THERMOPLASTICALLY MOLDABLE COMPOSITIONS

Abstract: Difficult to mold polyester resin containing compositions are made thermoplastically moldable by the addition of an aromatic polycarbonate and mold-release additives of the formula:- R-Y wherein R is selected from saturated and unsaturated hydrocarbyl having 13 to 44 carbon atoms, inclusive; and Y is selected from monovalent moieties of the formulae:- -H, -COOR′, and -O-R″ wherein R′ is selected from hydrogen and hydrocarbyl of 1 to 36 carbon atoms, inclusive; and R″ represents one of lower alkyl and lower alkenyl.

Description: The invention relates to thermoplastically moldable polyester resin compositions. Polyester resins having properties useful for thermoplastic molding, such as injection molding, are well known. However, not all of the known polyester resins are useful for injection molding. Especially difficult to injection mold are those polyester resins which possess hot-melt adhesive properties. Other polyester resins, although not considered to be hot-melt adhesives, are difficult to injection mold because they adhere strongly to metallic surfaces when in a heat-softened condition or following cooling and re-solidification. One class of such polyester resins are those obtained by the reaction of aromatic dicarboxylic acids with cyclo-aliphatic dialkanols. An example of such polyester resins is the one described in U.S-A-2,901,466. It will be appreciated by those skilled in the art of injection molding that these polyesters are generally unsuited for molding in conventional injection molding apparatus. The polyester wraps itself around the screw and adheres to the metallic surfaces of the injection molding machine. However, these polyester resins have other physical properties which may be desirable in molded articles and in articles molded from blends of resins with compatible synthetic polymeric resins which are not themselves difficult to mold by thermoplastic molding techniques. We have found that a particular class of mold release agents, added to these polyesters blended with polycarbonates provide thermoplastic compositions which are useful to injection mold a wide variety of articles. The agents do not significantly degrade the molded resin articles, in the proportions employed. The invention comprises a thermoplastically moldable, synthetic resin composition, which comprises; a) a polyester resin which is the condensation product of a diol selected from the cis- and trans- isomers of 1,4-cyclohexanedimethanol with an acid selected from isophtalic acid, terephtalic acid, or mixtures thereof; b) 5 to 85 weight %, based on the amount of polyester plus polycarbonate, of an aromatic polycarbonate resin; and c) 0.001 to 0.45 weight %, based on the amount of polyester plus polycarbonate, of a compound of the formula R-COOR' (I) wherein R is an alkyl groups containing 13 to 44 carbon atoms, and R' is hydrogen or an alkyl group, containing 1 to 36 carbon atoms. Representative of alkyl of 1 to 44 carbon atoms, inclusive, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonodecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonoacosyl, triacontyl, hentriacontyl, dotriacontyl, tritriacontyl, pentatriacontyl, hexatriacontyl, tetratetracontyl and isomeric forms thereof. The compositions of the invention are useful for injection molding of complex parts such as valves and the like. The preferred molded articles may be sterilized by radiation and are stable in clarity and at elevated temperatures. The polyester resins of the present invention are derived from the reaction of either the cis- or trans- isomers (or a mixture thereof) of 1,4-cyclohexanedimethanol with isophtalic acid, terephtalic acid, or a mixture thereof. These polyesters have recurring units of the formula: and these polyesters may be produced by well known methods in the art such as those set forth in U.S-A-2,901,466. The above-described polyesters generally have an intrinsic viscosity between 0.40 and 2.0 dl/g measured in a mixture of 40% tetrachloroethane/60% phenol solution or a similar solvent at 25°C. Especially preferred polyesters will have an intrinsic viscosity in the range of 0.6 to 1.2 dl/g. A wide variety of compatible (for blending) aromatic polycarbonate resins are well known and are characterized in part by having recurring polymer units of the formula:- wherein each -E- is selected from the group consisting of phenylene, halo-substituted phenylene and alkyl substituted phenylene and A and B are each selected from the group consisting of hydrogen, hydrocarbyl radicals free from aliphatic unsaturation and radicals which together with the adjoining atom form a cycloalkane radical, the total number of carbon atoms in A and B being up to 12. The