrocarbyl, a substituted C1 to C20 hydrocarbyl, or two or more of R″, R′″, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, R27, and R28 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
Clause 19. The catalyst system of Clause 18, wherein, for the catalyst compound of formula (IV) or (V), one or more of R″, R′″, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 R24, R25, R26, R27, and R28 is independently selected from the group consisting of 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4-dimethylaminophenyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, trifluoromethyl, fluoromethyl, trichloromethyl, chloromethyl, mesityl, methylthio, phenylthio, (trimethylsilyl)methyl, and (triphenylsilyl)methyl).
Clause 20. The catalyst system of any of Clauses 17 to 19, wherein, for the catalyst compound of Formula (IV) or (V), each of R1, R2, R3, R4, R5, R10, R14, R15, R16, R17, and R18 is independently selected from the group consisting of hydrogen, a C1-C20 hydrocarbyl, and a substituted C1 to C20 hydrocarbyl, or two or more of R1, R2, R3, R4, R5, R10, R14, R15, R16, R17, and R18 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
Clause 21. The catalyst system of any of Clauses 17 to 20, wherein, for the catalyst compound of Formula (IV) or (V), R18 is independently selected from the group consisting of carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, substituted fluorenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, and substituted phenanthryl.
Clause 22. The catalyst system of any of Clauses 17 to 21, wherein, for the catalyst compound of Formula (IV) or (V), each of G* and J* is CR′″ and each R′″ is independently a C1-C20 hydrocarbyl.
Clause 23. The catalyst system of any of Clauses 17 to 21, wherein, for the catalyst compound of Formula (IV) or (V), each of G* and J* is N.
Clause 24. The catalyst system of any of Clauses 1 to 23, wherein, for the catalyst represented by Formula (CI), (IV), or (V), M is hafnium, titanium, or zirconium.
Clause 25. The catalyst system of any of Clauses 1 to 24, wherein, for the catalyst represented by Formula (CI), (IV), or (V), each of X1 and X2 is independently selected from the group consisting of a C1-C20 hydrocarbyl, hydride, amide, alkoxyl, sulfide, phosphide, halide, amino, phosphine, and ether.
Clause 26. The catalyst system of Clause 25, wherein, for the catalyst represented by Formula (CI), (IV), or (V), each of X1 and X2 is benzyl.
Clause 27. The catalyst system of any of claims 1 to 26, wherein, for the catalyst represented by Formula (CI), (IV), or (V), Y is —CH2CH2— or —CH2CH2CH2—.
Clause 28. The catalyst system of any of claims 1 to 27, wherein the catalyst compound is the catalyst compound represented by Formula (CI) and is selected from the group consisting of:
Clause 29. The catalyst system of Clause 28, wherein the catalyst compound is selected from the group consisting of:
Clause 30. The catalyst system of any of Clauses 1 to 16, wherein the catalyst compound is the catalyst compound represented by Formula (CII) and is further represented by the Formula (VI) or (VII):
wherein:
M is a Group 3, 4, 5 or 6 transition metal;
X1 and X2 are independently selected from the group consisting of a C1 to C20 hydrocarbyl, a C1 to C20 substituted hydrocarbyl, a heteroatom, and a heteroatom containing group, or X1 and X2 join together to form a C4 to C62 cyclic or polycyclic ring structure; wherein if M is trivalent then X2 is not present;
Y is a divalent C1 to C20 hydrocarbyl or substituted divalent C1 to C20 hydrocarbyl;
Q* is a group 15 or 16 atom;
z is 0 or 1;
J* is CR′″ or N;
G* is CR′″ or N; and
each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R′″, R*, and R″ is independently selected from the group consisting of hydrogen, a C1-C40 hydrocarbyl, a substituted C1-C40 hydrocarbyl, a heteroatom, and a heteroatom containing group, or two or more of R1 to R27, R′″, R*, and R″ may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
Clause 31. The catalyst system of Clause 30, wherein, for the catalyst compound of Formula (VI) or (VII), each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R′″, R*, and R″ is selected from the group consisting of hydrogen, halide, a C1-C20 hydrocarbyl, and a substituted C1 to C20 hydrocarbyl, or two or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R′″, R*, and R″ may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
Clause 32. The catalyst system of Clause 31, wherein, for the catalyst compound of Formula (VI) or (VII), one or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R′″, R*, and R″ is independently selected from the group consisting of 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4-dimethylaminophenyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, trifluoromethyl, fluoromethyl, trichloromethyl, chloromethyl, mesityl, methylthio, phenylthio, (trimethylsilyl)methyl, and (triphenylsilyl)methyl).
