MXPA00010288A - Polyesters including isosorbide as a comonomer and methods for making same - Google Patents

Abstract

An isotropic polyester polymer and method for making the polyester is prepared by (1) combining in a reactor a monomer containing a terephthaloyl moiety;optionally, one or more other monomers containing an aromatic diacid moiety;a monomer comprising an ethylene glycol moiety;a monomer containing an isosorbide moiety;optionally, one or more other monomers containing a diol moiety;and optionally, a monomer containing a diethylene glycol moiety;with a condensation catalyst suitable for condensing aromatic diacids and glycols;and (2) heating the monomers and catalyst to polymerize the monomers to yield a polyester having an inherent viscosity of at least about 0.35 dL/g.

Description

POLYESTERS THAT INCLUDE ISOSORBIDE AS A COMONOMER AND METHODS TO MAKE THEMSELVES FIELD OF THE INVENTION The invention relates to polyesters and methods for making polyesters, and more specifically to polyesters containing an isosorbide portion, and methods for making them.

ANTECEDENTS OF THE TECHNIQUE The 1, 4: 3, 6-dianhydro-D-sorbitol diol, referred to in the following as isosorbide, the structure of which is illustrated below, is easily manufactured 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: 123436 Isosorbide or monomer has been incorporated into the polyester which 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 (1993). 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 moieties 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. Polymer 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 including 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 the 1, 4: 3, 6-dianhydrosorbitol portion has not been made. Published PCT applications WO 97/14739 and 0 96/25449 disclose cholesteric and nematic liquid crystal polyesters including isosorbide moieties as monomer units. Such polyesters have relatively low molecular weights and are not isotropic.

BRIEF DESCRIPTION OF THE INVENTION Contrary to the teachings and 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 process conditions of the present invention, particularly the amounts of monomers given, depends on the polymer composition desired. The amount of monomer is desirably chosen so that the final polymer product contains the desired amounts of the various monomer units, desirably with equimolar amounts and monomer units derived from a diol and a diacid. Due to the volatility of some of the monomers, which include isosorbide, and depending on such variables for example if the reactor is sealed (ie, under pressure) and the efficiency of the distillation columns used in synthesizing the polymer, some of the the monomers are desirably included in excess at the start of the polymerization reaction and are removed by distillation as the reaction proceeds. This is particularly true for ethylene glycol and isosorbide. In the polymerization process, the monomers are combined, and heated gradually with mixing with a catalyst or catalyst mixture to a temperature in the range of about 260 ° C to about 300 ° C, desirably 280 ° C to about 285 ° C.

