MXPA00010291A - Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers - Google Patents

Abstract

A polymer blend including a polyester and another thermoplastic polymer. The polyester includes terephtaloyl moieties and, optionally, other aromatic diacid moieties;and ethylene glycol moieties;optionally diethylene glycol moieties;isosorbide moieties;and, optionally one or more other diol moieties. The polyester has an inherent viscosity of at least about 0.35dL/g.

Description

PQLIÉSTERES THAT INCLUDE ISOSORBIDE AS A COMONOMER COMBINED WITH OTHER THERMOPLASTIC POLYMERS FIELD OF THE INVENTION This description relates to polyester blends and methods for making polyester blends, and more specifically to polyesters containing a portion of isosorbide, combined with other thermoplastic polymers and methods for their manufacture.

ANTECEDENTS OF THE DESCRIPTION The diol 1,: 3,6-dianhydro-D-sorbitol, hereinafter referred to as isosorbide, the structure of which is illustrated below, is easily prepared from renewable sources, such as sugars and starches. For example, isosorbide can be made from D-glucose by hydrogenation, followed by acid-catalyzed dehydration.

Ref: 123440 Isosorbide has been incorporated as a monomer within the polyester that also includes terephthaloyl moieties. See, for example, R. Storbeck et al-, Makromol. Chem. F vol. 194, p. 53-64 (1993); R. Storbeck et al., Polymer. vol. 34, p. 5003 C1993). However, it is generally considered that secondary alcohols such as isosorbide have little reactivity and are sensitive to acid catalyzed reactions. See, for example, D. Braun et al., J. Prakt. Chem .. vol. 334, p. 298-310 (1992). As a result of poor reactivity, polyesters made with an isosorbide monomer and terephthalic acid esters are expected to have a relatively low molecular weight. Ballauff et al., Polyesters _ (Derived from Renewable Sources), Polymeric Materials Encyclopedia, vol. 8, p. 5892 (1996). Copolymers containing isosorbide portions, ethylene glycol portions and terephthaloyl moieties have been reported only rarely. A copolymer containing these three portions, in which the molar ratio of ethylene glycol to isosorbide is about 90:10, are reported in the German patent application number 1,263,981 (1968). The polymer is used as a minor component (approximately 10%) of a combination with polypropylene to improve the dyeability of polypropylene fiber. It is manufactured by melt polymerization of dimethyl terephthalate, ethylene glycol and isosorbide, but the conditions, which are described only in general terms in the publication, have not provided a polymer having a high molecular weight. Copolymers of these same three monomers have recently been described again, where it is observed that the vitreous transition temperature Tg of the copolymer is increased with the isosorbide monomer content to about 200 ° C for the isosorbide terephthalate homopolymer. The polymer samples are made by reacting terephthaloyl dichloride in solution with the diol monomers. This method provides a copolymer with a molecular weight that is apparently higher than that obtained in the German patent application described above, but is still relatively low when compared to other polyester polymers and copolymers. In addition, these polymers are manufactured by polymerization and solution and are therefore free of diethylene glycol portions as a polymerization product. See R. Storbeck, Dissertation Universitát Karlsruhe (1994); R. Storbeck et al., J. Appl. Polvmer Science, vol. 59, p. 1199-1202 (1996). U.S. Patent 4,418,174 describes a process for the preparation of polyesters useful as raw materials in the production of aqueous baked lacquers. The polyesters are prepared with an alcohol and an acid. One of the many preferred alcohols is dianhydrosorbitol. However, the average molecule weight of the polyesters is from 1000 to 10,000, and a polyester containing a dianhydrosorbitol moiety has not actually been made. U.S. Patent 5,179,143 describes a process for the preparation of compression molded materials. In addition, polyesters containing hydroxyl are described herein. These hydroxyl-containing polyesters are listed to include polyhydric alcohols that include 1, 4: 3, 6-dianhydrosorbitol. However, again, the highest molecular weights reported are relatively low, that is, from 400 to 10,000, and in fact a polyester containing portion 1,: 3, 6-dianhydrosorbitol has not been made. Published PCT applications WO 97/14739 and W0 96/25449 disclose cholesteric and nematic liquid crystal polyesters that include isosorbide moieties as monomer units. Such polyesters have relatively low molecular weights and are not isotropic. Currently, high molecular weight polyesters containing an isosorbide moiety have not been combined with other thermoplastic polymers.

BRIEF DESCRIPTION OF THE INVENTION Contrary to the teachings and the expectations that have been published in the prior art, the isotropic, ie, semicrystalline and amorphous or non-liquid crystalline copolyesters containing terephthaloyl moieties, ethylene glycol moieties, isosorbide moieties and, optionally, diethylene glycol moieties, are easily synthesized in molecular weights that are suitable for manufacturing manufactured products, such as films, beverage bottles, molded products, films and fibers, on an industrial scale. The polymers used depend on the polymer composition desired. The amount of each polymer is desirably chosen so that the final polymer product possesses the desired property. Desirably, the polyester contains portions of terephthaloyl, portions of ethylene glycol, portions of isosorbide and, optionally, portions of diethylene glycol arranged to provide a useful high molecular weight polymer which can be combined with one or more of the thermoplastic polymers. In a preferred embodiment, the number of terephthaloyl moieties in the polyester polymer is in the range of from about 25% to about 50 mole% (moles% of the total polymer). The polyester polymer may also include amounts of one or more aromatic diacid portions such as, for example, those derived from isophthalic acid, 2,5-furanedicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid, , 7-naphthalenedicarboxylic acid, and 4, '-benzoic acid, at combined concentrations of up to about 25 mol% (moles of total polymer). In a preferred embodiment, the ethylene glycol monomer units are present in the polyester polymer in amounts of about 5 moles, to about 49.75 moles%. The polyester polymer may also contain portions of diethylene glycol. Depending on the manufacturing method, the amount of diethylene glycol portions in the polyester polymer is in the range of about 0.0 mole% to about 25 mole%. In a preferred embodiment, the isosorbide is present in the polyester polymer in amounts in the range of about 0.25 moles, to about 40 moles. One or more diol monomer units may also be included in the polyester polymer in amounts up to a total of about 45 moles. Of course, all percentages depend on the particular application desired. Desirably, however, equimolar amounts of diacid monomer units and diol monomer units are present in the polyester polymer. This equilibrium is desirable to obtain a high molecular weight of polyester polymer. The polyester polymer has an inherent viscosity, which is an indicator of molecular weight, of at least about 0.35 dl / g, measured in a 1% (w / v) solution of the polymer in o-chlorophenol at a temperature of 25. ° C. This inherent viscosity is sufficient for some applications, such as some optical articles and coatings. For other applications, such as compact discs, an inherent viscosity of at least about 0.4 dl / g is preferred. Superior inherent viscosities, such as at least about 0.5 dl / g are necessary for many other applications (for example bottles, films, foils, molded resin). Further processing of the polyester polymer can obtain inherent viscosities that are even higher. The polyester polymer is combined with one or more additional thermoplastic polymers. The other thermoplastic polymers suitable for use in the combinations of the present invention include polycarbonates; styrene resins; alkyl acrylate resins; polyurethanes; vinyl chloride polymer; polyarylethers; ester copolyether block polymers; polyhydroxyethers; polyarylates; other polyesters or mixtures thereof. The ratio of polyester polymer to other thermoplastic polymer can vary widely depending on the desired properties.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES OF THE DESCRIPTION The combinations of the present invention are described below in terms of the polyesters and other thermoplastic polymers that can be included within the combinations.

POLYMER POLYMERS CONTAINING ISOSORBIDE PORTIONS The polyester polymer, described in detail in the following, may be made by melt condensation of a combination of monomers containing a portion of ethylene glycol, an isosorbide portion and a terephthaloyl portion. Small amounts of other monomers may be added during the polymerization or may be produced as by-products during the reaction. In a preferred embodiment, the ethylene glycol monomer units are present in amounts of about 5 mole% to about 49.75 mole, preferably 10 mole% to about 49.5 mole, and most preferably about 25 mole. at about 48 mol%, even more preferably from about 25 mol, to about 40 mol. "The polyester polymer may also contain diethylene glycol monomer units, depending on the manufacturing method, the amount of diethylene glycol monomer units is in the range from about 0.0 moles, to about 25 moles%, preferably, 0.25 moles, to about 10 moles, and more preferably from 0.25 moles, to about 5 moles. Diethylene glycol can be produced as a byproduct of the process of polymerization and can also be added to help accurately regulate the amounts of diethylene glycol monomer units that are in the polyester polymer In a preferred embodiment, the isosorbide portions are present in the polyester polymer in amounts in the range of about 0.25 moles, to about 40 moles, preferably to approve most preferably 0.25 mole% to about 30 mole., and most preferably from about 0.5 mole% to 20 mole. Depending on the application, the isosorbide can be present in any desirable range such as 1 mol% to 3 moles, 1 mol% to 6 moles, 1 mol% to 8 moles, and 1 mol% to 20 moles%. Optionally one or more monomer units of another diol may be included in amounts up to a total of about 45 mole%, preferably less than 20 mole% and even more preferably less than 15 mole%, even more preferably less than 10 mole ., and even more preferably less than 2 moles. Examples of these different optional diol units include aliphatic alkylene glycols having 3-12 carbon atoms and having the empirical formula H0-CnH2n-0H, wherein n is a 3-12 whole number, including branched diols such as 2,2-dimethyl-1,3-propanediol; cis or trans-1,4-cyclohexanedimethanol and mixtures of cis and trans isomers; triethylene glycol; 2, 2-bis [4- (2-hydroxyethoxy) phenyl] propane; 1,1-bis [4- (2-hydroxyethoxy) phenyl] cydohexane; 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene; 1.4: 3, 6-dianhydromanitol; 1, 4: 3, 6-dianhydroiditol; and 1, -anhydroerythritol. In a preferred embodiment, the number of terephthaloyl moieties in polyester polymer is in the range of about 25 mole% to about 50 mole%, more preferably about 40 mole. to about 50 mole%, even more preferably from about 45 mole% to about 50 mole% (moles, of the total polymer). The polyester polymer may also include amounts of one or more aromatic diacid portions such as, for example, those derived from isophthalic acid, 2,5-furanodicarboxylic acid, 2,5-thiophenecarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, and 4, '-benzoic acid, at combined levels of up to about 25 mole%, preferably up to 10 mole, much more preferably up to about 5 mole! (moles of the total polymer).