Clause 33. The catalyst system of any of Clauses 30 to 32, wherein, for the catalyst compound of Formula (VI) or (VII), each of R3, R4, R5, R15, R16, R17, and R18 is independently selected from the group consisting of hydrogen, a C1-C20 hydrocarbyl, and a substituted C1 to C20 hydrocarbyl, or two or more of R3, R4, R5, R15, R16, R17, and R18 may independently join together to form a C4 to C62 cyclic or polycyclic ring structure.
Clause 34. The catalyst system of any of Clauses 30 to 33, wherein, for the catalyst compound of Formula (VI) or (VII), R18 is selected from the group consisting of carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, substituted fluorenyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, and substituted phenanthryl.
Clause 35. The catalyst system of any of Clauses 30 to 34, wherein, for the catalyst compound of Formula (VI) or (VII), each of G* and J* is CR′″ and each R′″ is independently a C1-C20 hydrocarbyl.
Clause 36. The catalyst system of any of Clauses 30 to 34, wherein, for the catalyst compound of Formula (VI) or (VII), each of G* and J* is N.
Clause 37. The catalyst system of any of Clauses 1 to 16 or 30 to 36, wherein, for the catalyst represented by Formula (CII), (VI), or (VII), M is hafnium, titanium, or zirconium.
Clause 38. The catalyst system of any of Clauses 1 to 16 or 30 to 36, wherein, for the catalyst represented by Formula (CII), (VI), or (VII), each of X1 and X2 is independently selected from the group consisting of a C1-C20 hydrocarbyl, hydride, amide, alkoxyl, sulfide, phosphide, halide, amino, phosphine, and ether.
Clause 39. The catalyst system of Clause 38, wherein, for the catalyst represented by Formula (CII), (VI), or (VII), each of X1 and X2 is benzyl.
Clause 40. The catalyst system of any of Clauses 1 to 16 or 30 to 39, wherein, for the catalyst represented by Formula (CII), (VI), or (VII), Y is —CH2CH2— or —CH2CH2CH2—.
Clause 41. The catalyst system of any of Clauses 30 to 40, wherein z is 0.
Clause 42. The catalyst system of any of Clauses 30 to 41, wherein Q* is an amine group.
Clause 43. The catalyst system of any of Clauses 1 to 16 or 30 to 42, wherein the catalyst compound is the catalyst compound represented by Formula (CII) and is selected from the group consisting of:
44. The catalyst system of Clause 43, wherein the catalyst compound is selected from the group consisting of:
Clause 45. The catalyst system of any of Clauses 1 to 44, further comprising a support material, preferably selected from Al2O3, ZrO2, SiO2, SiO2/Al2O3, SiO2/TiO2, silica clay, silicon oxide/clay, or mixtures thereof.
Clause 46. A method of polymerizing olefins to produce at least one polyolefin, the method comprising contacting at least one olefin with the catalyst system of any of Clauses 1 to 45, and obtaining a polyolefin.
Clause 47. The method of Clause 46, wherein two or more different olefins (e.g., the at least one olefin and a second olefin different from the at least one olefin) are contacted with the catalyst system.
Clause 48. The method of Clause 47, wherein the two or more olefins are ethylene and octene.
Clause 49. The method of any of claims 46 to 48, wherein the two or more olefins further comprise a diene.
Clause 50. The method of any of Clauses 46 to 49, wherein the method is performed in the gas phase or slurry phase.
Clause 51. The method of any of Clauses 46 to 49, wherein the method is performed in the solution phase.
Clause 52. The method of any of Clauses 46 to 51, wherein the polyolefin has a comonomer content of about 8 wt % or greater, a number average molecular weight value of 100,000 g/mol or greater, and a melt temperature of about 95° C. or greater.
Clause 53. The method of any of Clauses 46 to 51, wherein the polyolefin has a comonomer content of less than 8 wt %, a number average molecular weight value of 100,000 g/mol or greater, and a melt temperature of about 110° C. or greater.