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 catalyst used can be modified as the reaction progresses. The heating and stirring continue for a sufficient time and at a sufficient temperature, generally with removal by distillation of excess reagents, to provide a molten polymer having a molecular weight high enough to be suitable for making manufactured products. In a preferred embodiment, the number of terephthaloyl moieties in the polymer is in the range of from about 25% to about 50 mole% (moles% of the total polymer). The 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-thiophenecarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2, 7 acid. -naphthalenedicarboxylic acid, and 4, t-benzoic acid, at combined concentrations of up to about 25 mole% (moles% of total polymer). In a preferred embodiment, the ethylene glycol monomer units are present in amounts of about 5 moles to about 49.75 moles%. The polymer may also contain portions of diethylene glycol. depending on the manufacturing method, the amount of diethylene glycol portions is in the range of about 0.0 mole% to about 25 mole%. In a preferred embodiment, the isosorbide is present in the polymer in amounts in the range of about 0.25 mole% to about 40 mole%. One or more diol monomer units may also be included in amounts up to a total of about 45 mole%. 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 polymer. This equilibrium is desirable to obtain a high molecular weight. The polyester 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 items and coatings. For other applications, such as compact discs, an inherent viscosity of at least about 0.4 dl / g is preferred. Higher inherent viscosities, such as at least about 0.5 dl / g are necessary for many other applications (eg bottles, films, foils, molded resin). Further processing of the polyester can obtain inherent viscosities that are even higher.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES OF THE DESCRIPTION The isotropic polyester polymer, described in detail in the following, can 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 moles! at about 49.75 moles%, preferably 10 moles! at about 49.5 moles, and much more preferably about 25 moles! to approximately 48 moles!, even more preferably approximately 25 moles! to approximately 40 moles !. The polymer may also contain diethylene glycol monomer units. Depending on the manufacturing method, the amount of diethylene glycol monomer units is in the range of about 0.0 moles! to approximately 25 moles !. Preferably, 0.25 moles! to about 10 moles, and more preferably Q.25 moles! to approximately 5 moles !. Diethylene glycol can be produced as a byproduct of the polymerization process and can also be added to help accurately regulate the amounts of diethylene glycol monomer units that are in the polymer. In a preferred embodiment, the isosorbide portions are present in the polymer in amounts in the range of about 0.25 moles! to about 40 moles, preferably about 0.25 moles! at about 30 moles, and more preferably about 0.5 moles! to 20 moles ?. Depending on the application, the isosorbide can be present in any desirable range such as 1 mol! to 3 moles, 1 mole! to 6 moles !, 1 mole! to 8 moles !, and 1 mole! to 20 moles !. Optionally, one or more monomer units of another diol may be included in amounts up to a total of about 45 moles, preferably less than 20 moles! and even more preferably less than 15 moles, even more preferably less than 10 moles, 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 HO-CnH2n-OH, wherein n is an integer of 3-12, including branched diols such as 2, 2-dimethyl-1-, 3-propanediol; cis or trans-1,4-cyclohexanedi-methanol and mixtures of cis and trans isomers; 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. In a preferred embodiment, the number of terephthaloyl moieties in polymer is in the range of about 25 moles! to about 50 moles, more preferably about 40 moles! to about 50 moles, even more preferably about 45 moles! at approximately 50 moles! (moles of the total polymer). The 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, acid 2, 7-naphthalenedicarboxylic acid, and 4, 4-benzoic acid, at combined levels of up to about 25 moles, preferably up to 10 moles, much more preferably up to about 5 moles! (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 polymer. This equilibrium is desirable to obtain a high molecular weight. Polyester has an inherent viscosity, which is an indicator of molecular weight, of at least about 0.35 dl / g, measured in a solution 1! (weight / volume) 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 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. Some of the polyesters of the invention can be manufactured 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 diol monomers with the acid chlorides of terephthalic 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 solvent (for example toluene) in the presence of a base, such as pyridine, which neutralizes 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 can also be used using terephthaloyl dichloride (for example interfacial polymerization) or the monomers can simply be stirred together while heating. - When the polymer is made using acid chloride, the ratio of monomer units in the product polymer is about 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. Desirably a stoichiometric equivalent of the diol and the diacid is used to obtain a high molecular weight polymer. The polymers can also be made by a melt polymerization process, in which the acid component is either 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, and 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 distilled from the reactor as the polymerization proceeds. The conditions of the melt process of the present invention, particularly the amounts of monomers used, depend on the polymer composition desired. 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 approximately 100 moles!, more 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. The 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 other optional diols are charged in an amount of up to about 100 moles! of the diacid monomers. The ranges provided for the monomers are very wide due to the wide variation in monomer loss during polymerization, depending on the efficiency of the installation columns and other kinds of recovery and recycling systems, and 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 melt polymerization process of the invention, the monomers are combined, and gradually heated by mixing with a catalyst or catalyst mixture to a temperature in the range of about 260 ° C to about 300 ° C, desirably from 280 ° C to 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 temperature is sufficient, generally with removal with distillation of the excess reagents, to provide a molten polymer having a sufficiently high molecular weight to be suitable for manufacturing manufactured products. . 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 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 of about 0.1! to about 10, preferably about 0.25! at about 5! on a molar basis of isosorbide portions, about 49.9 to about 33% on a molar basis of ethylene glycol portions, about 0.0 to 5.0%, preferably 0.25% to about 5% on a molar basis of diethylene glycol portions, and at most about 2% on a molar base of other diol portions, such as 1,4-cyclohexanedimethanol. For bottle resins, the diacid comprises portions of terephthaloyl at a level of from about 35% to about 50% on a molar basis, and optionally the aromatic diacid portions at levels of up to about 15% on a molar basis, wherein the optional aromatic diacid portions from 2-6-naphthalenedicarboxylic acid, isophthalic acid, 4,4'-dibenzoic acid and mixtures of the same. For applications where it is desirable to obtain 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% to about 30% on a molar basis, the portions of ethylene glycol are present in an amount of about 10% to about 48% on a molar basis, optionally other diols such as the 1,4-cyclohexanedimethanol portions are present in a maximum amount of about 45% on a molar basis, the diethylene glycol portions they are present in an amount of from about 0.0% to about 5%, preferably 0.25! at about 5! in a molsr base, the terephthaloyl moieties are present at a level of about 25% to about 50% and other optional diacid moieties, such as 2,6-naphthalene dicarboxylic acid, isophthalic acid, 4,4'-dibenzoic acid and mixtures of they 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 low conditions. which can crystallize. The melt polymerization process of the present invention is desirably carried out either using dimethyl esters (for example dimethyl terephthalate) as reactants, or using the free diacid as a reagent. Each process has its own preferred catalyst and its preferred conditions. These are generally described in the following. These are analogues which are well-known processes for the preparation of poly (ethylene terephthalate). The utility of these methods for obtaining a high molecular weight polymer is surprising in view of the descriptions by others who have worked with isosorbide polyesters and in view of what is generally expected to be that the secondary diols have low reactivities and the esters of secondary alcohols have reduced thermal stability. These two processes are a little different and are described later.