Of course, the totality of the percentages depends on the particular application desired. However, desirably, equimolar amounts of diacid monomer units and diol monomer units are present in the polyester polymer. This equilibrium is desirable to obtain a high molecular weight. The polyester polymer has an inherent viscosity, which is an indicator of molecular weight, of at least about 0.35 dl / g, measured in a 1% (w / v) solution of the polymer in o-chlorophenol at a temperature of 25. ° C. This inherent viscosity is sufficient for some applications, such as some optical articles and coatings. For other applications, such as compact discs, an inherent viscosity of approximately 0.4 dl / g is preferred. Higher inherent viscosities are required for many other applications (eg bottles, films, foils, molding resins). The conditions can be adjusted to obtain desired inherent viscosities up to at least about 0.5 and desirably greater than 0.65 dl / g. Further processing of the polyester can obtain inherent viscosities of 0.7, 0.8, 0.9, 1.0, 1.5, 2.0 dl / g, and even higher. Molecular weights are usually not measured directly. Instead, the inherent viscosity of the polymer in solution or the molten viscosity is used as an indicator of molecular weight. For the present polyester polymers, the inherent viscosity is measured by the method previously described, with a molecular weight corresponding to an inherent viscosity of about 0.35 or greater which is sufficient for some uses. Higher molecular weights, corresponding to inherent viscosities of about 0.45 or greater, may be required for other applications. Generally, the inherent viscosity / molecular weight ratio can be adjusted to the linear equation: log (IV) = 0.5856 x log (Mw) - 2.9672 The inherent viscosities are a better indicator of molecular weight for sample comparisons and are used as the molecular weight indicator in the present. The conditions of the melt process for making the polyester polymer, particularly the amounts of monomers used, depends on the desired polyester polymer composition. The amount of diol and diacid or dimethyl ester thereof is desirably chosen so that the final polymer product contains the desired amounts of the various monomer units, desirably with equimolar amounts of monomer units derived from the diols and from the diacids Due to the volatility of some of the monomers, including isosorbide, and depending on variables such as whether the reactor has been sealed (ie, under pressure), and the efficiency of the distillation columns used to synthesize the polymer, some of the monomers may need to be included in excess at the beginning of the polymerization reaction and are removed by distillation as the reaction proceeds. This is particularly true for ethylene glycol and isosorbide. The exact amount of monomers to be charged in a particular reactor is easily determined by a person skilled in the art, but will often be in the following ranges. The excess ethylene glycol and isosorbide are loaded in a desirable manner, and the excess ethylene glycol and isosorbide are removed by distillation or other evaporation medium as the polymerization reaction progresses. Terephthalic acid or dimethyl terephthalate is desirably included in an amount of about 50% to about 100 moles, most preferably 80 moles! to approximately 100 moles! of the diacid monomers that are charged, the remainder is optionally diacid monomers. The isosorbide is desirably loaded in an amount of about 0.25 moles! to approximately 150 moles! or more, compared to the total amount of diacid monomers. The use of diethylene glycol monomer is optional, and often it is made in itself. If diethylene glycol is added, it is charged in an amount of up to about 20 moles! of the total amount of the diacid monomers. Ethylene glycol is charged in an amount in the range of about 5 moles! to approximately 300 moles, desirably 20 moles! to approximately 300 moles! of the diacid monomers and the optional additional diols are charged in an amount of up to about 100 moles! of the diacid monomers. The ranges given for the monomers used to make the polyester polymer are very wide due to the wide variation in monomer loss during polymerization, depending on the efficiency of the distillation columns and other kinds of recovery and recycling systems, and they are only an approximation. The exact amounts of monomers that are charged to a specific reactor to obtain a specific composition is easily determined by one skilled in the art. In the polymerization process of the polyester, the monomers are combined, and gradually heated by mixing with a catalyst or a mixture of catalysts to a temperature in the range of about 260 ° C to about 300 ° C, desirably of 280 ° C. C at approximately 285 ° C. The exact conditions and catalysts depend on whether the diacids are polymerized as true acids or as dimethyl esters. The catalyst may be initially included with the reagents, or it may be added one or more times to the mixture, as it is heated. The catalysts used can be modified as the reaction progresses. Heating and stirring is continued for a sufficient time and at a sufficient temperature, generally with distillation of the excess reactants, to provide a molten polyester polymer having a sufficiently high molecular weight to be suitable for the manufacture of products. manufactured Catalysts that may be used include Li, Ca, Mg, Mn, Zn, Pb, Sb, Sn, Ge, and Ti salts, such as salts and acetate oxides, including glycol adducts and Ti alkoxides. These are generally known in the art, and the specific catalyst or combination or sequence of catalysts used can be easily selected by one skilled in the art. The preferred catalyst and preferred conditions differ on the basis of whether the diacid monomer is polymerized as the free diacid or as the dimethyl ester. The most preferred catalysts are those containing germanium and antimony. The monomeric composition of the polyester polymer is chosen for specific uses and for a specific set of properties. For uses where a partially crystalline polymer is desired, for example for food and beverage containers, such as hot-filled or cold-filled bottles, fibers and films, the polymer will generally have a monomeric composition in the range from about 0.1% to about 10%, preferably from about 0.25% to about 5% on a molar basis of isosorbide portions, about 49.9 to about 33% on a molar basis of ethylene glycol moieties, about 0.0 to 5.0, preferably 0.25 ! at about 5! on a molar basis of diethylene glycol portions, and at most about 2% on a molar basis of other diol portions, such as 1,4-cyclohexanedimethanol. For bottle resins, the diacid comprises portions of terephthaloyl at a level of about 35% to about 50%! on a molar basis, • and optionally aromatic diacid portions at levels up to about 15! on a molar basis, wherein the optional aromatic diacid portions can be derived from 2,6-naphthalenedicarboxylic acid, isophthalic acid, 4, β-benzoic acid and mixtures thereof. For applications where it is desirable to have an amorphous polymer, such as would be used to make transparent optical articles, the amount of isosorbide portion is in the range of about 2! at about 30! on a molar basis, the ethylene glycol moieties are present in an amount of about 10% to about 48% on a molar basis, optionally other diols such as the 1,4-cyclohexanedimethanol moieties are present in a maximum amount of about 45%. % on a molar basis, diethylene glycol portions are present in an amount of from about 0.0% to about 5%, preferably from 0.25% to about 5% on a molar basis, the terephthaloyl moieties are present at a level of about 25% at about 50% and other optional diacid portions, such as 2,6-naphthalene dicarboxylic acid, isophthalic acid, 4,4'-benzoic acid and mixtures thereof, are present in amounts up to a total of about 25% on a molar basis . Some of these compositions (ie, those that have isosorbide at concentrations less than about 12%) are semicrystalline if they are cooled slowly from the melt or if they are recosed above their vitreous transition temperatures, but are amorphous if cooled rapidly of the melt. In general, compositions that can be semicrystalline are slower to crystallize than poly (ethylene terephthalate) compositions, so that it is easier to make transparent articles that remain transparent using crystallizable copolymers even though they may be exposed to conditions under the which can crystallize. The polyesters of the invention can be made by any of several methods. The product compositions vary to some extent depending on the method used, particularly in the amount of diethylene glycol portions that are present in the polymer. These methods include the reaction of the disl monomers with the acid chlorides of terephthaloyl acid and any other acid that may be present. The reaction of terephthaloyl dichloride with isosorbide and ethylene glycol is easily carried out by combining the monomers in a single solvent (for example toluene) in the presence of a base, such as pyridine, which neutralizes the HCl as it is produced. This procedure is described in R. Storbeck et al., J. Appl. Polymer Science, vol. 59, p. 1199-1202 (1996). Other well known variations using terephthaloyl dichloride can also be used (for example interfacial polymerization), or the monomers can simply be stirred together while heating. When the polymer is made using the acid chlorides, the ratio of monomer units in the product polymer is approximately the same as the ratio of reactive monomers. Therefore, the ratio of monomers charged to the reactor is about the same as the desired ratio in the product. A stoichiometric equivalent of the diol and the diacids will generally be used to obtain a high molecular weight polymer, for example, one with an inherent viscosity of at least about 0.35 dl / g, suitable for making films. The polymers can also be made by a melt polymerization process, in which the acid component is terephthalic acid or dimethyl terephthalate, and can also include the free acid or the dimethyl ester of any other aromatic diacid that may be desired in the polyester polymer composition. The diacids or dimethyl esters are heated with the diols (ethylene glycol), isosorbide, optional diols) in the presence of a catalyst at a high enough temperature so that the monomers combine to form esters and diesters, then oligomers and finally polymers. The polymer product at the end of the polymerization process is a molten polymer. The diol monomers (eg, ethylene glycol and isosorbide) are volatile and are distilled from the reactor as the polymerization proceeds. Therefore, an excess of these diols is desirably loaded into the reaction to obtain a polymer, and the amounts must be adjusted according to the characteristics of the polymerization vessel, such as the efficiency of the distillation column and the monomer recovery efficiency and recycling. Such modifications in the amounts of monomers and the like, according to the characteristics of a reactor, can be easily established by those skilled in the art. The melt polymerization process described above is a preferred method for making the polymer and is described in detail in commonly assigned U.S. Application Co-pending No. 08 / (attorney's file No. 032358-001). The melt polymerization process using dimethyl terephthalate and terephthalic acid is also summarized below.