Clause 54. The method of any of Clauses 46 to 51, wherein the polyolefin has a number average molecular weight value of less than 100,000 g/mol and a melt temperature of about 110° C. or greater.
Clause 55. The method of any of Clauses 46 to 51, wherein the polyolefin has a number average molecular weight value of 100,000 g/mol or greater and a melt temperature of about 110° C. or greater.
Lithium tetrakis(pentafluorophenyl)borate etherate (Li—BF20) was purchased from Boulder Scientific. N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate (DMAH-BF20) was purchased from Grace Davison and converted to sodium tetrakis(heptafluoronaphthalen-2-yl)borate (Na—BF28) by reaction with sodium hydrogen in toluene. N,N-dimethylanilinium tetrakis(heptafluoronaphthalen-2-yl)borate (DMAH-BF28) were purchased from Grace Davison. All other reagents were purchased from Sigma-Aldrich and used as received. All anhydrous solvents were purchased from Sigma-Aldrich. Solvents (Sigma-Aldrich) were sparged with nitrogen and stored over molecular sieves.
BF20 is tetrakis(pentafluorophenyl)borate.
BF28 is tetrakis(heptafluoronaphthalen-2-yl)borate.
1H NMR for Compound Characterization: Chemical structures are determined by 1H NMR. 1H NMR data are collected at room temperature (e.g., 23° C.) in a 5 mm probe. The NMR measurements were recorded on a 400 MHz or 500 MHz Bruker spectrometer with chemical shifts referenced to residual solvent peaks (CDCl3: 7.27 ppm for 41, 77.23 ppm for 13C).
Borate anions and ammonium cations used as activator components are shown in Scheme 1.
N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate (DMAH-BF20) was purchased from Albemarle. Sodium tetrakis(heptafluoronaphthalen-2-yl)borate (Na—BF28) and N,N-dimethylanilinium tetrakis(heptafluoronaphthalen-2-yl)borate (DMAH-BF28) were purchased from Grace Davison. Methyl aluminoxane (MAO) was purchased from Albemarle.
N-methyl-N-octadecylaniline: N-methylaniline (10.2 g, 96 mmol), bromooctadecane (38.4 g, 115 mmol), and triethylamine (19.9 mL, 144 mmol) were dissolved in 400 mL of DMSO and heated overnight at 100° C. The solution was diluted with water and extracted three times with ethyl acetate. The organic fractions were combined, rinsed with brine, dried with MgSO4 and concentrated to yield a yellow oily solid. The product was purified by silica gel chromatography (2% ethyl acetate/isohexane) and isolated as a white solid. 1H NMR (400 MHz, CDCl3, δ): 0.88 (t, J=8.0 Hz, 3H), 1.25 (m, 32H), 1.56 (m, 2H), 2.92 (s, 3H), 3.29 (m, 2H), 6.68 (m, 3H), 7.22 (m, 2H).
4-(methyl(octadecyl)amino)benzaldehyde: To DMF (0.34 mL, 4.4 mmol) cooled to 0° C., was added phosphoryl chloride (0.49 mL, 5.3 mmol) dropwise. The reaction was warmed to room temperature over 30 minutes, turning bright red. It was cooled to 0° C. and a solution of the above alkylated was aniline (1.6 g, 4.4 mmol) in 20 mL of THF added. After stirring for 20 minutes, the reaction was heated at 80° C. for 2 hours. The cooled solution was quenched by dropwise addition of 20 mL of 1M KOH. The mixture was extracted with three portions of 15 mL EtOAc. The organic fractions were combined, rinsed with brine, dried with MgSO4, and concentrated. The orange residue was purified by silica gel chromatography (2% ethyl acetate/isohexane) and isolated as a pale pink crystalline solid in 70% yield. 1H NMR (400 MHz, CDCl3, δ): 0.88 (t, J=7.0 Hz, 3H), 1.25 (m, 30H), 1.61 (m, 2H), 3.04 (s, 3H), 3.39 (t, J=8.0 Hz, 2H), 6.69 (d, J=7.0 Hz, 2H), 7.72 (d, J=7.0 Hz, 2H), 9.72 (s, 1H).