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 diester 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 these dimethyl 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. The catalysts carrying out the ester exchange include salts (usually acetates) of the following metals: Li, Ca, Mg, Mn, Zn, Pb and combinations thereof, Ti (OR) 4, wherein R is an alkyl group 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 (II) 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.

The 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). • 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, more preferably. preferably between about 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 polycondensation reaction temperature 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 0.5 dl / g, and generally up to about 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 process of dimethyl terephthalate except that the initial esterification 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 (approximately 10% to approximately 60%) of diols is used (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. There is no need to add catalyst in the esterification reaction. 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 that 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), Sb (III) oxide and Ge (IV) , and Ti (OR) 4 (wherein R is an alkyl group having 2 to 12 carbon atoms). Oxides solubilized with glycol from 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 reagents and catalyst can be charged to the reactor at room temperature and then can be gradually heated up 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 about 275 ° C at about 285 ° C under high vacuum (less than 10 Torr, preferably less than 1 Torr). The vacuum is necessary to remove the residual ethylene glycol, the isosorbide. and the water vapor of the reaction to increase the 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 observed facially by the torque required to maintain the stirring of the molten polymer.

POLYMERIZATION IN 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 product, isosorbide and terephthalic acid compositions having isosorbide in an amount of about 0.25! at about 10! on a molar basis they 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 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. 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; auxiliaries in the processing of ultraviolet light stabilizers, impact modifiers, flow improver additives, nucleating agents to increase crystallinity and the like. Other possible additives include polymeric additives including ionomers, liquid crystal polymers, fluoropolymers, olefins including cyclic olefins, polyamides, copolymers of ethylene and vinyl acetate and the like. This invention is further illustrated by the following non-limiting examples.

EXAMPLES 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 acid, depending on which monomer is used.