PROCESS FOR DIMETILO TEREFTALATE It is this process, which is carried out in two stages, using terephthalic acid and the optional diacid monomers, if present, as their dimethyl ester derivatives. In smaller amounts, for example 1-2% by weight, free diacids can also be added. The diols (for example ethylene glycol and isosorbide) are mixed with dimethyl esters of the aromatic diacid (for example dimethyl terephthalate) in the presence of an ester exchange catalyst, which causes the exchange of the ethylene glycol by the methyl group of the esters of dimethyl through a transesterification reaction. This results in the formation of methanol, which is removed by distillation from the reaction flask, and bis (2-hydroxyethyl terephthalate). Due to the stoichiometry of this reaction, a little more than 2 moles of ethylene glycol are desirably added as reactants for the ester exchange reaction. Catalysts that carry out the ester exchange include salts (usually acetates) of the following metals: Li, Ca, Mg, Mn, Zn, Pb and combinations thereof, Ti (OR) 4 / where R is a group alkyl having 2-12 carbon atoms, and PbO. The catalyst components are generally included in an amount of about 10 ppm to about 100 ppm. Preferred catalysts for ester exchange include Mn (OAc) 2, Co (OAc) 2 and Zn (OAc) 2, where OAc is the abbreviation for acetate, and combinations thereof. The polycondensation catalyst in the second stage of the reaction, preferably Sb (III) oxide can now be added or at the start of polycondensation. A catalyst that has been used with particularly good success is based on salts of Mn (II) and Co (II) at levels of about 50 to about 100 ppm, each. These are used in the form of Mn (II) tetrahydrate acetate and Co (II) acetate tetrahydrate, although other salts of the same metals can also be used. Ester exchange is desirably carried out by heating and stirring the reagent mixture under an inert atmosphere (eg nitrogen) at atmospheric pressure from room temperature to a temperature high enough to induce ester exchange (approximately 150 ° C). The methanol is formed as a by-product and is distilled off from the reactor. The reaction is gradually heated to about 250 ° C until the production of methanol ceases. The end of methanol production can be recognized by a decrease in the upper temperature of the reaction vessel. A small amount of an additive having a boiling point of 170-240 ° C can be added to the ester exchange to aid in heat transfer within the reaction medium and to help retain volatile components in the container that can Sublimate to the packed column. The additive must be inert and not react with alcohols or dimethyl terephthalate at temperatures below 300 ° C. Preferably, the additive should have a boiling point greater than 170 ° C, more preferably within the range of 170 ° C to 240 ° C, and is used in an amount between about 0.05 and 10% by weight, so more preferable between approximately 0.25 and 1! by weight of the reaction mixture. A preferred additive is tetrahydronaphthalene. Other examples include diphenylether, diphenylsulfone and benzophenone. Other such solvents are described in U.S. Patent 4,294,956, the content of which is incorporated herein by reference. The second stage of the reaction is initiated by adding a polycondensation catalyst and a sequestering agent for the transesterification catalyst. The polyphosphoric acid is an example of a sequestering agent that is normally added in an amount of about 10 to 100 ppm phosphorus per g of dimethyl terephthalate. An example of a polycondensation catalyst is antimony (III) oxide, which can be used at a concentration of 100 to approximately 400 ppm. The polycondensation reaction is typically carried out at a temperature of about 250 ° C to 285 ° C. During this time, ethylene glycol is distilled off from the reaction due to the condensation of bis (2-hydroxyethyl) terephthalate to form the polymer and a by-product of ethylene glycol, which is collected as a distillate. The polycondensation reaction described above is preferably carried out under vacuum, which can be applied while the reactor is heated to the reaction temperature of. polycondensation after polyphosphoric acid and Sb (III) oxide have been added. Alternatively, vacuum may be applied after the polycondensation reaction temperature reaches 280 ° C-285 ° C. In any case, the reaction is accelerated by the application of vacuum. Heating under vacuum is continued until the molten polymer reaches the desired molecular weight, usually recognized by an increase in the melt viscosity to a predetermined level. This is observed as an increase in the torque required for the agitation motor to maintain agitation. An inherent viscosity of at least 0.65 dl / g or more can be obtained by this melt polymerization process without additional efforts at increasing molecular weights. For certain ranges of composition, the molecular weight can be further increased by solid state polymerization, described below.

TEREFTAL ACID PROCESS The process of terephthalic acid similar to the dimethyl terephthalate process except that the initial steckification reaction leads to bis (2-hydroxyethylterephthalate) and other low molecular weight esters are carried out at a slightly higher pressure (autogenous pressure, approximately 172 to 345 kPa (25-50 psi)). Instead of a double excess of diols, a smaller excess is used (approximately 10% to approximately 60%) of diols (ethylene glycol, isosorbide and other diols, if any). The intermediate esterification product is a mixture of oligomers, since sufficient diol is not present to generate a diester of terephthalic acid. The catalyst is also different. No need to add catalyst in the reaction, of esterification. A polycondensation catalyst (for example salts of Sb (III) or Ti (IV)) are still desirable to obtain a high molecular weight polymer. The catalyst that is needed to obtain a high molecular weight can be added after the esterification reaction, or it can be conveniently charged with the reactants at the beginning of the reaction. Catalysts which are useful for making the high molecular weight polymer directly from terephthalic acid and the diols include acetate and other salts of Co (II) alkanoate and Sb (III), oxide of Sb (III) and Ge (IV) ), and Ti (0R) 4 (wherein R is an alkyl group having 2 to 12 carbon atoms). The oxides solubilized with glycol of these metal salts can also be used. The use of this and other catalysts in polyester preparations is well known in the art. The reaction can be carried out in discontinuous steps, but this is not necessary. In large-scale practice, it can be carried out in stages to the extent that reagents and intermediates are pumped from the reactor into a reactor at increasing temperatures. In a batch process, the reactants and catalyst can be charged to the reactor at room temperature and then gradually heated to about 285 ° C as the polymer is produced. The pressure is vented in the range of about 200 ° C to about 250 ° C, and vacuum is then applied in a desirable manner. The esterification to form bis (2-hydroxyethylterephthalate) esters and the oligomers is brought to elevated temperatures (between room temperature and about 220 ° C to 265 ° C under autogenous pressure), and a polymer is processed at temperatures in the range of approximately 275 ° C to approximately 285 ° C under high vacuum (less than 10 Torr, preferably less than 1 Torr). Vacuum is necessary to remove residual ethylene glycol, isosorbide and water vapor from the reaction to increase molecular weight. A polymer having an inherent viscosity of at least 0.5 dl / g, and generally up to about 0.65 dl / g, can be obtained by a direct polymerization process, without subsequent solid state polymerization. The progress of the polymerization can be monitored by the melt viscosity, which is easily observed by the torque required to maintain the stirring of the molten polymer.

POLYMERIZATION. IN A SOLID STATE Polymers can be made by the melt condensation process described above having an inherent viscosity of at least about 0.5 dl / g, and often as high as about 0.65 dl / g or greater, without additional treatment, as measured by the method described. before. This corresponds to a molecular weight that is suitable for many applications (for example molded products). Polymers can also be made with lower inherent viscosities, if desired, for example for compact discs. Other applications, such as bottles, may require an even higher molecular weight. The compositions of ethylene glycol, isosorbide and terephthalic acid having isosorbide in an amount of about 0.25% to about 10% on a molar basis can have a molecular weight further increased by the solid state polymerization. The product made by fusion polymerization, after extrusion, cooling and grit formation, it is essentially not crystalline. The material can be rendered semi-crystalline by heating to a temperature in the range of about 115 ° C to about 140 ° C for an extended period of time (about 2 to about 12 hours). This induces crystallization so that the product can then be heated to a much higher temperature to increase the molecular weight. The process works best for low levels of isosorbide (approximately 0.25 mol to approximately 3 mol!), Because the polyester crystallizes more easily with low levels of isosorbide. The polymer can also be crystallized prior to polymerization in the solid state by treatment with a relatively poor solvent for polyesters such as acetone which induce crystallization. Such solvents reduce the vitreous transition temperature (Tg) allowed for crystallization. Solvent-induced crystallization is known for polyesters and is described in U.S. Patent Nos. 5,164,478 and 3,684,766 which are incorporated herein by reference. The crystallized polymer is subjected to polymerization in the solid state by placing the pelletized or pulverized polymer in a stream of an inert gas, usually nitrogen, or under a vacuum of 1 Torr, at an elevated temperature, above about 140 ° C, but by below the melting temperature of the polymer for a period of about 2 to 16 hours. The polymerization in the solid state is generally carried out at a temperature in the range of about 190 ° to about 210 ° C for a period of about 2 to about 16 hours. Good results are obtained by heating the polymer at about 195 ° to about 198 ° C for about 10 hours. This polymerization in the solid state can increase the inherent viscosity to about 0.8 dl / g or higher.

ERMOPLASTIC POLYMERS Suitable thermoplastic polymers for use in this invention are polycarbonates, styrene resins, alkyl acrylate resins, polyurethanes, vinyl chloride polymer, polyarylethers, ester copolyether block polymers, polyhydroxy ethers, polyarylates, and other polyesters or mixtures of the same. The thermoplastic polymers for use in the present application further include those polymers known to those skilled in the art for combination with, for example, polyesters based on polyethylene terephthalate and polybutylene terephthalate as described on page 42 of Encyclopedia of Commercial Polymer Blends, Chem Tech Publishing, Toronto (1994), whose content is incorporated herein by reference, and as described in Appendices IB, IC and ID, and each of the patents described in Appendices II. B, II. E and II. F of Polymer Alloys and Blends Thermodynamics and Rheology, Hanser Publishers, distributed in the United States by Oxford University Press, NY (1990), the contents of each of the appendices and patents included herein are incorporated by reference including specifically the lists of compositions of Appendices II. B, II. E and II. F. Thermoplastic polymers are also specifically contemplated which are described in U.S. Patent 4,259,458, the content of which is incorporated herein by reference. These thermoplastic polymers are discussed more specifically in the following.

A. Polycarbonate The thermoplastic aromatic polycarbonates which can be used herein are homopolymers and copolymers, and mixtures thereof, which have an intrinsic viscosity of 0.35 to 2.0 dl / g, as measured in the foregoing. Typical samples of some of the dihydric phenols that can be used in the practice of this invention are bisphenol-A (2,2-bis (4-hydroxyphenyl) propane), bis (4-hydroxyphenyl) methane), 2, 2- bis (4-hydroxy-3-methylphenyl) propane), 4, -bis (4-hydroxyphenyl) heptane), 4,4 '- (3,3,5-trimethylcyclohexylidene) diphenol, 2,2- (3,5, 3 ', 5'-tetrachloro-4,4'-dihydroxydiphenyl) propane, 2,2- (3,5,3', 5'-tetrabromo-4,4'-dihydroxydiphenyl) propane, (3,3'-dichloro) -4,4'-dihydroxydiphenyl) methane. Other dihydric phenols of the bisphenol type are also available and are described in U.S. Patent Nos. 2,999,835, 3,028,365 and 3,334,154. Of course, it is possible to use two or more different dihydric phenols or a copolymer of a dihydric phenol with a glycol or with a polyester terminated with hydroxy or acid, or with a dibasic acid in the case that a carbonate copolymer is desired or an interpolymer instead of a homopolymer, for use in the preparation of the aromatic carbonate polymers of this invention. The carbonate precursor can be a carbonyl halide, a carbonate ester or a haloformate. The carbonyl halides which may be used herein are carbonyl bromide, carbonyl chloride, and mixtures thereof. Typical of the carbonate esters which may be used herein are diphenyl carbonate, di- (halophenyl) carbonates, such as di (chlorophenyl) carbonate, di (bromophenyl) carbonate, di (trichlorophenyl) carbonate, carbonate di (tribromophenyl), etc., carbonates of di- (alkylphenyls), such as di (tolyl) carbonate, etc., di- (naphthyl) carbonate, di- (chloronaphthyl) carbonate, phenyl tolyl carbonate, carbonate of chlorophenylchloridaphthyl, etc., or mixtures thereof. Haloformates suitable for use herein include bis-haloformates of dihydric phenols (eg bisphenol-A bischloroformates or hydroquinone, etc.), or glycols (eg, ethylene glycol bishaloformates, neopentyl glycol, polyethylene glycol, etc.). Although other carbonate precursors will occur to those skilled in the art, carbonyl chloride is preferred., also known as phosgene. The carbonate polymers of this invention can be prepared by the use of phosgene or a haloformate and by the use of a molecular weight regulator, an acid acceptor and a catalyst. Molecular weight regulators which can be used to carry out the process of this invention include monohydric phenols such as phenol, para-tert-butylphenol, para-bromophenol, primary and secondary amines, etc. Preferably, a phenol is used as the molecular weight regulator. A suitable acid acceptor can be an organic acid or an inorganic acid acceptor. A suitable organic acid acceptor is a tertiary amine and includes materials such as pyridine, triethylamine, dimethylaniline, tributylamine, etc. The inorganic acid acceptor can be one. which can be a hydroxide, a carbonate, a bicarbonate or a phosphate of an alkali metal or alkaline earth metal. The catalysts which are used herein may be any of the suitable catalysts that aid in the polymerization of bisphenol-A with phosgene. Suitable catalysts include tertiary amines such as, for example, triethylamine, tripropylamine, N, N-dimethylaniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyltriethylammonium bromide, tetra-n-heptylammonium iodide, bromide tetra-n-propylammonium, tetramethylammonium chloride, tetramethylammonium hydroxide, tetra-n-butylammonium iodide, benzyltrimethylammonium chloride, and quaternary phosphonium compounds such as, for example, n-butyltriphenylphosphonium bromide, and methyltriphenylphosphonium bromide. Polycarbonates can be prepared in one-phase (homogeneous solution) or two-phase (interfacial) systems, when phosgene or a haloformate is used. Volume reactions are possible with the diaryl carbonate precursors.

