Patent Application
20100227960
This invention is directed to process of making a poly(trimethylene terephthalate) resin having low cyclic dimer content.
Poly(trimethylene terephthalate) (PTT) polyester, is an attractive material for use in engineering resin applications as it provides physical properties and processing characteristics similar to other polyester resins, namely poly(butylene terephthalate) (PBT). In addition, PTT can be a sustainable product being partially derived from renewably-sourced materials. One such PTT renewably-sourced material is Sorona® polymer, available from E.I. du Pont de Nemours & Co., Inc. Wilmington, Del., USA.
PTT has a higher equilibrium cyclic oligomer concentration, typically about 2.5% by weight based on the resin weight, when compared to similar polyesters such as poly(ethylene terephthalate) (PET) or PBT, that typically have 1.4-1.8% by weight of cyclic oligomer. The most abundant cyclic oligomer of PTT is the cyclic dimer. When PTT resin molded parts are subjected to higher than normal temperature conditions (80° C. to 160° C.) the cyclic dimer of PTT is observed to bloom to the surface of the molded part, resulting in an undesirable cosmetic defect. The surface of a black part (containing carbon black) whitens with a crystalline powder of cyclic dimer. A related problem for polymer compositions, in particular polyester compositions and polymer compositions having a polyester component, is the release of low molecular weight components when heated, referred to as “outgassing”. This can be a particular problem in polymer parts that are often or even constantly subjected to high temperatures, such as a bezel, a housing for a lamp or a reflector for a lamp, all of which are heated by the lamp.
Outgassing can be classified as “volatile” or “condensable”. Volatile outgassing consists of lower molecular weight gaseous components, such as flavorants or odorants. In motor vehicle applications, volatile outgassing is often detectable as an undesirable smell in the car interior and can cause such problems as allergic reactions and respiratory problems in sensitive individuals. In motor vehicle applications, condensable outgassing refers to components that are driven off under heat or ambient conditions, and which condense on relatively cooler surfaces, forming an oily, waxy or solid deposit, which may be perceived as a haze or film. This effect is also known as logging'.
Condensable outgassing is a particular problem in components which must have a high degree of surface perfection, and in optical components where a film or deposit may be easily perceived and good transmission of light is important. For example, conventional bezels for headlamps are often made of thermoplastics, such as polyester, for instance, PBT. The automotive headlamp assembly is an enclosed system containing metalized reflectors, light components and electrical connectors, headlamp adjusters etc., enclosed within a housing and a transparent lens cover which is usually produced from polycarbonate. Within this assembly, the bezel is a cover which is fitted around the light bulbs and reflectors to hide the internal workings. The bezel is an aesthetic/visible part, and is designed to look good. A high degree of surface perfection is required. There are several design types of thermoplastic bezels:
The bezel surrounds the reflector and light bulbs and is enclosed behind the transparent lens/headlamp cover. On prolonged heat exposure, due to the heat of the light bulb, or ambient conditions, such as strong sunlight, condensable outgassing from a conventional polyester bezel can condense on the transparent headlamp cover, leading to a visible film or deposit on the lens that is not only unattractive but which causes a decrease in light transmission.
In addition, condensable outgassing can cause problems in molding of a polymer part. During the production of polymer parts by injection molding, gradual release of condensable outgassing species onto, for example, the mold/tool surface, can result in the appearance of cloudy surface defects on the molded part. Such defects are particularly undesirable in parts such as bezels, in which a smooth, defect-free finish is desired. Such defects can sometimes be visible on parts molded in dark colors, and may become more visible after a direct metallization step. To avoid build up of this defect during a continuous molding operation, manufacturers must periodically shut down their molding machine for tool cleaning. This results in loss of time, increasing the cost of the molded part. The build up of such low a molecular weight film on the mould/tool is called mold deposit.
Furthermore, condensable outgassing species can lead to defects on directly metalized polymer surfaces. For example, microcracking of the metal coating on directly metalized thermoplastic bezels can sometimes occur on heating. Condensable outgassing species may migrate through these cracks onto the metalized surface, leading to cloudiness or loss of reflectance (“haze”) of the high gloss metalized surface.
WO 2004/106405 discloses a method for reducing condensable outgassing in polybutylene terephthalate (PBT) compositions comprising using PBT compositions having a “cyclic dimer” content of less than 0.3 wt %.
A need remains for polyester compositions or polymers having a polyester component with reduced levels of condensable outgassing and heat-age derived blooming, and for new methods of producing such compositions.
U.S. Pat. No. 6,441,129, Duh, et al, discloses a process for producing PTT at an increased solid state polymerization rate. The concentration of cyclic oligomer in the PTT provided by the process is not disclosed. Duh also discloses specific solid state polymerization processes in J. Appl. Polymer Sci., Vol 89, 3188-3200 (2003).
U.S. Pat. No. 7,332,561 discloses a PTT composition in the form of fine particles having a cyclic dimer content of 1.5% by weight or less, and a process for making the composition.