(4-(methyl(octadecyl)amino)phenyl)nonadecanol: Bromooctadecylmagnesium chloride was prepared from bromooctadecane (1.03 g, 2.5 mmol) and magnesium turnings (88 mg, 3.5 mmol) in THF. It was filtered into a solution of the above aminobenzaldehyde (1.0 g, 2.5 mmol) in THF and stirred at ambient temperature overnight. The reaction was quenched with water and extracted with ethyl acetate. Organic fractions were combined, rinsed with brine, dried with MgSO4, filtered and concentrated. The product was used without further purification. 1H NMR (400 MHz, CDCl3, δ): 0.88 (m, 6H), 1.24-1.80 (m, 67H), 2.92 (s, 3H), 3.28 (t, J=8.0 Hz, 2H), 4.55 (br s, 1H), 6.66 (d, J=8.0 Hz, 2H), 7.20 (d, J=8.0 Hz, 2H).
N-methyl-4-nonadecyl-N-octadecylaniline (NOMA): To the above alcohol (1.6 g, 2.5 mmol) dissolved in 50 mL of THF was added 27 mg of 10% Pd/C and 0.5 mL conc. HCl. The reaction was stirred under an atmosphere of hydrogen for over 48 h. It was filtered through Celite, concentrated, and purified by silica gel chromatography (2% ethyl acetate/isohexane). 1H NMR (400 MHz, CDCl3, δ): 0.89 (m, 6H), 1.27 (m, 62H), 1.56 (m, 4H), 2.50 (m, 2H), 2.90 (s, 3H), 3.26 (m, 2H), 6.65 (m, 2H), 7.04 (m, 2H).
N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate (NOMAH-BF28): N-methylaniline (15 g, 24 mmol) was dissolved in 250 mL of hexane in a 500 mL round bottom flask. A 2 M solution of HCl in ether (12 mL, 24 mmol) was added slowly, causing a white precipitate to appear, and the mixture was allowed to stir overnight. The solid was collected by gravity filtration, washed with hexane, and dried under vacuum. The HCl salt (13.1 g, 20 mmol) and Na—BF28 (20.7 g, 20 mmol) was heated at reflux for 1.5 hours in 100 mL of cyclohexane. Once cooled to ambient, the mixture was filtered and concentrated to a brown oil. The oil was redissolved in hexane and filtered through Celite. The filtrate was concentrated to give the product as a thick oil in 57% yield.
N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis(pentafluorophenyl)borate (NOMAH-BF20): Made from N-methyl-4-nonadecyl-N-octadecylanilinum chloride (1.50 g, 2.26 mmol) and Li—BF20 (1.72 g, 2.26 mmol) in a similar procedure as described above. The product was obtained as a colorless oil in 61% yield.
N,N-dioctadecyl-4-methylaniline (DOdT): p-Toluidine (1.5 g, 14.0 mmol), bromooctadecane (10.2 g, 31 mmol), potassium carbonate (5.8 g, 42 mmol), and a catalytic amount of tetrabutylammonium iodide (approx. 100 mg) were combined in 150 mL of DMF and heated at 120 for over 72 hours. After cooling, the solution was diluted with water and extracted with three portions of ethyl acetate. Combined organic fractions were washed twice with water and once with brine, then dried (MgSO4), filtered, and concentrated to a yellow solid. The dialkylated product was purified by silica gel chromatography using isohexane as eluent. It was obtained as a white powder in 20% yield. 41 NMR (400 MHz, CDCl3, δ): 0.90 (t, J=6.7 Hz, 6H), 1.25 (m, 64H), 2.23 (s, 3H), 3.20 (m, 4H), 6.56 (d, J=8.6 Hz, 2H), 7.01 (d, J=8.4 Hz, 2H).
4-methyl-N,N-dioctadecylbenzenaminium tetrakis(pentafluorophenyl)borate (DOdTH-BF20): Dioctadecyl toluidine (1.68 g, 3 mmol) was dissolved in 150 mL of hexane. A 2 M ethereal solution of HCl (1.3 mL, 3 mmol) was added slowly, causing a white precipitate to form. After stirring for 30 minutes, the white solid was collected, washed with fresh hexane, and dried under vacuum. A slurry of dioctadecyl toluidine HCl salt (500 mg, 0.77 mmol) and Li—BF20 (959 mg, 0.77 mmol) in 100 mL of cyclohexane was heated at reflux for 1.5 hours. Once cooled to ambient temperature, the mixture was filtered. The filtrate was concentrated, redissolved in dichloromethane, filtered through Celite, and then concentrated to give the product as a white powder in quantitative yield. 1H NMR (400 MHz, CDCl3, δ): 0.87 (d, J=6.9 Hz, 6H), 1.20 (m, 64H), 2.48 (s, 3H), 3.49 (m, 4H), 7.00 (d, J=8.6 Hz, 2H), 7.40 (d, J=8.1 Hz, 2H).