B. Styrene resin Styrene resins suitable for use herein include polymers of the ABS type, which molecules consist of two or more polymeric parts of different compositions that chemically bind. The polymer is preferably prepared by polymerizing a conjugated diene such as butadiene or a conjugated diene with a monomer copolymerizable therewith such as styrene, to provide a polymeric backbone. After the formation of the main structure, at least one graft monomer and preferably two are those that are polymerized in the presence of the prepolymerized backbone to obtain the graft polymer. As mentioned, the main structure polymer preferably is a conjugated diene polymer such as polybutadiene polyisoprene, or a copolymer such as butadiene-styrene, butadiene-acrylonitrile, or the like. The specific conjugated diene monomers normally used to prepare the main structure of the graft polymer portion of the combinations of this invention are described generically by the formula: wherein X can be selected from the group consisting of hydrogen, alkyl groups containing from 1 to 5 carbon atoms, chlorine and bromine. Examples of dienes that can be used are butadiene, isoprene; 1,3-heptadiene; methyl-1,3-pentadiene; 2, 3-dimethyl-1,3-butadiene; 1,3-pentadiene; 2-methyl-3-ethyl-l, 3-butadiene 2-ethyl-l, 3-pentadiene; 1,3- and 2,4-hexadienes; butadiene substituted with chlorine and bromine such as dichlorobutadiene, bromobutadiene, dibromobutadiene and mixtures thereof, and the like. The preferred conjugated diene used herein is butadiene. A group of monomers that can be polymerized in the presence of the prepolymerized backbone are preferably monovinylaromatic hydrocarbons. The monovinylaromatic monomers are described generically by the formula: wherein X can be selected from the group consisting of hydrogen, alkyl groups containing from 1 to 5 carbon atoms, chlorine and bromine. Examples of the monovinylaromatic compounds and substituted monovinylaromatic compounds that can be used are styrene and other vinyl-substituted aromatic compounds including alkyl-, cycloalkyl-, aryl-, alkaryl-, aralkyl-, alkoxy-, aryloxy-, and other vinylaromatic compounds replaced. Examples of such compounds are 3-methylstyrene; 3, 5-diethylstyrene and 4-n-propylstyrene, α-methylstyrene, α-methylvinyl toluene, α-chlorostyrene, α-bromostyrene, dichlorostyrene, dibromostyrene, tetra-chlorostyrene, mixtures thereof and the like. The preferred monovinylaromatic hydrocarbons used herein are styrene or α-methylstyrene. A second group of monomers that can be polymerized in the presence of the prepolymerized backbone are acrylonitrile, substituted acrylonitrile and / or acrylic acid esters exemplified by acrylonitrile and alkyl acrylates such as methyl methacrylate. Acrylonitrile, substituted acrylonitrile or acrylic acid esters are generically described by the formula: wherein X can be selected from the group consisting of hydrogen, alkyl groups containing from 1 to 5 carbon atoms, chlorine and bromine, and Y is selected from the group consisting of cyano and carbalkoxy, wherein the alkyl group of the carbalkoxy group contains from 1 to about 12 carbon atoms. Examples of the monomers of this description are acrylonitrile, ethacrylonitrile, methacrylonitrile, a-chlorocarboxylic acid, beta-1-chlorocarbon, and a-bromoacrylonitrile, and beta-bromoacrylonitrile, methyl acrylate, methacrylate. of methyl, ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, isobutyl acrylate, mixtures thereof and the like. The preferred acrylic monomer used herein is acrylonitrile and the preferred acrylic acid esters are ethyl acrylate and methyl methacrylate. In the preparation of the graft polymer, the conjugated diolefin polymer or copolymer exemplified by the 1,3-butadiene polymer or copolymer comprises from about 50% by weight to about 5% by weight of the total graft polymer composition and the monomers polymerized in the presence of the structure The principal exemplified by styrene and acrylonitrile comprise from about 40 to about 95! by weight of the total graft polymer composition.

The second group of graft monomers, exemplified by acrylonitrile, ethyl acrylate or methyl methacrylate, of the graft polymer composition, preferably comprise about 10 μl. at about 40! by weight of the total graft copolymer and the monovinylaromatic hydrocarbon composition exemplified by styrene comprise from about 30 to about 70% by weight of the total graft polymer composition. When preparing the polymer, it is normal to have a certain percentage of polymerizing monomers that are grafted onto the main structure and that combine with each other, which occurs as with the free copolymer. If styrene is used as one of the graft monomers and acrylonitrile as the second graft monomer, a certain portion of the composition will copolymerize as a styrene-acrylonitrile free copolymer. In the case where α-methylstyrene (or other monomer) is substituted by styrene in the compositions used to prepare the graft polymer, a certain percentage of the composition can be a copolymer of α-methylstyrene-acrylonitrile. In addition, there are occasions when a copolymer, such as α-methylstyrene-acrylonitrile, is added to the combination of graft polymer and copolymer. When referring to the graft-copolymer polymer combination herein, it is meant optionally to include at least one copolymer combined with a graft polymer. In this invention it is contemplated that the graft polymer composition may contain up to 90! of the free copolymer. Optionally, the elastomeric backbone can be an acrylate rubber such as one based on n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and the like. Additionally, minor amounts of a diene may be copolymerized in the acrylate rubber backbone to provide improved grafting with the matrix polymer. Although not mentioned previously, polymers of the styrene-maleic anhydride type can be used in the combinations of the present invention.

C. Alkyl Acrylate Resin The alkyl acrylate resin used in the present invention includes a homopolymer of methyl methacrylate (ie, polymethyl methacrylate) or a copolymer of methyl methacrylate with a vinyl monomer (eg, acrylonitrile, N-allylmaleimide, N-vinylmaleimide or an alkyl acrylate or methacrylate in which the alkyl group contains from 1 to 8 carbon atoms such as methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate and butyl methacrylate). The amount of methyl methacrylate is not less than 70! by weight of this co-polymer resin. The methyl methacrylate resin may have a reduced viscosity of 0.1 to 2.0 dl / g in a 1% chloroform solution at 25 ° C. The alkyl acrylate resin can be grafted onto an unsaturated elastomeric backbone such as polybutadiene, polyisoprene, and / or butadiene or isoprene copolymers. In the case of the graft copolymer, the alkyl acrylate resin comprises more than 50! by weight of the graft copolymers.

Polyurethanes These thermoplastic polyurethanes can be synthesized by methods described in U.S. Patent No. 3,214,411, incorporated herein by reference. A particularly useful polyester resin, used as an initial material for the thermoplastic polyurethane are those produced from adipic acid and a glycol having at least one primary hydroxyl group. The adipic acid is condensed with a suitable glycol or a mixture of glycols which have at least one primary hydroxyl group. The condensation stops when an acid number of about 0.5 to about 2.0 is reached. The water that is formed during the reaction is removed simultaneously with the same or subsequently the same so that the final water content is from about 0.01 to about 0.2!, preferably from about 0.01 to 0.05 !. Any suitable glycol can be used in the reaction with the adipic acid such as, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, bis- (hydroxymethylcyclohexane), 1,4-butanediol, diethylene glycol, 2,2-dimethylpropylene glycol, 1,3 -propylene glycol, and the like. In addition to the glycols, a small amount of trihydric alcohol of up to about 1% may be used together with the glycols such as, for example, trimethylolpropane, glycerol, hexanetriol and the like. The resulting hydroxyl polyester has a molecular weight of at least about 600, a hydroxyl number of from about 25 to about 190, and preferably between about 40 and about 60, and an acid number of between about 0.5 and about 2, and a water content of 0.01 to about 0.2 !. The organic diisocyanate to be used in the preparation of the elastomer preferably is 4,4'-diphenylmethane diisocyanate. It is desired that the 4,4'-diphenylmethane diisocyanate contains less than 5% of 2,4'-diphenylmethane diisocyanate and less than 2% of the diphenylmethane diisocyanate dimer. It is further desired that the acidity, calculated as HCl, is from about 0.0001 to about 0.02%. The acidity, calculated as a percentage of HCl, is determined by extracting the isocyanate chloride in a hot aqueous solution of methanol or by releasing the chloride by hydrolysis by water and titrating the extract with a standard solution of silver nitrate to obtain the concentration of the chloride ion present. Other diisocyanates may be used to prepare the processible thermoplastic polyurethanes such as ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1, 2 -diisocyanate, 2-tolylene diisocyanate, 2,6-toluylene diisocyanate, 2,2-diphenylpropane-4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, diisocyanate 1 , 4-naphthylene, 1,5-naphhenylene diisocyanate, dipheny1-4, 4'-diisocyanate, azobenzene-4,4'-diisocyanate, diphenylsulfone-4, -diisocyanate, dichlorohexamethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate , l-chlorobenzene-2,4-diisocyanate, furfurylidene diisocyanate and the like. Any suitable chain extender having groups containing active hydrogens, reactive with isocyanate groups, can be used, for example, diols including ethylene glycol, propylene glycol, 1,4-butanediol, butenediol, butynediol, xylylene glycols, amylene glycols, , 4-phenylene-bis-β-hydroxyethyl ether, 1,3-phenylene-bis-β-hydroxyethyl ether, bis- (hydroxymethylcyclohexane), hexanediol, thiodiglycol and the like; diamines including ethylene diamine, propylene diamine, butylene diamine, hexamethylenediamine, cyclohexylenediamine, phenylenediamine, toluylenediamine, xylylenediamine, 3,3-r-dichlorobenzidine, 3,3 '-dinitrobenzidine and the like; alkanolamines such as, for example, ethanolamine, amino propyl alcohol, 2,2-dimethylpropanolamine, 3-aminocyclohexyl alcohol, p-aminobenzyl alcohol and the like. The difunctional chain extenders mentioned in U.S. Patent Nos. 2,620,516, 2,621,166 and 2,729,618 incorporated herein by reference can be used. If desirable, a small amount of polyfunctional material can be used. However, this polyfunctional chain extender must not be present in an amount greater than approximately 1! in weigh. In this application, any suitable polyfunctional compound such as, for example, glycerol, trimethylolpropane, hexanetriol, pentaerythritol and the like can be used. According to. process of this invention, the polyester, the organic diisocyanate and the chain extender can be individually heated, preferably at a temperature from about 60 ° to about -135 ° C, and then the polyester and the chain extender are mixed substantially simultaneously with the diisocyanate. Of course, to increase the reaction rate, any suitable catalyst can be added to the reaction mixture such as tertiary amides and the like as set forth in U.S. Patent Nos. 2,620,516, 2,621,166 and 2,729,618. Although adipate polyesters are preferred, polyesters can be used which are based on succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid and Similar. Polyesters based on e-caprolactone are also preferred. A polyether can be used in place of the polyester in the preparation of a thermoplastic polyurethane and preferably polytetramethylene glycol having an average molecular weight between about 600 and 2000 and preferably about 1000. Other psylesters such as polypropylene glycol, polyethylene glycol and the like can be used, with the condition that its molecular weight is greater than about 600. The above polyurethanes and other thermoplastic polyurethanes such as those described in U.S. Patent Nos. 2,621,166, 2,729,618, 3,214,411, 2,778,810, 3,012,992, Canadian Patent Nos. 754,233, 733,577 and 842,325, all incorporated herein by reference, can be used to produce the thermoplastic polyesters.