One aspect of the invention is a process of making a high viscosity poly(trimethylene terephthalate) resin having a low cyclic dimer content comprising
providing an initial poly(trimethylene terephthalate) resin composition comprising poly(trimethylene terephthalate) repeat units, in the form of a plurality of pellets having a pellet size of 3.0-4.0 g/100 pellets, said initial poly(trimethylene terephthalate) resin composition having an initial cyclic dimer content and one or more a condensation catalyst; and said initial poly(trimethylene terephthalate) resin composition having an intrinsic viscosity of 0.50 to 0.89 dL/g;
heating and agitating the plurality of resin pellets to a condensation temperature for a condensation time to provide said high viscosity poly(trimethylene terephthalate) resin having poly(trimethylene terephthalate) repeat units and having a low cyclic dimer content of less than or equal to 1.1 wt % as determined with nuclear magnetic resonance analysis and an intrinsic viscosity in the range of 0.9 to 2.0 dL/g; wherein the cyclic dimer content is based on the weight of said poly(trimethylene terephthalate) repeat units and said cyclic dimer.
Another embodiment of the invention is a poly(trimethylene terephthalate) resin composition comprising a plurality of pellets, said resin composition comprising a poly(trimethylene terephthalate) repeat units, end groups, and one or more condensation catalyst, said poly(trimethylene terephthalate) resin composition having a cyclic dimer content of less than or equal to 1.1 wt % as determined with nuclear magnetic resonance analysis, based on the weight of said poly(trimethylene terephthalate) repeat units and said cyclic dimer; and said pellets having an average weight of 3.0 to 4.0 g/100 pellets.
Another embodiment of the invention is a thermoplastic molded article comprising the poly(trimethylene terephthalate) resin composition as disclosed above.
The process disclosed herein defines a set of operating parameters for providing an improved PTT resin composition having high viscosity and low cyclic dimer content. The process described herein is, in more general terms in the art, referred to as “solid state polymerization.” However, solid state polymerization of a polymer, herein specifically PTT, is considered in the art as a continuum of a broad spectrum of operating conditions from which a specific set, or family, of operating conditions may be identified that provide a set of desirable properties. The solid state polymerization process disclosed herein defines a process including specific operating parameters for providing an improved PTT resin composition. The compositions provided by the process exhibit surprising and unexpected properties in terms of (1) rate of cyclic dimer formation upon melt testing; (2) blooming of cyclic dimer to the surface of molded parts; (3) outgassing of cyclic dimer and other oligomers upon heat aging molded parts. In addition the process disclosed herein does not require post treatment of the PTT resin with solvents or polar reagents, in order to achieve the desired properties, which makes the process very attractive for commercial production of the improved PTT resin.
The initial PTT resin composition useful in the process of the invention comprises poly(trimethylene terephthalate) repeat units and end groups, and is in the form of a plurality of pellets having a pellet size of 3.0-4.0 g/100 pellets; and in one embodiment 3.0 to 3.4 g/100 pellets. The initial PTT resin composition has an initial cyclic dimer content, typically about 2.5%, but can range from about 1.5 to about 3.0 wt %. In various embodiments the initial cyclic dimer content is about 2.0 to 3.0 wt % and about 2.3 to about 2.8 wt %, based on the weight of said poly(trimethylene terephthalate) repeat units and said cyclic dimer. The initial PTT resin composition has an intrinsic viscosity of 0.50 to 0.89 dL/g, and in other embodiments, an intrinsic viscosity of 0.60 to 0.89 dL/g, 0.63 to 0.89 dL/g, and 0.63 to 0.80 dL/g.
PTT useful as the initial PTT resin composition is of the type made by polycondensation of terephthalic acid or acid equivalent and 1,3-propanediol; with the 1,3-propane diol preferably being of the type that is obtained biochemically from a renewable source, that is “biologically-derived” 1,3-propanediol.
As indicated above, the initial PTT resin composition comprises a predominant amount of a poly(trimethylene terephthalate).
Poly(trimethylene terephthalate) suitable for use in the invention are well known in the art, and conveniently prepared by polycondensation of 1,3-propane diol with terephthalic acid or terephthalic acid equivalent.
By “terephthalic acid equivalent” is meant compounds that perform substantially like terephthalic acids in reaction with polymeric glycols and diols, as would be generally recognized by a person of ordinary skill in the relevant art. Terephthalic acid equivalents include, for example, esters (such as dimethyl terephthalate), and ester-forming derivatives such as acid halides (e.g., acid chlorides) and anhydrides.
Preferred are terephthalic acid and terephthalic acid esters, more preferably the dimethyl ester. Methods for preparation of PTT are discussed, for example in US2003/0220465A1 and commonly owned U.S. patent application Ser. No. 11/638,919 (filed 14 Dec. 2006, entitled “Continuous Process for Producing Poly(trimethylene Terephthalate)”).
A particularly preferred source of 1,3-propanediol is via a fermentation process using a renewable biological source. As an illustrative example of a starting material from a renewable source, biochemical routes to 1,3-propanediol (PDO) have been described that utilize feedstocks produced from biological and renewable resources such as corn feed stock. For example, bacterial strains able to convert glycerol into 1,3-propanediol are found in the species Klebsiella, Citrobacter, Clostridium, and Lactobacillus. The technique is disclosed in several publications, including U.S. Pat. No. 5,821,092, hereby incorporated by reference. U.S. Pat. No. 5,821,092 discloses, inter alia, a process for the biological production of 1,3-propanediol from glycerol using recombinant organisms. The process incorporates E. coli bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for 1,2-propanediol. The transformed E. coli is grown in the presence of glycerol as a carbon source and 1,3-propanediol is isolated from the growth media. Since both bacteria and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of 1,3-propanediol monomer.