above-described aromatic polycarbonate resins may be prepared by methods well known in the art; see for example the method described in U.S-A-3,989,672. Thus, they may be prepared in the conventional manner by reacting a dihydric phenol with a carbonate precursor in an interfacial polymerization process. Typical of some of the dihydric phenols that may be employed are bisphenol-A, (2,2-bis(4-hydroxy-3-methylphenyl)propane,4,4 -bis(4-hydroxyphenyl)heptane, 2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl)propane, (3,3'-dichloro-4,4'-dihydroxyphenyl)methane, bis 4-hydroxy phenyl sulfone and bis 4-hydroxy phenyl sulfide. Other dihydric phenols of the bisphenol type are also available and are disclosed in U.S-A-2,999,835; 3,028,365 and 3,334,154. Bisphenol-A is preferred. It is, of course, possible to employ two or more different dihydric phenols or a copolymer of a dihydric phenol with a glycol or with hydroxy or acid terminated polyester, or with a dibasic acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired for use in this invention. Also employed in the practice of this invention may be blends of any of the above materials to provide the aromatic carbonate polymer component. The carbonate precursor may be either a carbonyl halide, a carbonate ester or a haloformate. The carbonyl halides which can be employed are carbonyl bromide, carbonyl chloride and mixtures thereof. Carbonyl chloride, also known as phosgene, is preferred. Within the definition of polycarbonate also are copolyester-carbonates, that is the polymer made from a dihydric phenol, a dibasic acid and a phosgene precursor. U.S-A-3,169,121 discloses such copolyester-carbonates and methods of preparing them. Also included herein are branched polymers wherein a polyfunctional aromatic compound is reacted with the dihydric phenol and carbonate precursor to provide a thermoplastic randomly branched polycarbonate polymer, wherein the recurring units of formulae (III) and (IV) above contain branching groups. The method of their preparation is described in U.S-A-4,001,184. Also included herein are blends of a linear polymer and a branched polymer. Preferred polycarbonate resins employed in blends with the polyester resins previously described have an intrinsic viscosity between 0.3 and 1.0 deciliters/gram (dl/g), most preferably from 0.40 to 0.65 dl/g as measured at a temperature of 25°C in methylene chloride or a like solvent. The blends of polyester and polycarbonate resins are well known as are methods of their preparation; see for example the description given in U.S-A-4,188,314. In general, the blends may be prepared under extrusion conditions (melt blending). The blends mentioned above may comprise from 10 to 95 parts by weight of the polyester resin and from 5 to 90 parts by weight of the polycarbonate resin, preferably a maximum amount of polyester is about 50 percent of the blend of polyester and polycarbonate. The thermoplastically moldable compositions of the invention are prepared by the method of the invention, which comprises blending into the polyester resins or blends thereof with a polycarbonate resin, an effective amount for mold release of a compound of the formula (I) given above. An effective amount is generally within the range of from 0.001 to 0.45 weight percent of resin, preferably 0.1 to 0.3 weight percent. Greater amounts generally are unnecessary or undesirable. Higher amounts may result in resin degradation, particularly at elevated temperatures. The mold release additives may be added to the polyester resin or blend thereof in the same manner as any conventional additive, for example, in the dry state and coextruded or in a solvent and melt extruded with the resin. Other additives in common use in thermoplastic resins may also be added. For example with respect to blends with an aromatic polycarbonate, additives which are commonly known to stabilize the resin thermally such as a phosphite can be employed. Hydrolytic stabilizers such as epoxides may also be employed as well as agents which are flame retardants, drip inhibitors, ductility enhancers, anti-oxidants, solvent resistance enhancers, ultraviolet light stabilizers and various inert fillers. Mold-release additive compounds of the formula (I) wherein R' is hydrogen are well known and include saturated and unsaturated fatty acids having from 14 to 45 carbon atoms, inclusive. Representative of such fatty acids are tetradecanoic, pentadecanoic, hexadecanoic, heptadecanoic, octadecanoic, nonadecanoic, eicosanoic, henecosanoic, decosanoic, tricosanoic, tetracosanoic, pentacosanoic, hexacosanoic, triacontanoic, hentriacontanoic, dotriacontanoic, tetratriacontanoic, pentatriacontanoic, hexatriacontanoic acids. Hold-release agents of the formula I