E. Vinyl Chloride Polymers The vinyl chloride polymers for the purpose of this invention are polyvinyl chloride and vinyl chloride copolymers with olefinically unsaturated polymerizable compounds which contain at least 80% by weight of vinyl chloride incorporated therein. Olefinically unsaturated compounds which are suitable for copolymerization are, for example, vinylidene halides such as vinylidene chloride and vinylidene fluoride, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate, benzoate of vinyl, acrylic and a-alkylacrylic acids and their esters of alkyl, amides and nitriles, methacrylic acid, methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, acrylamide, N-methylacrylamide, acrylonitrile, and methacrylonitrile , aromatic vinyl compounds such as styrene and vinylnaphthalene, and olefinically unsaturated hydrocarbons such as ethylene, bicyclo- [2, 2, 1] -hept-2-ene and bicyclo- [2, 2, 1] -hepta-2, 5 -Dienos. These vinyl chloride polymers are known and can be prepared by customary emulsion, suspension or volume or bulk polymerizations. Preferred are vinyl chloride polymers which have molecular weights of 40,000 to 60,000.

. Poly (aryl) ethers The poly (aryl ether) resin useful in the combination can be described as a linear thermoplastic polyarylene polyether polysulfone, wherein the arylene units are interposed with ether and sulfone bonds. These resins can be obtained by reaction of a double alkali metal salt of a dihydric phenol and a dihalobenzene compound, wherein either or both contain a sulfone bond -S02- between arylene groups, to provide sulfone units in the polymer chain, in addition to arylene units and ether units. The polysulfone polymer has a basic structure consisting of recurring units of the formula O-E-O-E'- wherein E is the residue of the dihydric phenol and E is the residue of the benzenoid compound having an inert electrowinning group in at least one of the ortho and para positions relative to the valence bonds; both residues are linked by valence to the ether oxygens through aromatic carbon atoms. Such polysulfones are included within the polyarylene polyether resin class described in U.S. Patent No. 3,264,536, the disclosure of which is incorporated herein by reference, for the purpose of describing and exemplifying E and E 'in greater detail, including the preferred forms of E derived from dinuclear phenols that have the structure: HO Ar is an aromatic group and preferably a phenylene group. A and Ax can be groups of same or different inert substituents such as alkyl groups having from 1 to 4 carbon atoms, halogen atoms, i.e., fluorine, chlorine, bromine or iodine, or alkoxy radicals having from 1 to 4 carbon atoms, ryr? are integers having a value of 0 to 4, inclusive, and Rx is a representative of a bond between aromatic carbon atoms such as in dihydroxydiphenyl, or is a divalent radical, including, for example, CO, O, S, SS , S02 and divalent organic hydrocarbon radicals such as alkylene, alkylidene, cycloalkylene or halogen, alkyl, aryl or similar substituted alkylene, alkylidene and cycloalkylene radicals, as well as alkarylene and aromatic radicals, and a ring fused to both Ar groups. Typical preferred polymers are constituted of. recurring units that have the formula: in the following, the formula A and R? they can be the same or different inert substituent groups such as alkyl groups having from 1 to 4 carbon atoms, halogen atoms (for example, fluorine, chlorine, bromine or iodine) or alkoxy radicals having from 1 to 4 carbon atoms, r and r - are integers that have a value from 0 to 4, inclusive. Typically, R x is representative of a bond between aromatic carbon atoms or a divalent linking radical, and R 2 represents sulfone, carbonyl, sulfoxide. Preferably, Rx represents a bond between aromatic carbon atoms. Even the thermoplastic polyarylene polysulfones of the above formula wherein r and rx are 0 are further preferred. Rx is a divalent linking radical of the formula: R "-C-R" wherein R "represents a member of the group consisting of alkyl, lower aryl and halogen substituted groups thereof, and R2 is a sulfone group Typical examples of these reaction products prepared from 2,2-bis- (4-hydroxyphenyl) propane (source of residue E) with 4,4'-dichlorodiphenylsulfone (source of residue E ') and the equivalent reaction products such as those formed from 4,4'-dichlorodiphenylsulfone with benzophenone bisphenol (4,4'-dihydroxydiphenyl ketone), or the bisphenol of acetophenone [1,1-bis (4-hydroxyphenyl) ethane], or the bisphenol of vinylcyclohexane [1-ethyl-1- (4-hydroxyphenyl) -3 - (4-hydroxyphenylcyclohexane)], or 4,4'-dihydroxydiphenylsulfone or alpha, alpha '-bis (4-hydroxyphenyl) -p-diisopropylbenzene A further useful discussion of the polysulfone resins which can be used are found in British Patent Number 1,060,546.

G. Copolyether Block Copolymer The polyether esters consist essentially of a multiplicity of long-chain ester units and recurring short interline chain connected head to tail through ester bonds, the long chain ester units are represented by the following structure: and the short chain ester units are represented by the following structure: wherein: G is a divalent radical that remains after the removal of the terminal hydroxy groups from a poly (alkylene oxide) glycol having a molecular weight of about 400-3500; D is a divalent radical that remains after the removal of the hydroxyl groups from a low molecular weight diol having a molecular weight of less than about 250; and R2 is a divalent radical that remains after the removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300; with the conditions that the short chain ester units constitute approximately 25-65% by weight of the copolyester, at least about 70% of the R2 groups should be 1,4-phenylene radicals, at least about 70% of the groups D must be 1, 4-butylene radicals, and the sum of the percentages of the R2 groups which are not 1, 4-phenylene radicals, and of the D groups which are not 1,4-butylene radicals, can not be exceed approximately 30 !. The term "long chain ester units", as applied to the units in a polymer chain refers to the reaction product of a long chain glycol with a dicarboxylic acid. The long chain glycols of the present invention are poly (alkylene oxide) glycols having a molecular weight of between about 400 and 3500, preferably between about 600 and 2000. The copolyesters prepared from poly (alkylene oxide) glycols having a molecular weight of about 600-2000 are those which are preferred because they show useful properties over a wide range of temperatures, in combination with a limited water expansion. Copolyesters prepared from poly (alkylene oxide) glycols having a molecular weight exceeding about 3500 may crystallize and lose their elastomeric character and good properties at low temperature. The copolyester prepared from glycols having molecular weights less than about 400, have useful properties only within a narrow temperature range and are less suitable for injection molding and extrusion due to a slower rate of crystallization of the resulting block copolymer . The long chain glycols contain a higher proportion of tetramethylene oxide units. In a preferred embodiment of the present invention, the long chain glycols will be completely poly (tetramethylene oxide) glycol. In some cases, it may be desirable to use random or block copolymers of tetramethylene oxide containing minor proportions of a second alkylene oxide. Typically, the second monomer will constitute less than about 40 mole percent of the poly (alkylene oxide) glycols, and preferably less than 2Q mole percent. Representative examples of the second monomer include 1,2- and 1,3-propylene oxides, 1,2-butylene oxide and ethylene oxide. The term "short chain ester units", as applied to the units in a polymer chain refer to low molecular weight compounds or polymer chain units having molecular weights less than about 550. They are made by reacting a low molecular weight diol (less than about 250) with a dicarboxylic acid. Included among the low molecular weight diols (other than 1,4-butanediol) which react to form short chain ester units are the dihydroxyacyclic, alicyclic and aromatic compounds. Diols with 2-15 carbon atoms such as ethylene, propylene, isobutyl, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene and decamethylene glycols, dihydroxy cyclohexane, cyclohexane dimethanol, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, are preferred. etc. Aliphatic diols containing 2-8 carbon atoms are especially preferred. Included among the bisphenols which may be used are bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) methane and bis (p-hydroxyphenyl) propane. Derivatives formed from equivalent esters of diols are also useful (for example ethylene oxide or ethylene carbonate which can be used in place of ethylene glycol). The term "low molecular weight diols", as used herein, should be constructed to include such equivalent ester derivatives: under the conditions, however, that the molecular weight requirement pertains to the diol only and not to its derivatives. Dicarboxylic acids (other than terephthalic acid) which react with the above long chain glycols or low molecular weight diols to produce the copolyesters of this invention are aliphatic, cycloaliphatic or aromatic dicarboxylic acids of low molecular weight. The term "dicarboxylic acids", as used herein, include acid equivalents of dicarboxylic acids having two functional carboxyl groups which function substantially as dicarboxylic acids in reaction with glycols and diols to form copolyester polymers. These equivalents include esters and ester-forming derivatives such as acid halides and anhydrides. The molecular weight requirement belongs to the acid and not to its equivalent ester or ester-forming derivative. Therefore, an ester of a carboxylic acid having a molecular weight greater than 300 or an acid equivalent of a carboxylic acid having a molecular weight greater than 300 is included, provided that the acid has a lower molecular weight to about 300. The dicarboxylic acids may contain any substituent group or combinations which do not substantially interfere with the formation of the copolyester polymer and the use of the polymer in the elastomeric compositions of this invention. Aliphatic dicarboxylic acids, as the term is used herein, refers to carboxylic acids having two carboxyl groups, each bonded to a saturated carbon atom. If the carbon atom to which the carboxyl group is attached is saturated and is in a ring, the acid is cycloaliphatic. Aliphatic or cycloaliphatic acids that have conjugated unsaturations can often not be used due to homopolymerization. However, some unsaturated acids such as maleic acid can be used.