The biologically-derived 1,3-propanediol, such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the 1,3-propanediol. In this way, the biologically-derived 1,3-propanediol preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel-based or petroleum-based carbon. The PTT based thereon utilizing the biologically-derived 1,3-propanediol, therefore, has less impact on the environment as the 1,3-propanediol used does not deplete diminishing fossil fuels and, upon degradation, releases carbon back to the atmosphere for use by plants once again. Thus, the compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based diols.
The biologically-derived 1,3-propanediol, and PTT based thereon, may be distinguished from similar compounds produced from a petrochemical source or from fossil fuel carbon by dual carbon-isotopic finger printing. This method usefully distinguishes chemically-identical materials, and apportions carbon material by source (and possibly year) of growth of the biospheric (plant) component. The isotopes, 14C and 13C, bring complementary information to this problem. The radiocarbon dating isotope (14C), with its nuclear half life of 5730 years, clearly allows one to apportion specimen carbon between fossil (“dead”) and biospheric (“alive”) feedstocks (Currie, L. A. “Source Apportionment of Atmospheric Particles,” Characterization of Environmental Particles, J. Buffle and H. P. van Leeuwen, Eds., 1 of Vol. I of the IUPAC Environmental Analytical Chemistry Series (Lewis Publishers, Inc) (1992) 3-74). The basic assumption in radiocarbon dating is that the constancy of 14C concentration in the atmosphere leads to the constancy of 14C in living organisms. When dealing with an isolated sample, the age of a sample can be deduced approximately by the relationship:
t=(−5730/0.693)In(A/A0)
wherein t=age, 5730 years is the half-life of radiocarbon, and A and A0 are the specific 14C activity of the sample and of the modern standard, respectively (Hsieh, Y., Soil Sci. Soc. Am J., 56, 460, (1992)). However, because of atmospheric nuclear testing since 1950 and the burning of fossil fuel since 1850, 14C has acquired a second, geochemical time characteristic. Its concentration in atmospheric CO2, and hence in the living biosphere, approximately doubled at the peak of nuclear testing, in the mid-1960s. It has since been gradually returning to the steady-state cosmogenic (atmospheric) baseline isotope rate (14C/12C) of ca. 1.2×10−12, with an approximate relaxation “half-life” of 7-10 years. This latter half-life must not be taken literally; rather, one must use the detailed atmospheric nuclear input/decay function to trace the variation of atmospheric and biospheric 14C since the onset of the nuclear age. It is this latter biospheric 14C time characteristic that holds out the promise of annual dating of recent biospheric carbon. 14C can be measured by accelerator mass spectrometry (AMS), with results given in units of “fraction of modern carbon” (fM). fM is defined by National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) 4990B and 4990C, known as oxalic acids standards HOxI and HOxII, respectively. The fundamental definition relates to 0.95 times the 14C/12C isotope ratio HOxI (referenced to AD 1950). This is roughly equivalent to decay-corrected pre-Industrial Revolution wood. For the current living biosphere (plant material), fM≈1.1.
Biologically-derived 1,3-propanediol, and compositions comprising biologically-derived 1,3-propanediol, therefore, may be completely distinguished from their petrochemical derived counterparts on the basis of 14C (fM), indicating new compositions of matter. The ability to distinguish these products is beneficial in tracking these materials in commerce. For example, products comprising both “new” and “old” carbon isotope profiles may be distinguished from products made only of “old” materials. Hence, the instant materials may be followed in commerce on the basis of their unique profile and for the purposes of defining competition, for determining shelf life, and especially for assessing environmental impact.
Preferably the 1,3-propanediol used as a reactant or as a component of the reactant in making PTT will have a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis. Particularly preferred are the purified 1,3-propanediols as disclosed in U.S. Pat. No. 7,038,092.
The purified 1,3-propanediol preferably has the following characteristics:
(1) an ultraviolet absorption at 220 nm of less than about 0.200, and at 250 nm of less than about 0.075, and at 275 nm of less than about 0.075; and/or
(2) a composition having a CIELAB “b*” color value of less than about 0.15 (ASTM D6290), and an absorbance at 270 nm of less than about 0.075; and/or
(3) a peroxide composition of less than about 10 ppm; and/or
(4) a concentration of total organic impurities (organic compounds other than 1,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and still more preferably less than about 150 ppm, as measured by gas chromatography.
PTT useful in this invention can be PTT homopolymers (derived substantially from 1,3-propane diol and terephthalic acid and/or equivalent) and copolymers, by themselves or in blends. PTT used in the invention preferably contain about 70 mole % or more of repeat units derived from 1,3-propane diol and terephthalic acid (and/or an equivalent thereof, such as dimethyl terephthalate).
In one embodiment the initial poly(trimethylene terephthalate) resin useful in the process further comprises 0.1 to 30 mole % repeat units, other than poly(trimethylene terephthalate), made from monomers selected from the group consisting of: terephthalic acid, isophthalic acid, 1,4-cyclohexane dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecane dioic acid, and the derivatives thereof such as the dimethyl, diethyl, or dipropyl esters of these dicarboxylic acids; and diols ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,2-propanediol, diethylene glycol, triethylene glycol, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, 1,2-, 1,3- and 1,4-cyclohexane dimethanol.