wherein R' is alkyl of 1 to 36 carbon atoms, inclusive, include esters which may be prepared by the esterification of a fatty acid within the scope of the formula (I) as described above, with preferably an alcohol of the formula:- R-OH (V) wherein R is as defined above, limited to a carbon content of from 1 to 36 carbon atoms, inclusive. Alcohols of the formula (V) given above are well known and are represented, for example, by methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, triaconanol and the like. The esterification may be carried out by known and conventional methods; see for example the methods of Walden, Ber. 36,781 (1903) or Smith, J. Chem. Soc., 802 (1931). Representative of fatty acid esters advantageously employed as mold release agents in the method of the invention are methyl tetradecanate, methyl docosanate, stearyl docosanate, butyl pentacosanate and the like. The following examples describe the manner and process of making and using the invention and set forth the best mode contemplated by the inventor of carrying out the invention. All proportions of the mold releasing additives are in weight percent (parts by weight) of the base thermoplastic resin. The mold-release pressures obtained with the various mold-release additives were obtained on an injection molding machine with a 118cc shot capacity. The mold is a 7.62cm x 7.62cm box with a 3.8 cm wall height. It has ejector pins at four corners with two of the pins being attached to strain gauge transducers for measuring the part ejection pressure. The mold is designed with very little draft so that the part would tend to stick to the core unless mold-release is used. The pressures reported are an average of a number of mold ejections. The number of ejections averaged is also reported. The yellowing Index (YI), where reported, was determined by the method of ASTM-D-1925-70. EXAMPLES 1-6 A resin blend of 50 parts of poly(1,4-cyclohexane-dimethanol-terephthalate-co-isophthalate) [Kodar® A-150, Eastman Kodak Co.] and 50 parts of a polycarbonate resin (LEXAN® 105, General Electric Co.) stabilized with 0.1 parts of an aqueous solution of phosphorous acid (70%) is provided. The polycarbonate resin is the product of reaction of bisphenol-A and phosgene and has an inherent viscosity of from 0.40 to 0.65 dl/g measured at 25°C in methylene chloride. The resin mixture (100 parts) is separately dry formulated with a variety of mold-release agents, blended and melt extruded from a conventional extruder into the box mold described above. After cooling to a demolding temperature, the molding is ejected. The agent and the proportion added (PBW) together with the averaged observed ejector pin pressures are set forth in the following Table , with the number of readings of pin pressure averaged, the yellowing index (YI) observed, the light transmittance of the molded product and the percent of haze observed for the molded product where such data was available. EXAMPLE 7 The procedure of Examples 1-6, supra., is repeated except that no additive is added to the resin blend. The molding results are set forth in the Table , below is a control. EXAMPLE 17 The procedure of Examples 1-6, supra., is repeated except that in place of the resin blend as used therein, 100 parts of the Kodar® A-150 polyester alone are used. The resin cannot be molded. EXAMPLE ADDITIVE PBW EJECTOR PIN PRESSURE bar (Kp/cm²) NO. READINGS Y.I. TRANSMITTANCE (%) HAZE (%) 1 DOCOSANOIC ACID 0.06 427,8 (436.5) (11) 2.5 89.8 0.6 2 DOCOSANOIC ACID 0.2 416 (220.4) (10) 2.3 89.5 0.5 3 DOCOSANOIC ACID 0.3 416 (220.5) (12) 2.6 89.8 0.7 4 OCTADECANOIC ACID 0.1 353,8 (361.0) (10) 2.4 89.8 0.6 5 METHYL DOCOSANATE 0.3 247,5 (252.5) (25) 2.7 89.1 1.4 6 STEARYL DOCOSANATE 0.3 239,9 (244.8) (11) 2.5 89.3 0.8 7 (Control) NONE 0 Parts broke - could not be ejected

Claims: A thermoplastically injection moldable, synthetic resin composition, which comprises; a) a polyester resin which is the condensation product of a diol selected from the cis- and trans- isomers of 1,4-cyclohexanedimethanol with an acid selected from isophthalic acid, terephthalic acid, or mixtures thereof; b) 5 to 85 weight %, based on the amount of polyester plus polycarbonate, of an aromatic polycarbonate resin; and c) 0.001 to 0.45 weight %, based on the amount of polyester plus polycarbonate, of a compound of the formula R-COOR' (I) wherein R is an alkyl group containing 13 to 44 carbon atoms, and R' is hydrogen or an alkyl group containing 1 to 36 carbon atoms. The composition of claim 1 wherein the polycarbonate comprises about 50 weight percent of the composition.

Inventors: BOUTNI, OMAR MOHAMED
Applicants: GENERAL ELECTRIC COMPANY
Application year: 1986
Main classification: C08L69
IPC codes: C08K5, C08L69, C08L67