Aromatic dicarboxylic acids, as the term is used herein, are dicarboxylic acids having two carboxyl groups attached to a carbon atom in an isolated or fused benzene ring. It is not necessary that both carboxyl functional groups be linked to the same aromatic ring and when more than one ring is present, they can be linked by aliphatic or aromatic divalent radicals such as -O- or -S02-, alkylene, alkylidene, etc. Representative aliphatic and cycloaliphatic acids which can be used for this invention are sebacic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, glutaric acid, succinic acid, carbonic acid, oxalic acid, azelaic acid, diethylmalonic acid, allylmanic acid, 4-cyclohexane-1,2-dicarboxylic acid, 2-ethylsuberic acid, 2,2,3,3-tetramethyl-succinic acid, cyclopentanedicarboxylic acid, decahydro-1,5-naphthylenedicarboxylic acid, 4,4 acid -bicyclohexyldicarboxylic acid, decahydro-2,6-naphthylenedicarboxylic acid, 4-me ti -lebisbis- (cyclohexyl) carboxylic acid, 3-furanodicarboxylic acid, and 1,1-cyclobutanedicarboxylic acid. Preferred aliphatic acids are cyclohexanedicarboxylic acids and adipic acid.

Representative aromatic dicarboxylic acids which may be used include phthalic, terephthalic and isophthalic acids, dicarboxy compounds substituted with two benzene nuclei such as bis (p-carboxyphenyl) -methane, p-carboxyphenyl / oxybenzoic acid, ethylenebis (p-oxybenzoic acid) ), 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, phenanthrenodicarboxylic acid, anthracenedicarboxylic acid, 4,4'-sulphunyldibenzoic acid and C 1 -C 4 alkyl and substituted derivatives in the ring the same, such as halo, alkoxy, and aryl derivatives. Hydroxy acids such as p (β-hydroxyethoxy) benzoic acid may also be used provided that an aromatic dicarboxylic acid is also present. Aromatic dicarboxylic acids are a preferred class for preparing copolyester polymers useful for the compositions of this invention. Among the aromatic acids, those with 8-16 carbon atoms are preferred, particularly the dicarboxylic acids of phenylene, ie, terephthalic and isophthalic acids. The most preferred copolyesters of this invention are those prepared from dhyl terephthalate, 1,4-butanediol and poly (tetramethylene oxide) glycol having a molecular weight of about 600-1500.

Desirable polyether esters are described, for example, in U.S. Patent Nos. 3,784,520 and 3,766,146.

H. Polihidroxiéter The thermoplastic polyhydroxy ethers in the present invention have the general formula: wherein D is a radical residue of a dihydric phenol, E "is a radical residue of an epoxide which is selected from mono- and di-epoxides and containing from 1 to 2 hydroxyl groups, and n is an integer which represents the degree of polymerization and is at least 30, and preferably is greater than about 80. In general, the thermoplastic polyhydroxyethers are prepared by contacting a dihydric phenol and an epoxide containing 1 to 2 epoxide groups under polymerization conditions. in substantially equimolar quantities The product made by the reaction between bisphenol-A and epichlorohydrin have the repeated unit and may be referred to as a poly (monohydroxy ether) of bis-phenol-A. The product made by the reaction between hydroquinone and butadiene dioxide have the repeated unit and may be referred to as a poly (dihydroxyether) or hydroquinone. By using both a monoepoxide and a diepoxide, poly (hydroxy dihydroxyethers) can be obtained, the relative amounts of mono- and diepoxide determine the final concentration of the repeating E "units containing mono- and dihydroxy in the polymer. Any dihydric phenol can be used in the formation of the poly (hydroxyethers) The illustrative dihydric phenols are mononuclear dihydric phenols such as hydroquinone, resorcinol and the like, as well as the polynuclear phenols which are preferred.The polynuclear dihydric phenols have the general formula : wherein: Ar is an aromatic divalent hydrocarbon radical such as naphthylene and phenylene, with phenylene being preferred for the thermoplastic polyhydroxyethers used in this invention; B and Blf which may be the same or different, are alkyl radicals such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl and the like, preferably alkyl radicals having a maximum of 4 carbon atoms; or halogen atoms, i.e., chlorine, bromine, iodine or fluorine; or alkoxy radicals such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butyloxy, amyloxy and the like, preferably an alkoxy radical having a maximum of 4 carbon atoms, a and a: are independently integers from 0 to 4, R 'is alkylene, alkylidene, cycloalkylene or a saturated divalent group. Particularly preferred are dihydric polynuclear phenols having the general formula: where B, Bl tay ax are as previously defined, and R3 is an alkylene or alkylidene group, preferably having 1 to 3 carbon atoms, inclusive, or cycloalkylene, or R3 is a saturated divalent group such as that obtained starting from the compounds such as vinylcyclohexane and dipentene and their isomers by reaction with two moles of phenol per mole of the compound. Preferably, R3 contains from 1 to 9 carbon atoms. The diepoxides useful for the preparation of polyhydroxyethers can be represented by the formula wherein R 4 is representative of a bond between adjacent carbon atoms or a divalent inorganic or organic radical such as an arrangement of aliphatic, aromatic, homocyclic, heterocyclic or acyclic atoms. By the term "diepoxide" is meant a compound containing two epoxide groups, ie, groups containing an oxirane oxygen atom bonded to two vicinal aliphatic carbon atoms. Saturated diepoxides which both oxirane oxygen atoms are bonded to carbon atoms of a saturated aliphatic hydrocarbon chain are those that are particularly preferred. The term "saturated diepoxides" refers to diepoxides which are free of ethylenic unsaturation, ie, -C = C- and acetylenic unsaturation, ie, -C = C-. Diepoxides which contain only carbon, hydrogen and oxygen atoms are especially preferred. Oxygen atoms can be (in addition to oxirane oxygen), ether oxygen, that is, -0-, oxacarbonyl oxygen, that is, OR II - c- o- carbonyl oxygen, that is, OR II -c- and similar. A single diepoxide or a mixture of at least two diepoxides can be used in the preparation of the polyhydroxyethers of the present invention, and the term "diepoxide" is intended to include a mixture of at least two diepoxides. Other diepoxides which may be mentioned include those in which the two oxirane groups are linked through an aromatic ether, ie, compounds having the grouping wherein R 4 is a divalent organic radical, W is a residue of a divalent aromatic radical of a dihydric phenol such as those previously included in the description of the dihydric phenols, and d is an integer from 0 to 1, inclusive. Other additional diepoxides include ethers wherein the oxirane groups are connected to vicinal carbon atoms, at least a pair of which is a part of a cycloaliphatic hydrocarbon. These polyhydroxy ethers are prepared by methods well known in the art such as those detailed in, for example, U.S. Patent Nos. 3,238,087; 3,305,528; 3,294,747 and 3,277,051.

. Polyarylates The polyarylates of this invention are desirably derived from a dihydric phenol and an aromatic dicarboxylic acid. A particularly desirable dihydric phenol is of the following formula: wherein Y is selected from alkyl groups of 1 to 4 carbon, chlorine or bromine atoms, z has a value of 0 to 4, inclusive, and R 'is a divalent saturated aliphatic hydrocarbon radical, particularly alkylene and alkylidene radicals having from 1 to 3 carbon atoms, and cycloalkylene radicals , and that include 9 carbon atoms.

The preferred dihydric phenol is bisphenol-A. The dihydric phenols can be used individually or in combination. Additionally, such dihydric phenols can be used in combination with a dihydric phenol of the following formula: where Y and z with as previously defined. Suitable aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids and mixtures thereof, as well as homologs substituted with alkyls of these carboxylic acids wherein the alkyl groups contain from 1 to about 4 carbon atoms, and acids containing a inert substituent such as halides, alkyl or aryl ethers, and the like. The polyarylates contain from about 95 to 0 mole percent terephthalic acid and from about 5 to 100 mole percent isophthalic acid. Most preferably, the polyarylates contain a mixture of about 25 to about 75 mole percent terephthalic acid and about 75 to about 25 mole percent isophthalic acid. A polyarylate containing a mixture of 50 mole percent terephthalic acid and 50 mole percent isophthalic acid is preferred. The polyarylates of the present invention can be prepared by any of the well-known prior art polyester forming reactions., such as the reaction of the acid chlorides of the aromatic dicarboxylic acids with the dihydric phenol, the reaction of the diaryl esters of the aromatic dicarboxylic acids with the dihydric phenols, and the reaction of the aromatic diacids derived from the diester of the dihydric phenol . These processes are described, for example, in U.S. Patent Nos. 3,317,464; 3,948,856; 3,780,148; 3,824,213 and 3,133,898.

J. Other Polyesters Other polyesters which are suitable for use herein are derived from an aliphatic or cycloaliphatic diol, or mixtures thereof, containing from 2 to about 10 carbon atoms and at least one aromatic dicarboxylic acid. The polyesters which are derived from an aliphatic diol and an aromatic dicarboxylic acid have repeating units of the following general formula: 0 II -c- (I) wherein n is an integer from 2 to 4. Desirably, these other polyesters do not contain the isossrbide portion. However, combinations of different polyesters both containing an isosorbide portion are contemplated. Also contemplated are polyesters described in co-pending application 09 / 064,720 [attorney's file number 032358-008]. The preferred polyester is poly (ethylene terephthalate).