More preferably, the initial PTT resin composition contains at least about 80 mole %, or at least about 90 mole %, or at least about 95 mole %, or at least about 99 mole %, of repeat units derived from 1,3-propane diol and terephthalic acid (or equivalent). The most preferred polymer is poly(trimethylene terephthalate) homopolymer (polymer of substantially only 1,3-propane diol and terephthalic acid or equivalent).
For PTT resin the cyclic dimer is of the following formula (I)
For determination of cyclic dimer content, many alternative methods are available including soxhlet extraction, high pressure liquid chromatography, and NMR analysis. For the purposes herein 1H NMR analysis of the resin samples, in solution, has been chosen and is the basis for defining the bounds and limits of all claims herein. The analysis directly measures the content of all terephthalate groups in the polymer repeat units including the terepthalate present in any end groups, and in a separate and distinct region the terepthalate groups of the cyclic dimer.
The initial PTT resin has one or more a condensation catalyst. In one embodiment the process is performed in the presence of one or more condensation catalyst at about 25 to about 200 ppm based on the weight of said initial poly(trimethylene terephthalate) resin composition. Preferred condensation catalysts are selected from the group consisting of titanium (IV) butoxide, titanium (IV) propoxide, antimony (III) oxide, dibutyltin oxide, germanium oxide, zirconium(IV) bis(diethyl citrato)dipropoxide, and combinations thereof.
The heating and agitating the plurality of resin pellets to a condensation temperature can be done in any manner known to provide adequate and uniform heating and agitation sufficient to prevent the resin pellets sticking to one another. In various embodiments a rotary dryer, fluidized bed, and fluidized column reactor are used in the performing the solid state polymerization process.
When the heating and agitating the plurality solid state polymerizing of PTT is done in a rotary tumble dryer, temperatures in the range of 180° C. and 215° C. are required. At temperatures lower than 180° C., the rate polymerization is slow. At temperature of 215° C. or higher pellets begin to stick together.
In a preferred embodiment the heating and agitating is performed in a rotary dryer and the condensation temperature is about 200 to about 210° C. Preferably the heating and agitating is performed under reduced pressure, that is lower than atmospheric pressure. In various embodiments a reduced pressure of about 0.1 to about 10 mm Hg, 0.1 to 1 mm Hg, and 0.3 to 0.8 mm Hg is applied to the rotary dryer during heating and agitating.
In another preferred embodiment the heating and agitating is performed in a fluidized column and the condensation temperature is about 200 to about 220° C. In one embodiment the heating and agitating in a fluidized bed column is preformed in the presence of a stream of inert gas. A preferred inert gas in nitrogen.
One embodiment is a more specific process of making a poly(trimethylene terephthalate) resin having low cyclic dimer content consisting essentially of providing an initial poly(trimethylene terephthalate) resin composition comprising poly(trimethylene terephthalate) repeat units, in the form of a plurality of pellets having a pellet size of 3.0-4.0 g/100 pellets, said initial poly(trimethylene terephthalate) resin composition having an initial cyclic dimer content and a condensation catalyst; said initial poly(trimethylene terephthalate) resin composition having an intrinsic viscosity of 0.50 to 0.89 dL/g;
heating and agitating the plurality of resin pellets to a condensation temperature for a condensation time to provide said high viscosity poly(trimethylene terephthalate) resin having poly(trimethylene terephthalate) repeat units and having a low cyclic dimer content of less than or equal to 1.1 wt % as determined with nuclear magnetic resonance analysis and an intrinsic viscosity in the range of 0.9 to 2.0 dL/g; wherein the cyclic dimer content is based on the weight of said poly(trimethylene terephthalate) repeat units and said cyclic dimer. All the parameters disclosed above including preferred ranges for the initial cyclic dimer content, initial viscosity, low cyclic dimer content, the viscosity of the high viscosity PTT resin, and various temperature and vacuum ranges, are applicable to this more specific process.
Another embodiment is a poly(trimethylene terephthalate) resin composition comprising a plurality of pellets, said resin composition comprising a poly(trimethylene terephthalate) repeat units, end groups, and one or more condensation catalyst, said poly(trimethylene terephthalate) resin composition having a cyclic dimer content of less than or equal to 1.1 wt %, as determined with nuclear magnetic resonance analysis, based on the weight of said poly(trimethylene terephthalate) repeat units and said cyclic dimer; and said pellets having an average weight of 3.0 to 4.0 g/100 pellets. In various embodiments the poly(trimethylene terephthalate) resin composition has a cyclic dimer content of about 0.65 to about 1.1 wt % and 0.7 to 1.0 wt %, based on the weight of said poly(trimethylene terephthalate) repeat units and said cyclic dimer.
In one embodiment the one or more condensation catalyst is present in about 25 to about 200 ppm, based on the total weight of the poly(trimethylene terephthalate) repeat units, end groups, and one or more condensation catalyst. In various embodiments the one or more condensation catalyst comprises organic titanates; and are selected from the group consisting of titanium (IV) butoxide, titanium (IV) propoxide, antimony (III) oxide, dibutyltin oxide, germanium oxide, zirconium(IV) bis(diethyl citrato)dipropoxide, and combinations thereof.
In various embodiments the poly(trimethylene terephthalate) resin composition the poly(trimethylene terephthalate polymer has an intrinsic viscosity of about 0.9 to about 2.0 dL/g, 0.9 to 1.3 dL/g and 1.0 to 1.10 dL/g.
Other materials also may optionally be present in the PTT composition such as one or more filler(s), including reinforcing agent(s).