4-methyl-N,N-dioctadecylbenzenaminium-tetrakis(perfluoronaphthalen-2-yl)borate (DOdTH-BF28): A slurry of the above toluidine HCl salt (500 mg, 0.77 mmol) described above and Na—BF28 (847 mg, 0.77 mmol) in 100 mL of cyclohexane was heated at reflux for 1.5 hours. Once cooled to ambient temperature, the mixture was filtered. The filtrate was concentrated, redissolved in dichloromethane, filtered through Celite, and then concentrated to give the product as a clear brownish oil. 1H NMR (400 MHz, CDCl3, δ): 0.86 (d, J=7.0 Hz, 6H), 1.16 (m, 60H), 1.67 (m, 4H), 2.39 (s, 3H), 3.31 (m, 2H), 3.45 (m, 2H), 7.28 (s, 4H).
Di(hydrogenated tallow)methylamine-BF28 (M2HTH-BF28): Di(hydrogenated tallow)methylamine (M2HT) (10.0 g, 18.66 mmol) was dissolved in 600 mL of hexane. A 2 M ethereal solution of HCl (11.2 mL, 22.4 mmol) was added slowly, causing a white precipitate to form. After stirring for 1 hour, the white solid was collected, washed with fresh hexane, and dried under vacuum to give the amine-HCl salt in 65% yield. The salt (500 mg, 0.873 mmol) was combined with Na—BF28 (914 mg, 873 mmol) and suspended in 100 mL of cyclohexane. The mixture was heated at reflux for 1.5 hours, then cooled to ambient temperature and filtered. The filtrate was concentrated under vacuum to give a viscous yellow oil in 61% yield. 1H NMR (500 MHz, CDCl3, δ): 0.88 (d, J=6.6 Hz, 6H), 1.26 (m, 60H), 1.61 (m, 4H), 2.87 (d, J=4.3 Hz, 3H), 3.03 (m, 2H), 3.16 (m, 2H), 5.44 (br s, 1H).
Di(hydrogenated tallow)methylamine-BF20 (M2HTH-BF20): The M2HT-HCl salt (1.1 g, 1.92 mmol) described above, was suspended in 100 mL of cyclohexane and combined with a suspension of Li—BF20 (1.4 g, 1.92 mmol) in 100 mL of cyclohexane. The mixture was heated at reflux for 1.5 hours, then cooled to ambient and filtered. The filtrate was concentrated, redissolved in isohexane, filtered through Celite, and then concentrated to a viscous white oil to give the product in 67% yield. 1H NMR (500 MHz, CDCl3, δ): 0.85 (m, 6H), 1.22 (m, 60H), 1.61 (m, 4H), 2.85 (m, 3H), 3.01 (m, 2H), 3.13 (m, 2H).
Catalysts 1-4 are Represented by the Following Structures:
Catalyst 5 is Represented by the Structure:
Catalyst 25 is Represented by the Structure:
Catalyst 26 is Represented by the Structure:
Catalyst 27 is Represented by the Structure:
The catalysts used were synthesized according to conventional procedures known in the art, such as those described in WO 2016/153682 or Organometallics (2001) v. 20, pp. 3017-3028 and Organometallics (2002) v. 21, pp. 662-670.
Solvents, polymerization-grade toluene, and isohexane were supplied by ExxonMobil Chemical Company and purified by passing through a series of columns: two 500 cc Oxyclear cylinders in series from Labclear (Oakland, Calif.), followed by two 500 cc columns in series packed with dried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dried 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company). 1-octene (C8) (98%, Aldrich Chemical Company) were dried by stirring over NaK overnight followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).
Polymerization-grade ethylene (C2) was used and further purified by passing the gas through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company) and a 500 cc column packed with dried 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company).