Also contemplated herein are the above polyesters with minor amounts, for example from about 0.5 to about 2 percent by weight, of units derived from aliphatic acids or aliphatic polyols, or both, to form copolyesters. Aliphatic polyols include glycols such as poly (ethylene glycol). These can be made following the teachings, for example, of U.S. Patent Nos. 2,465,319 and 3,047,539. Among the units among which copolyesters may be present are those derived from aliphatic dicarboxylic acids, for example, up to about 50 carbon atoms, including cycloaliphatic straight or branched chain acids, such as adipic acid, cyclohexane diacetic acid, C16-C18 unsaturated acids dimerized (which have 32 to 36 carbon atoms), trimerized acids and the like. In addition, there may be minor amounts of units derived from aliphatic glycols and polyols, for example, up to about 50 ~ carbon atoms including, among others, propylene glycol, glycerol, diethylene glycol, triethylene glycol and the like. The polyesters which are derived from a cycloaliphatic diol and an aromatic dicarboxylic acid are prepared by condensing either the cis or trans isomer (or-10 mixtures thereof), for example, of 1,4-cyclohexanedimethanol with the acid aromatic dicarboxylic so that it produces a polyester having recurring units having the following formula: wherein the cyclohexane ring is selected from the cis and trans isomers thereof, and R represents an aryl radical containing 6 to 20 carbon atoms and which is the dicarboxylic residue derived from an aromatic dicarboxylic acid. Examples of aromatic dicarboxylic acids indicated by R in formula II include isophthalic or terephthalic acid, 1,2-di (p-carboxyphenyl) ethane, 4,4'-dicarboxydiphenylether, etc., and mixtures thereof. All these acids contain at least one aromatic nucleus. Fused rings such as in the 1,4- or 1,5- or 2,6- or 2,7-naphthalenedicarboxylic acids may also be present. Preferred dicarboxylic acids are terephthalic acid or mixtures of terephthalic and isophthalic acid. A preferred polyester can be derived from the reaction of either the cis or trans isomer (or a mixture thereof) of 1,4-cyclohexanedimethanol with a mixture of iso- and terephthalic acids. These polyesters have repeating units of the formula: Another preferred polyester is a copolyester derived from a cyclohexanedimethanol, an alkylene glycol and an aromatic dicarboxylic acid. These copolyesters are prepared by condensing either the cis or trans isomer (or mixtures thereof) of, for example, 1-cyclohexanedimethanol and an alkylene glycol with an aromatic dicarboxylic acid so as to produce a copolyester having repeated units of the following formula: (IV wherein the cyclohexane ring is selected from the cis and trans isomers thereof, R is previously defined, n is an integer from 2 to 4, the x units comprise from about 10 to 90 percent by weight, and the units and units comprise about 10 to about 90 percent by weight. The preferred copolyester can be derived from the reaction of either the cis or trans isomer (or mixtures thereof) of 1,4-cyclohexanedimethanol and ethylene glycol with terephthalic acid in a molar ratio of 1: 2: 3. These copolyesters have repeating units of the following formula: (v) where x and y are as previously defined.

POLYMER COMBINATIONS The polyester polymer of the present invention is desirably used in amounts of about 5 to about 95, preferably about 40 to about 60 percent by weight, and even more desirably about 45 to about 55 percent by weight . The exact composition and the amounts of the various components depend mainly on the desired product. The compositions of this invention are prepared by any conventional mixing method. The preferred method includes mixing the polyester and the thermoplastic polymer or mixtures thereof in pulverized or granular form in an extruder and extruding the mixture into strands, chopping or cutting the strands into granules and molding the granules in the desired article.

ADDITIVES Of course, it will be apparent to those skilled in the art that other additives may be included in the present compositions. These additives include plasticizers; pigments; flame retardant additives, particularly decabromodiphenylether and triaryl phosphates such as triphenyl phosphate; reinforcing agents such as glass fibers; thermal stabilizers; ultraviolet light stabilizers; processing aids; impact modifiers; flow improver additives; nucleating agents to increase crystallinity; and similar. Other possible additives include polymeric additives such as ionomers, liquid crystalline polymers, fluoropolymers, olefins including cyclic olefins, polyamides and ethylene vinyl acetate copolymers. This invention is further illustrated by the following non-limiting examples.

EXAMPLES This section describes the synthesis of polymers used to make combinations with polycarbonate, polybutylene terephthalate (PBT), reinforcing glass fibers, core cover elastomers for hardening and nucleating agents to increase the crystallinity and heat deflection temperatures. The molecular weights of the polymers are estimated based on the inherent viscosity (I.V.) which is measured for a solution 1! (weight / volume) of the polymer in o-chlorophenol at a temperature of 25 ° C. Levels of catalyst components are expressed as ppm, based on a comparison of the weight of the metal with the weight of either dimethyl terephthalate or terephthalic itide, depending on which monomer is used.

Example 1 The following polymerization reagents are added in a Hastalloy B polymerization reactor with a maximum capacity of 189 1 (50 gallons), to which a radius of 15 cm (6") of radius is placed, of a reflux column cooled with water Hastalloy B packed with stainless steel rings, a stainless steel propeller stirrer, a water cooled condenser and a bypass, 78.02 kg of dimethyl terephthalate, 15.42 kg of isosorbide and 49.90 kg of ethylene glycol, which corresponds to a molar ratio of 1: 0.26: 2.00 The catalyst is also charged and consists of 29.57 g of Mn (II) acetate tetrahydrate, 21.43 g of Co (II) acetate tetrahydrate and 35.02 g of Sb (III) oxide. 85 ppm manganese (weight of the metal as a fraction of the weight of dimethyl terephthalate), 90 ppm of cobalt and 375 ppm of antimony, the stirred reactor is purged (50 rpm) with a stream of nitrogen while the temperature is increased to 250 ° C for a period of e 4 hours The reactor is coated and a system of a hot oil circuit, of controlled temperature, is used as a heating medium. The methanol is continuously collected as the reaction is heated above about 150 ° C. By noting the moment when the temperature descends in the upper part of the packed reflux column, it is possible to determine the end of the methanol production, which indicates the completion of the first stage of the reaction, which is the transesterification of the diols and dimethyl terephthalate. At this point, 77 ppm of phosphorus is added in the form of a solution of polyphosphoric acid in ethylene glycol. In this case, 153 ml of the solution is used, which has a concentration of 10.91 g of phosphorus per 100 g of polyphosphoric acid solution. Also this time, the nitrogen purge stops. Heating is continued. The reaction is heated to 285 ° C over a period of about 2 hours. After vacuum is gradually applied using a vacuum pump with a multiple vacuum with a fan with a power of 20 horsepower. Obtaining a complete vacuum, preferably less than 1 Torr, requires approximately 1 hour. During this time, the ethylene glycol is removed by distillation, and a low molecular weight polymer is formed. The molten polymer is heated under vacuum at 285 ° C for about 2 hours, until the polymer obtains a sufficient molten viscosity, determined by an increase in the torque of the agitator. When sufficient viscosity is obtained, the polymerization is stopped, and the reactor is emptied through a heated die in the lower part. The molten polymer emerges as a filament that, when cooled by immersion in a cold water channel, can be chopped or cut into granules. The polymer granules are dried overnight in a rotating drum heated to 120 ° C. The cooled polymer is removed from the flask and crushed. The inherent viscosity of the solution (I.V.) of the material is 0.64 dl / g. The monomeric unit composition of the polymer, determined by NMR of the proton, is about 6% isosorbide, 42% ethylene glycol, 2% diethylene glycol and 50% terephthalic acid, all expressed as moles% of the polymer. It is notable that the amount of isosorbide in the polymer is about half the amount that is charged, when compared to the amount of terephthalic acid. The unreacted isosorbide is found in the distillates, especially in ethylene glycol. The amount of isosorbide in the polymer by this process therefore depends a lot on the efficiency of the distillation or other separation methods that are used in the process. One skilled in the art can easily establish the specific process details according to the characteristics of the reactor, distillation columns and the like.

Example 2 The second example is prepared in a manner similar to the first, except that a smaller reactor is used (maximum capacity of 19 1 (5 gallons)). Equivalent ratios also change in order to prepare a polymer with higher isosorbide content. Therefore, 10,680 g of dimethyl terephthalate, 5,787 g of isosorbide and 4,881 g of ethylene glycol are charged, which corresponds to a molar ratio of 1: 0.72: 1.43 and are charged to the reactor in a manner similar to the foregoing together with the catalyst consisting of 4.76 g of Mn (II) acetate tetrahydrate and 4.66 g of Ge (IV) oxide. This corresponds to 100 ppm manganese (weight of metal as a fraction of the weight of dimethyl terephthalate) and 300 ppm of germanium. The germanium oxide is added in the form of a solution in ethylene glycol (0.100N of Ge02 in ethylene glycol). A solution of polyphosphoric acid in ethylene glycol is added in a manner similar to the above, in this case 9.6 ml, which has a concentration of 3.45 g of P per 100 ml of polyphosphoric acid solution, which is the one used. The polymerization proceeds in a manner similar to the foregoing, however, the resulting finished resin does not obtain the same inherent viscosity within the given time. In this case, an I.V. of solution of 0.42 dl / g. It is also observed that the composition of the polymer monomer unit, determined by proton NMR, is approximately 13% isosorbide, 34% ethylene glycol, 3% diethylene glycol and 50% terephthalic acid, all expressed as moles! of the polymer. The degree of incorporation of isosorbide is a little lower in this case compared to the previously observed, but it reflects the efficiency of the different reactors instead of the polymer that is made.

Example 3 The third example is prepared in a manner similar to the first except that a larger reactor (378 1 (100 gallons)) equipped with a stainless steel anchor type stirrer is used. The monomers that are charged are such that the content of isosorbide in the finished polymer would be 1 mol !, assuming that part of the entering isosorbide is removed by distillation during the polymerization. In this way, 197 kg of dimethyl terephthalate, 5.12 kg of isosorbide and 135 kg of ethylene glycol are used, together with the catalysts: 72.1 g of Mn (II) acetate tetrahydrate, 54.1 g of Co (II) acetate tetrahydrate and 88.5 g of Sb (III) oxide. This corresponds to 82 ppm of manganese, 65 ppm of Co and 375 ppm of Sb, calculated using the same base as in example 1. The transesterification process is carried out analogously to that of example 1. A solution is added of polyphosphoric acid in ethylene glycol so that 80 ppm of P are used to sequester the transition metals after the. transesterification step and before polycondensation, as indicated in example 1. The polycondensation is also similar to that of the previous example. The polymer is extruded or granulated to provide a clear colorless resin.