Typically, the filler is any material commonly used in thermoplastic compositions, such as pigments, reinforcing agents, and other fillers. The filler may or may not have a coating on it, for example, a sizing and/or a coating to improve adhesion of the filler to the polymers of the composition. The filler may be organic or inorganic. Useful fillers are those selected from the group consisting of minerals such as clay, sepiolite, talc, wollastonite, mica, and calcium carbonate; glass in various forms such as fibers, milled glass, solid or hollow glass spheres; carbon as black or fiber; titanium dioxide; aramid in the form of short fibers, fibrils or fibrids; flame retardants such as antimony oxide, sodium antimonate, and a combination of two or more thereof. In various embodiments the resin composition further comprises one or more fillers at about 1 to 50 wt %, about 5 to about 45 wt %; and about 10 to 40 wt %, based on the total weight of the resin composition. In various embodiments fillers are wollastonite, mica, talc, glass especially glass fiber, titanium dioxide, and calcium carbonate. A preferred filler is glass fiber and particularly at a level of about 10 to 35 weight percent.
In one embodiment the poly(trimethylene terephthalate) resin composition further comprises 0.1 to 30 mole % repeat units and end groups, other than poly(trimethylene terephthalate), made from monomers selected from the group consisting of: terephthalic acid, isophthalic acid, 1,4-cyclohexane dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecane dioic acid, and the derivatives thereof such as the dimethyl, diethyl, or dipropyl esters of these dicarboxylic acids; and diols ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,2-propanediol, diethylene glycol, triethylene glycol, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, 1,2-, 1,3- and 1,4-cyclohexane dimethanol.
The most preferred poly(trimethylene terephthalate) resin composition is poly(trimethylene terephthalate) homopolymer (polymer of substantially only 1,3-propane diol and terephthalic acid or equivalent).
The composition of this invention may also include, in addition to the above components, additives such as a lubricants, flow modifiers, heat stabilizer, antioxidant, dye, pigment, UV stabilizer, and the like, provided that they don't negatively impact the physical properties or flame resistance of the composition.
Preferred lubricants or mold release agents for various embodiments are selected from the group consisting of pentaerythritol tetramontanate, butylene glycol dimontanate, calcium montanate, and mixtures thereof.
The compositions of the present invention are in the form of a melt-mixed blend, wherein all of the polymeric components are well-dispersed within each other and all of the non-polymeric ingredients are homogeneously dispersed in and bound by the polymer matrix, such that the blend forms a unified whole. The blend may be obtained by combining the component materials using any melt-mixing method. The component materials may be mixed to homogeneity using a melt-mixer such as a single or twin-screw extruder, blender, kneader, Banbury mixer, etc. to give a resin composition. Or, part of the materials may be mixed in a melt-mixer, and the rest of the materials may then be added and further melt-mixed until homogeneous. The sequence of mixing in the manufacture of the compositions may be such that individual components may be melted in one shot, or the filler and/or other components may be fed from a side feeder, and the like, as will be understood by those skilled in the art.
The composition of the present invention may be formed into articles using methods known to those skilled in the art, such as, for example, injection molding. Such articles can include those for use in electrical and electronic applications, mechanical machine parts, and automotive applications. Various embodiments of the invention are molded articles provided by the injection molding of the poly(trimethylene terephthalate) resin composition, including non-metalized bezels, resistor blades of an air conditioning duct, electrical connectors, electrical housings, connector parts for fuel distribution.
PTT resin used as the initial PTT resin in the solid state polymerization process disclosed in the Examples was available from E.I. du Pont de Nemours & Co., Inc. Wilmington, Del., USA.
PTT-C is Sorona® Bright PTT resin, available from E.I. du Pont de Nemours & Co., Inc. Wilmington, Del., USA, having an IV of 1.02 dL/g and 2.7 wt % cyclic dimer.
CaCO3 is Albagloss® calcium carbonate available from Pfizer Inc., Minerals Pigments and Metals Division, Easton, Pa.
C-Black is a carbon black color concentrate consisting of a 50:50 wt blend of carbon black and PBT available from Clariant Corp. (Charlotte, N.C. 28205, USA).
EPON™ resin 1009F is an epoxy resin available from Hexion Specialty Chemicals, Columbus, Ohio.
Irganox® 1010 antioxidant is available from Ciba Specialty Chemicals, Tarrytown, N.Y.
Licomont ET141 is a pentaerythritol tetramontanate mold release lubricant available from Clariant Corp. (Charlotte, N.C. 28205, USA).
Licowax® OP lubricant is a partially saponified ester of montanic acid available from available Clariant Corp. (Charlotte, N.C. 28205, USA).
PPG-3563 glass fiber is available from PPG Industries, Pittsburgh Pa.
RYNRE5334 BKC is a concentrate pellet of 52.5 weight % polyethylene carrier and 47.5 weight % carbon black.
TSP is trisodium phosphate, anhydrous.
TiO2 is Millenium RCL4® titanium dioxide available from Ticona.
BaSO4 was provided by Sacht-Leben, Germany
Zinc stearate was provided by Aldrich Chemical Co. Milwaukee Wis.