Solutions of the metal complexes and activators were prepared in a drybox using toluene or methylcyclohexane. Concentrations were typically 0.2 mmol/L. Tri-n-octylaluminum (TNOAL, neat, AkzoNobel) was typically used as a scavenger. Concentration of the TNOAL solution in toluene ranged from 0.5 to 2.0 mmol/L.
Polymerizations were carried out in a parallel pressure reactor, as generally described in U.S. Pat. Nos. 6,306,658; 6,455,316; 6,489,168; WO 00/09255; and Murphy, V. et al. (2003) “A Fully Integrated High-Throughput Screening Methodology for the Discovery of New Polyolefin Catalysts: Discovery of a New Class of High Temperature Single-Site Group (IV) Copolymerization Catalysts,” J. Am. Chem. Soc., v. 125, pp. 4306-4317, each of which is fully incorporated herein by reference. The experiments were conducted in an inert atmosphere (N2) drybox using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor=23.5 mL for C2 and C2/C8; 22.5 mL for C3 runs), septum inlets, regulated supply of nitrogen, ethylene and propylene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves were prepared by purging with dry nitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5 hours. Although the specific quantities, temperatures, solvents, reactants, reactant ratios, pressures, and other variables are frequently changed from one polymerization run to the next, the following describes a typical polymerization performed in a parallel pressure reactor.
Catalyst systems dissolved in solution were used in the polymerization examples below, unless specified otherwise.
Ethylene-Octene Copolymerization (EO). A pre-weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels. The reactor was then closed and purged with ethylene. Each vessel was charged with enough solvent (typically isohexane) to bring the total reaction volume, including the subsequent additions, to the desired volume, typically 5 mL 1-octene, if required, was injected into the reaction vessel and the reactor was heated to the set temperature and pressurized to the predetermined pressure of ethylene, while stirring at 800 rpm. The aluminum compound (such as tri-n-octylaluminum) in toluene was then injected as scavenger followed by addition of the activator solution (typically 1.0-1.2 molar equivalents).
The catalyst (and activator solutions for the runs below) were all prepared in toluene. The catalyst solution (typically 0.020-0.080 μmol of metal complex) was injected into the reaction vessel and the polymerization was allowed to proceed until a pre-determined amount of ethylene (quench value typically 20 psi) had been used up by the reaction. Alternatively, the reaction may be allowed to proceed for a set amount of time (maximum reaction time typically 30 minutes). Ethylene was added continuously (through the use of computer controlled solenoid valves) to the autoclaves during polymerization to maintain reactor gauge pressure (P setpt, +/−2 psig) and the reactor temperature (T) was monitored and typically maintained within +/−1° C. The reaction was quenched by pressurizing the vessel with compressed air. After the reactor was vented and cooled, the glass vial insert containing the polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure. The vial was then weighed to determine the yield of the polymer product. The resultant polymer was analyzed by Rapid GPC to determine the molecular weight, by FT-IR to determine percent octene incorporation, and by DSC to determine melting point (Tm).
Polymer Characterization. Polymer sample solutions were prepared by dissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99% from Aldrich) at 165° C. in a shaker oven for approximately 3 hours. The typical concentration of polymer in solution was between 0.1 to 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB.
To determine various molecular weight related values by GPC, high temperature size exclusion chromatography was performed using an automated “Rapid GPC” system as generally described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. This apparatus has a series of three 30 cm×7.5 mm linear columns, each containing PLgel 10 μm, Mix B. The GPC system was calibrated using polystyrene standards ranging from 580 to 3,390,000 g/mol. The system was operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of 165° C. 1,2,4-trichlorobenzene was used as the eluent. The polymer samples were dissolved in 1,2,4-trichlorobenzene at a concentration of 0.28 mg/mL and 400 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using an evaporative light scattering detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected, unless indicated otherwise.
RAPID DSC: Differential Scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point (Tm) of the polymers. Samples were pre-annealed at 220° C. for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C./min and then cooled at a rate of 50° C./min. Melting points were collected during the heating period.
The weight percent of ethylene incorporated in polymers was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques. FT-IR methods were calibrated using a set of samples with a range of known wt % ethylene content. For ethylene-1-octene copolymers, the wt % octene in the copolymer was determined via measurement of the methyl deformation band at ˜1,375 cm−1. The peak height of this band was normalized by the combination and overtone band at ˜4,321 cm−1, which corrects for path length differences.
Equivalence is determined based on the mole equivalents relative to the moles of the transition metal in the catalyst complex.