Unlike the previous example, the resin produced with a lower isosorbide content can be polymerized in the solid state. The granulated polymer is It is loaded in a drum dryer and, under a stream of nitrogen, heated to 115 ° C for a period of 4 hours and then maintained at that temperature for another 6 hours'. This allows the polymer to partially crystallize. After this treatment, vacuum is applied to the drum dryer which finally generates a vacuum of less than 1 mm Hg. The heating continues and reaches a maximum of 213 ° C. It is then kept at this elevated temperature for a total of about 15 hours. This carries out a polymerization in the solid state and allows the molecular weight to be significantly increased, judging by the inherent viscosity (I.V.) of the polymer solution in ortho-chlorophenol. The I.V. of the material solution is increased from about 0.5 dl / g to about 0.7 dl / g during polymerization in the solid state.

Example 4 This polymer is prepared in a manner similar to that of Example 3, except that the amounts of diols are charged in order to result in a resin with a slightly increased isosorbide content. Therefore, the only alterations are in the amount of loaded isosorbide, 17.8 kg, and the amount of Mn (II) acetate tetrahydrate catalyst used, 79.2 g, corresponding to 90 ppm of Mn (II) calculated therein base than in the previous example. The transesterification and polycondensation are repeated as just described. In addition, the finished polymer is granulated, crystallized and polymerized in the solid state in a manner identical to the previous example. This results in a polymer with a content of about 3 moles! of isosorbide.

Example 5 This example describes a combination of polymers containing isosorbide with polycarbonate. A polymer made by Example 2 is combined with polycarbonate to make a more resistant material and at the same time maintain optical transparency on contact. The polycarbonate is obtained from Dow Chemical (caliber 302) and combined with the polymer of Example 2 in a Leistritz extruder (model MC 18GG / GL, Leistritz AG). The design of the twin screws consists of conveyor elements, 3 kneading blocks and then additional transport elements. The ratio of the length L to the diameter D is 30. The temperature of the barrel is 260 ° C and the rotation speed of the screw is 225 rpm. The extrudate is granulated, dried overnight and molded into tension and bending bars for mechanical testing. The molding machine is an Arburg Allrounder (model 220 M) manufactured by Arburg Maschinen Fabrik (Lossburg, Germany). The molding conditions are: barrel temperature, 280 ° C, the mold temperature is 50 ° C, the screw speed is 210 rpm and the injection pressure is 25 bar, with a cooling time of 25 seconds . The composition and physical properties of the combinations are shown in Table 1. The optical turbidity of the combinations is measured in a bending bar with a Macbeth Color Eye 7000 instrument (Kollmorgen Instruments) in accordance with ASTM D1003 (published by the American Society of Testing Materials, Philadelphia, Pennsylvania, vol 8.01). The molded samples have contact transparency.

Table 1 na: not available.

Example 6 This example describes a combination of polymers containing isosorbide together with PBT and a core shell elastomer to strengthen the combination. The polymer of Example 1 (PEIT-6) is combined with PBT (Celanex 1600) obtained from Hoechst Ticona (Summit, NJ) and E920 core shell elastomers obtained from Kanake (Kanake Texas Corporation, Houston, Texas) in a Leistritz extruder. as in the. example 5. The samples are injection molded and tested to determine their mechanical properties using the same procedures indicated in example 5. Table 2 shows the compositions and the mechanical results.

Table 2 rnb: without rupture Example 7 This example describes a combination of polymers containing isosorbide together with PBT and glass fiber. The fiberglass rigidifies and increases the module of the combination. The polymer of Example 1 (PEIT-6) is combined with PBT (Celanex 1600) obtained from Hoechst Ticona (Summit, NJ) and OCF 183 glass fiber (PPG, Pittsburgh, PA) in a Leistritz extruder as in Example 5. The samples are injection molded and tested to determine their mechanical properties using the same procedures indicated in example 5. Table 3 shows the compositions and mechanical results. Table 3 It should be understood that the modalities described in the foregoing are only illustrative and that any modification thereto may occur to a person skilled in the art. Accordingly, this invention is not considered limited to the modalities described herein. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention

Claims (23)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A polymer combination, comprising: (1) a polyester comprising portions of terephthaloyl and, optionally, other portions of aromatic diacid; portions of ethylene glycol; portions of diethylene glycol; portions of isosorbide and, optionally, one or more additional diol portions, wherein the polyester has an inherent viscosity of at least about 0.35 dl / g when measured as a 1%, weight / volume, solution of the polyester in o- chlorophenol at a temperature of 25 ° C; and (2) another thermoplastic polymer.

2. The polymer combination according to claim 1, characterized in that the other thermoplastic polymer is selected from the group consisting of polycarbonates, styrene resins, alkyl acrylate resins, polyurethane resins, vinyl chloride polymer, polyarylethers, copolyester ethers, polyhydroxyethers, polyarylates, and other polyesters.

3. The polymer blend according to claim 1, characterized in that the polyester comprises about 40% to about 50% of the terephthaloyl portions and a total of up to about 10 moles, of one or more optional additional aromatic diacid portions.

4. The polymer combination according to claim 3, characterized in that the terephthaloyl moieties are derived from terephthalic acid or dimethyl terephthalate.

5. The polymer combination according to claim 3, characterized in that the ethylene glycol portions are present in an amount of about 10 moles! at approximately 49.5% of the polyester, the portions of diethylene glycol are present in the amount of about 0.25 moles! to approximately 10 moles! of polyester, the isosorbide portions are present in an amount of about 0.25 moles! to approximately 40 moles! of the polyester, and one or more additional diol portions are present in an amount of about 15 moles! of polyester.

6. The polymer combination according to claim 1, characterized in that one or more additional diol portions are derived from aliphatic alkylene glycols, branched aliphatic glycols having 3-12 carbon atoms and having an empirical formula, HO-CnH; -? p, where n is an integer of 3-12; cis or trans-1,4-cyclohexanedimethanol or mixtures thereof; triethylene glycol; 2,2-bis [4- (2-hydroxy or i) phenyl] propane; 1, l-bis [4- (2-hydroxyethoxy) phenyl] cydohexane; 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene; 1.4: 3, 6-dianhydromannirol; 1,: 3, 6-dianhydroiditol; and 1, -anhydroerythritol.

7. The polyester combination according to claim 1, characterized in that the portions of additional aromatic diacids are derived from isophthalic acid, 2,5-furanodicarboxylic acid, 2,5-thiophenecarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2 - acid. Naphthalenedicarboxylic acid and ', -bibenzoic acid.

8. The polyester combination according to claim 1, characterized in that the terephthaloyl moieties are present in a range of about 45 moles, to about 50 moles, of the polyester, the portions of additional aromatic diacids are present in an amount of up to about 5 moles. moles! of polyester, portions of ethylene glycol are present in an amount of about 10 moles! at approximately 49.5 moles! of polyester, portions of diethylene glycol are present in an amount of about 0.25 moles! to approximately 5 moles! of polyester, the isosorbide portions are present in an amount of about 0.25 moles! to approximately 30 moles! of the polyester, and the other portions of the diol are present in an amount of up to about 10 moles! of polyester.

9. The polyester combination according to claim 8, characterized in that the other diol portions are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, or mixtures thereof.

10. The polyester combination according to claim 9, characterized in that optional additional aromatic diacid portions are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid or mixtures thereof.

11. The polyester combination according to claim 1, characterized in that the polyester has an inherent viscosity of at least about 0.50 dl / g.

12. The polyester combination according to claim 10, characterized in that the polyester has an inherent viscosity of at least about 0.65 dl / g.

13. A polyester combination, characterized in that it comprises: (1) a polyester comprising portions of terephthaloyl and, optionally, other aromatic diacid portions; portions of ethylene glycol; portions of isosorbide; and optionally, one or more additional diol portions, wherein the polyester has an inherent viscosity of at least about 0.5 dl / g when measured as a 1%, weight / volume solution of the polyester in o-chlorophenol at a temperature of 25 ° C, and (2) another thermoplastic polymer.

14. The polymer combination according to claim 1, characterized in that the other thermoplastic polymer is selected from the group consisting of polycarbonates, styrene resins, alkyl acrylate resins, polyurethane resins, vinyl chloride polymer, polyarylethers, copolyester esters, polyhydroxy ethers, polyarylates, copolymers of ethyl vinyl acetate and other polyesters.

15. The polyester combination according to claim 14, characterized in that the polyester comprises about 40% to about 50% terephthaloyl portions and a total of up to about 10 moles, of one or more optional additional aromatic diacid portions.

16. The polyester combination according to claim 14, characterized in that the terephthaloyl moieties are derived from terephthalic acid or dimethyl terephthalate.

17. The polyester combination according to claim 13, characterized in that the ethylene glycol portions are present in an amount of about 10 moles! at approximately 49.5! of polyester, portions of diethylene glycol are present in the amount of about 0.25 moles! to approximately 10 moles! of polyester, the isosorbide portions are present in an amount of about 0.25 moles! to approximately 40 moles! of the polyester, and one or more additional diol portions are present in an amount of about 15 moles! of polyester.

18. The polyester combination according to claim 13, characterized in that one or more additional diol portions are derived from aliphatic alkylene glycols or branched aliphatic glycols having 3-12 carbon atoms and having an empirical formula, H0-CnH2n-0H , where n is an integer of 3-12; cis or trans-1,4-cyclohexanedimethanol or mixtures thereof; triethylene glycol; 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane; 1, l-bis [4- (2-hydroxyethoxy) phenyl] cydohexane; 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene; 1.4: 3, 6-dianhydromanitol; 1.4: 3, 6-dianhydroiditol; and 1, 4 -anhydroerythritol.

19. The polyester combination according to claim 13, characterized in that one or more optional additional aromatic diacid portions are derived from isophthalic acid, 2,5-furanodicarboxylic acid, 2,5-thiophenecarboxylic acid, 2,6-naphthalene dicarboxylic acid, acid 2, 7-naphthalenedicarboxylic acid, and 4,4'-benzoic acid.

20. The polyester combination according to claim 13, characterized in that the terephthaloyl portions are present in an amount of - § 8 - approximately 45 moles! at approximately 50 moles! of polyester, optional additional aromatic diacid portions are present in an amount of up to about 5 moles! of polyester, portions of ethylene glycol are present in an amount of about 10 moles! at approximately 49.5 moles! of polyester, the isosorbide portions are present in an amount of about 0.25 moles! to approximately 30 moles! of polyester, and optional additional diol portions are present in an amount of up to about 10 moles! of polyester.

21. The polyester combination according to claim 20, characterized in that the additional diol portions are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, or mixtures thereof.

22. The polyester combination according to claim 13, characterized in that the additional aromatic diacid portions are derived from isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-bibenzoic acid or mixtures thereof.

23. The polyester combination according to claim 13, characterized in that the polyester has an inherent viscosity of at least about 0.65 dl / g.