Plaques (size 76.2 mm×127 mm×3.175 mm) were wrapped in aluminum foil and placed in aluminum pans and the pans placed in a closed oven in an air atmosphere with no purging for 24 h at 147° C. Part blooming was quantified using a DuPont Color Solutions X-Rite L*a*b* colorimeter to measure the whiteness (via L* reading observed at 110°, wherein higher L* values indicate a higher level of observed whiteness) of the surface of the black part, since the cyclic oligomer bloom covers its surface as a white powder when blooming is evident. The smaller the amount of cyclic oligomer on the surface, the more the carbon black pigment can be observed by incident light.
Observations made for the L* value on the 110° angle gave a quantitative measure of blooming that agreed well with a visual rating system. Low L* values (3-5) correspond to a low degree of blooming and higher L* values (20-25) correspond to a high degree of blooming.
The intrinsic viscosity (IV) was determined using viscosity measured with a Viscotek Forced Flow Viscometer Y-501 (Viscotek Corporation, Houston, Tex.) for the polymers dissolved in 50/50 weight % trifluoroacetic acid/methylene chloride at a 0.4 grams/dL concentration at 19° C. following an automated method based on ASTM D 5225-92. The measured viscosity was then correlated with standard viscosities in 60/40 wt % phenol/1,1,2,2-tetrachloroethane as determined by ASTM D 4603-96 to arrive at the reported intrinsic values.
4-6 pellets of PTT resin were melt pressed at 260° C. and melted for 5 minutes and subsequently pressed to 10,000 lbs of pressure to create a thin film (0.14 mm thick) to increase the surface area of the polymer for easy dissolution. The pressed film of polymer (15 mg) was added to CDCl3/TFA-d (5:1, 1 mL) mixture and dissolved. The solution was transferred to a 5 mm NMR tube and analyzed within one hour of sample preparation. 64 scans were run at 30° C. with a 16 second delay time on a Varian INOVA 500 MHz NMR with a proton/fluorine/carbon probe. The obtained spectrum was integrated at the terephthalate region (8.1 ppm) and the cyclic dimer region (7.65 ppm). The weight percent of cyclic dimer is calculated by dividing the integration value of the cyclic dimer region by the sum of the integration values of the cyclic dimer region and the terephthalate region multiplied by 100.
The melt test was the procedure as defined in U.S. Pat. No. 7,332,561, Column 15, method 8, with the exception that the cyclic dimer content was determined using the NMR method, as disclosed above. The test is a measure of the propensity for formation of cyclic dimer under melt conditions. The PTT pellet sample (1.0 g) was added to a glass ampule and sealed under vacuum. The ampule was heated at 260° C. for 30 minutes in a Bismuth/Tin alloy metal bath. After cooling to room temperature (RT), the ampule was broken and excess glass was removed from the polymer using liquid nitrogen.
The Fogging Test method was used to determine the tendency for molded parts to form sight reducing films of condensation on windows and automotive light bezel assemblies. A molded polymer disc was heated in a container at a programmed temperature and duration causing any volatile constituents to be condensed on a cooled glass disc. A fogging value was calculated as the quotient, in percent, of the reflectometer value of the glass disc with fogging condensates and the reflectometer value of the same glass disc without fogging condensates.
The test instrument consisted of a digital temperature controlled multi-position hot plate upon which were placed individual 83 mm×9.5 mm discs of aluminum into which was bored a hole to place a thermocouple for temperature control. A 63.5 mm diameter×50 mm tall vapor transmission cup containing a 50 mm×3.3 mm injection molded polymer test disc was placed onto each hotplate position. A 76.2 mm×3.175 mm clear silica glass disc was placed on each vapor cup, followed by a thin filter paper and then an aluminum condenser head, 90 mm×32 mm. The condenser head has a single center bore hole through which is piped a coolant solution at 80° C.
Measurements of the glass disc before and after the test were made using a glossmeter (Novo-Gloss) at a 60° measuring angle. Each disc was measured at four locations 90° rotation from each other, and the gloss value was recorded. The hot plates were programmed to a temperature of 160° C., and the test samples heated for 20 hours. The gloss value in the same locations as the clean measurements were measured and % fogging was calculated as F=(exposed disc gloss/clean disc gloss)*100 for each location and averaged for each sample. After heating, the test samples were visually inspected for the presence of white surface deposits referred to as “blooming”.
This example illustrates the process for solid phase polymerization of PTT.
Poly(trimethylene terephthalate) (PTT) resin (4680 Kg of pellets), provided from continuous polymerization of 1,3-propanediol with dimethyl terephthalate in the presence of titanium (IV) n-butoxide (100 ppm) having 33±2 mg per pellet with dimensions 2.9±0.2×2.8±0.2×4.1±0.2 mm, with an inherent viscosity of 0.76 dL/g, and with a PTT cyclic dimer concentration of 2.5 weight %, was charged to a dual cone tumble drier (ABBE rotating dryer, model 24, Patterson, N.J., USA) The tumble drier was rotated at a rate of 4 revolutions per minute while heating at a rate of 12° C./h up to 205° C. under vacuum 0.65 mm Hg (86.66 Pa). The temperature of the drier was held at 207±2° C. for 10 hours. The dryer was cooled under vacuum until pellet temperature reached 60° C.; the vacuum was broken with nitrogen and the reactor was packed out under positive nitrogen pressure. The dryer was cooled at a rate of 22° C./h to provide the solid phase polymerization pellets having a cyclic dimer concentration of 0.88 weight % as determined with NMR and the intrinsic viscosity (IV) of 1.04 dL/g.