Salan catalyst compounds 1-4 were evaluated using the parallel polymerization reactors for ethylene-octene (EO) copolymerization using activators that have good solubility in non-aromatic solvents. DMAH-BF20 and DMAH-BF28 were used as reference activators. In general, Catalysts 1 and 2 exhibited the highest average activity with DOdTH BF20/BF28 followed by DMAH BF20/BF28 and were least active with M2HTH BF20/BF28. The fluorenyl-substituted complexes, Catalysts 3 and 4, were significantly less active than Catalysts 1 and 2, and switching to the soluble activators did not appear to significantly boost the activity. (D4=BF20, D9=BF28).
The polymer number average molecular weight and comonomer content based on the polymer melting temperature did not appear to be significantly affected by the nature of ammonium moiety of the activator. These results indicate that the salan catalysts, or their more soluble analogs, can be used with the new activators potentially without major changes in product properties or significant reduction in catalyst activity.
Salan catalyst compounds Catalyst 5 and Catalyst 1 were evaluated using the parallel polymerization reactors for ethylene-octene (EO) copolymerization using activators that have good solubility in non-aromatic solvents. DMAH-BF20 and DMAH-BF28 were used as reference activators.
Catalyst 5 produces high molecular weight polymer (200K-250K g/mol) with low incorporation of octene (2.4-4.0 wt %) in the presence of the two experimental and two control activators. The catalyst/activator systems containing tetrakis(pentafluorophenyl)borate (BF20) give marginally lower molecular weight polymers than those produced by the catalyst/activator systems containing tetrakis(heptafluoronaphthalen-2-yl)borates (BF28).
Catalyst 1 produces significantly lower molecular weight polymer (14K-17K g/mol) with higher incorporation of octene (13-21 wt %) in the presence of the two experimental and two control activators, at very high activity. The catalyst/activator systems containing tetrakis(pentafluorophenyl)borate (BF20) produce marginally lower molecular weight polymers than those produced by the catalyst/activator systems containing tetrakis(heptafluoronaphthalen-2-yl)borates (BF28).
Two dimethylamino-salan compounds (Catalysts 25 and 26) and a methoxy-salan compound (Catalyst 27) were evaluated using the parallel polymerization reactors for ethylene-octene (EO) copolymerization using activators that have good solubility in non-aromatic solvents. DMAH-BF20 and DMAH-BF28 were used as reference activators. It was observed that activity is not affected by the soluble activators as compared to polymerizations using the catalysts with the control activators.
Overall, the present disclosure provides catalyst systems and methods thereof. The catalyst systems include one or more salan catalysts and one or more catalyst activators (having a non-coordinating anion) that are soluble in an aliphatic hydrocarbon solvent. It has been discovered that catalyst systems having a salan catalyst and a catalyst activator having, for example, a cation having 15 or more carbon atoms can provide catalyst systems having activators that are soluble in aliphatic hydrocarbons, and the catalyst systems are capable of producing polyolefins at the same or improved catalyst activities, as compared to conventional activators. In addition, the polymers produced using catalyst systems of the present disclosure can have the same or improved polymer properties, as compared to polymers produced using conventional catalyst systems. For example, polyolefins of the present disclosure can have (1) high comonomer incorporation, high molecular weight, and or a melt temperature of about 95° C. or greater, (2) low molecular weight and or a melt temperature of about 110° C. or greater, (3) high molecular weight and or a melt temperature of about 110° C. or greater, or (4) low comonomer incorporation, high molecular weight, and or a melt temperature of about 110° C. or greater. Accordingly, catalyst systems of the present disclosure provide soluble activators in addition to improved or maintained catalyst activities and polymer properties. Catalyst systems of the present disclosure therefore provide commercially viable catalyst systems without the use of toluene for preparation of the catalyst systems.
All documents described herein are incorporated by reference herein, including any priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.
This application claims the benefit of Provisional Application No. 62/926,942, filed Oct. 28, 2019, the disclosure of which is incorporated herein by reference. The present disclosure also relates to: U.S. Ser. No. 16/394,166, filed Apr. 25, 2019, and U.S. Ser. No. 16/394,197, filed Apr. 25, 2019.
| Number | Date | Country | |
|---|---|---|---|
| 62926942 | Oct 2019 | US |