The PTT pellets were melt tested at 260° C., as described in the melt test method disclosed above, and showed a cyclic dimer content of 1.07 wt. % by NMR analysis as disclosed above. The testing results for various examples and comparative examples are summarized in Table 1.
This result of melt testing can be contrasted with the results of melt testing of the solid state polymerized PTT fine powders disclosed in U.S. Pat. No. 7,332,561, described in Column 17 (Example 9, lines 63-68) wherein melt testing resulted in a significant increase in cyclic oligomer content from 0.9% by weight in the initial “Example 1” to 1.8% by weight in melt tested sample. In order to reduce the cyclic oligomer content in a melt tested sample, the '561 patent required that the initial PTT fine powder be treated in an atmosphere of steam at 205° C. (Example 9, lines 54-61) to maintain a cyclic dimer content less than 1.0%. Thus, the PTT resin provided by the process defined herein has a lower propensity for cyclic oligomer formation under melt test conditions than those of finer PTT powders, and without the need polar solvent treatments.
This example illustrates the process for solid phase polymerization of poly(trimethylene terephthalate).
PTT resin (11.3 Kg of pellets) provided from continuous polymerization of 1,3-propanediol with dimethyl terephthalate in the presence of titanium (IV) n-butoxide (100 ppm) having 38±1 mg per pellet with dimensions 2.9±0.2×2.8±0.2×4.1±0.2 mm, with an inherent viscosity of 0.76 dL/g, and with a PTT cyclic dimer concentration of 2.5 weight %, was charged to a dual cone tumble drier (#36 Conaform rotary dryer, Patterson Industries, Toccoa Ga. USA) The tumble drier was rotated at a rate of 6 revolutions per minute while heating at a rate of 36° C./h up to 205° C. vacuum 1.8 mm Hg (240 Pa) and nitrogen 3.7 L/min. The temperature of the drier was held at 202±0.65° C. for 10 h. The dryer was cooled under vacuum until pellet temperature reached 60° C.; the vacuum was broken with nitrogen and the reactor was packed out under positive nitrogen pressure. The dryer was cooled at a rate of 40° C./h to provide the solid phase polymerization pellets having a cyclic dimer concentration of 1.0 weight % as determined with NMR and the intrinsic viscosity (IV) of 1.05 dL/g.
The PTT pellets were melt tested at 260° C., as described in the melt test method disclosed above, and showed a cyclic dimer content of 1.26 wt. % by NMR analysis as disclosed above.
This example illustrates the process for compounding the solid phased poly(trimethylene terephthalate) pellets and testing of plaques.
PTT pellets from Example 1 were compounded using a twin screw extruder (Coperion ZSK58 SC, Ramsey, N.J., USA) using the following composition: 53 parts by wt solid phased PTT pellets, 0.30 parts zinc stearate, 0.20 parts Irganox® 1010, 0.20 parts Licowax® OP, 0.30 parts EPON 1009F, 45 parts PPG-3563 glass fiber, and 1.0 part RYNRE5334 BKC. The composition was extruded at a rate of 600 pounds per hour at a screw speed of 275 rpm and had a melt temperature of 323° C. to provide compounded pellets.
The compounded PTT pellets were molded into 76.2 mm×127 mm×3.175 mm plaques using a single screw injection molding machine (6 oz variable tonnage, HPM, Mount Gillian, Ohio, USA). The molding equipment was run at 150 tons. The melt temperature was 250° C. The mold temperature and cycle time of the plaques were 100° C. and 32 seconds respectfully.
The plaque of solid phase polymerized PTT resin subjected to the blooming test described above had an L value at 110° of 4.57.
This example illustrates the process for compounding a continuously polymerized poly(trimethylene terephthalate)
PTT pellets available from E.I. Du Pont provided from continuous polymerization of 1,3-propanediol with dimethyl terephthalate in the presence of titanium (IV) n-butoxide (100 ppm) with an inherent viscosity of 1.02 dL/g, and with a PTT cyclic dimer concentration of 2.5 weight % were compounded with the same materials as disclosed in example 1 using a screw speed of 250 rpm and had a melt temperature of 317° C. to provide continuously polymerized compounded PTT pellets.
The continuously polymerized compounded PTT pellets were molded into 76.2 mm×127 mm×3.175 mm plaques as disclosed in Example 3.
The plaque of continuously polymerized PTT resin subjected to the blooming test described above had an L value at 110° of 23.20.
Comparison of the blooming results of Example 3 and Comparative Example 1 indicate that the plaques of solid phase polymerized PTT resin with low cyclic oligomer content show significantly less blooming when heat treated at 147° C. for 24 h.
PTT resin (15 Kg pellets) provided from continuous polymerization of 1,3-propanediol with terephthalic acid in the presence of titanium (IV) n-butoxide (100 ppm) having 33±2 mg per pellet, with an inherent viscosity of 0.62 dL/g, and with a PTT cyclic dimer concentration of 2.5 weight %, was charged to a dual cone tumble drier ((#36 Conaform rotary dryer, Serial # 84-MX-0214. Built in 1984 by Patterson Industries, Toccoa Ga. USA) The tumble drier was rotated at a rate of 6 revolutions per minute while heating at a rate of 36° C./h up to 205° C. under vacuum (1.8 mm Hg, 240 Pa) and nitrogen (3.7 L/min). The temperature of the drier was held at 202±1° C. for 14 h. The dryer was cooled under vacuum until pellet temperature reached 37° C.; the vacuum was broken with nitrogen and the reactor was packed out under positive nitrogen pressure. The dryer was cooled at a rate of 40° C./h to provide the solid phase polymerization pellets having a cyclic dimer concentration of 0.87 weight % as determined with NMR and an IV of 0.88 dL/g. Thus the final IV was lower than 0.90 dL/g that is required of the process of the invention as disclosed herein.
The PTT pellets were melt tested at 260° C., as described in the melt test method disclosed above, and showed a cyclic dimer content of 1.89 wt. % by NMR analysis as disclosed above. Thus the solid state polymerized material having an IV below 0.90 undergoes rapid equilibration to provide relatively high cyclic dimer content under the melt test conditions. The testing results for various examples and comparative examples are summarized in Table 1.
This example illustrates the solid state polymerization of PTT in a fluidized column reactor
PTT resin prepared from 1,3-propanediol and dimethyl terephthalate (DMT) in a two-vessel process using tetraisopropyl titanate catalyst, Tyzor® TPT (a registered trademark of E.I. du Pont de Nemours and Company) at 60 ppm Ti, based on polymer. Molten DMT was added to 1,3-propanediol and catalyst at 185° C. in a commercial-scale transesterification vessel, and the temperature was increased to 210° C. while methanol was removed. The resulting intermediate was transferred to a polycondensation vessel where the pressure was reduced to one millibar (10.2 kg/cm2), and the temperature was increased to 255° C. When the desired melt viscosity was reached, the pressure was increased and the polymer was extruded, cooled, and cut into cylindrical pellets with a dimension of 3 mm×3 mm×4 mm. Pellets had an IV of 0.62 dl/g.
The polymer pellets (0.62 IV; 3.0 g/100 pellets) were further solid-state polymerized in a 5 inch diameter fluidized column reactor operated at a temperature of 215 to 220° C. Solid state polymerization took place inside the column as the PTT polymer pellets slowly moved downward while hot nitrogen gas flowed upward. Hold up time was about 7 hours at this temperature. Pellets were collected at the bottom of the reactor and had an IV of 1.0 dL/g.
PTT-A. PTT resin (4682 Kg of pellets, E.I. du Pont de Nemours & Co., Inc. Wilmington, Del., USA) provided from continuous polymerization of 1,3-propanediol with dimethyl terephthalate in the presence of titanium (IV) n-butoxide (100 ppm) having 33±2 mg per pellet with dimensions 2.9±0.2×2.8±0.2×4.1±0.2 mm, with an inherent viscosity of 0.76 dL/g, and with a PTT cyclic dimer concentration of 2.5 weight %, was charged to a dual cone tumble drier (ABBE rotating dryer, model 24, Patterson, N.J., USA) The tumble drier was rotated at a rate of 4 revolutions per minute while heating at a rate of 10° C./h up to 207° C. The heating occurred under vacuum (0.41 mm Hg). The temperature of the drier was held at 209±2° C. for 30 hours. The dryer was cooled under vacuum until pellet temperature reached 60° C.; the vacuum was broken with nitrogen and the reactor was packed out under positive nitrogen pressure. The dryer was cooled at a rate of 21° C./h to provide the PTT-A resin. The cyclic dimer concentration was measured after cool down. The cyclic dimer concentration was 0.77 weight %, as determined with NMR analysis disclosed in the Method Section, and the intrinsic viscosity (IV) was 1.25 dL/g as measured in the Method Section.
Using the PTT-A resin provided by Example 5, having cyclic dimer concentration of 0.82 weight % and the intrinsic viscosity (IV) was 1.14 dL/g, the resin compositions listed in Table 1 were prepared using a twin screw extruder (W&P 28/30 extruder) at a rate of 40-50 pounds per hour at a screw speed of 300 rpm, barrel temperature of 270° C. and a melt temperature of 306 to 314° C. to provide compounded pellets.
The compounded PTT-A pellets were molded into 50 mm×3.3 mm test discs using a single screw injection molding machine (6 oz variable tonnage, HPM, Mount Gillian, Ohio, USA. The molding equipment was run at 150 tons. The melt temperature was 270° C. The mold temperature and cycle time of the plaques were 90° C. and 30 seconds respectfully.
The test discs were subjected to the Light Bezel Fogging Test at as disclosed above. The condensibles %-gloss retention; and appearance of residue on test piece after the test are listed in Table 2.
A composition including components listed in C-3, Table 2, including a PTT resin not having undergone the solid state processing as disclosed herein, and having an IV of 1.02 dL/g and 2.7 wt % cyclic dimer, were compounded in a similar manner to Examples 6-11 with 260° C. barrel settings at 50 pounds per hour, 300 rpm and melt temperature of 294° C.
The results listed in Table 2 indicate that the composition of the invention having a cyclic dimer content of less than or equal to 1.1 wt %, and an intrinsic viscosity of about 0.9 to about 2.0 dL/g provides molded parts that do not exhibit surface deposits, or blooming upon heat treatment; whereas comparative example C-3, based on conventional PTT resin having about 2.7 wt % cyclic dimer does show significant surface deposits on heat treatment.
This application claims the benefit of U.S. Provisional Application No. 61/156,950, filed Mar. 3, 2009, which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61156950 | Mar 2009 | US |