Example 1 The following polymerization reagents are added to a 4-liter polymerization flask coated with a Vigreux column with air cooling, a mechanical stirrer and a water-cooled condenser; 780. 133 g of dimethyl terephthalate, 70,531 g of isosorbide and 531,211 g of ethylene glycol. The reagents are present in a molar ratio of 1: 0.12: 2.13, respectively. The catalyst is also charged and consists of 0.296 g of Mn (II) acetate tetrahydrate, 0.214 g of Co (II) acetate tetrahydrate and 0.350 g of Sb (III) oxide. This corresponds to 85 ppm manganese (weight of the metal as a fraction of the weight of dimethyl terephthalate), 65 ppm of cobalt and 375 ppm of antimony. The flask is purged with a stream of nitrogen while the temperature is increased to 150 ° C for a period of 1 hour, using a fluidized sand bath as a heating medium. At this time the nitrogen purge is stopped and the methanol production begins. The methanol is continuously collected as the reaction is further heated to 250 ° C over the course of about 2 hours. By noting the moment in which the temperature drops in the upper part of the Vigreux 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, 82 ppm of phosphorus is added in the form of a solution of polyphosphoric acid in ethylene glycol. In this case, 1854 g of the solution is used, which has a concentration of 10.91 g of P per 100 g of polyphosphoric acid solution. Heating is continued. The reaction is heated to 285 ° C over a period of about 2 hours. Then vacuum is applied. Alternatively, vacuum may be applied gradually after the polyphosphoric acid solution is added, which allows the heating to 285 ° C to be performed more quickly, and therefore a shorter time (approximately 12 hours) is required. During this time, ethylene glycol is distilled off, and a low molecular weight polymer is formed. Once the reaction reaches 285 ° C, it is placed under vacuum if it is not in advance placed under vacuum. It is preferred to obtain a vacuum of minus 1 Torr. The molten polymer is heated under vacuum at 285 ° C for about 2 hours, until the polymer acquires 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 flask is removed from the sand bath. The molten polymer is extruded and granules are formed, or the cooled polymer is removed from the flask and crushed. The polymer in the form of chopped or crushed granules is placed on an aluminum tray in an oven. Under a stream of nitrogen, the polymer is heated at 115 ° C for a period of 4 hours and then maintained at that temperature for another 6 hours. This allows the polymer flakes to partially crystallize. After this treatment, the polymer is placed in a stream of nitrogen and heated, again for a period of 4 hours, at 190 ° -195 ° C and maintained at this elevated temperature for another 12 hours. This accomplishes a solid state polymerization and allows the molecular weight to be significantly increased, judging by the inherent viscosity (I.V.) of the polymer solution in ortho-chlorophenol. The solution I.V. of the material is increased from about 0.5 dl / g to about 0.-7 dl / g during the solid state polymerization. The monomeric polymer unit composition, determined by proton NMR, is approximately 3! of isosorbide, 46% ethylene glycol, 1! of diethylene glycol and 50% terephthalic acid, 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, in this way depends a lot on the efficiency of the distillation or other separation methods that are used in the process. A person skilled in the art can easily establish the specific process details according to the characteristics of the reactor, the distillation columns and the like.

Example 2 The following monomers are added to a reactor 19 1 (5 gallons): 8,638.9 g of terephthalic acid; 911.9 g of isosorbide; and 3,808.5 g of ethylene glycol. The reagents are present in a molar ratio of 1: 0.12: 1.18, respectively. The catalyst components are also added at this time, as follows: 1825 g of Co (• II) acetate tetrahydrate; 3.103 g of Sb (III) oxide. The amounts of catalyst correspond to 50 ppm of cobalt and 275 ppm of antimony, expressed as the weight of the metal in comparison with the weight of the terephthalic acid. The polymerization reactor is equipped with a fractional distillation column and an agitator. The reactor is purged with nitrogen and then closed under 345 kPa (50 psi) of nitrogen pressure. The temperature is increased to 265 ° C for a period of about 5 hours while the reactants are stirred. The pressure is increased to 482 kPa (70 psi) during this time, as the esterification is carried out. At the end of this interval, the pressure is again vented to 345 kPa (50 psi). Water and ethylene glycol are distilled from the reactor. The temperature is maintained at 265 ° C. In the next hour, the content of the reactor is a viscous and transparent melt. The excess pressure in the reactor is then vented. A solution of ethylene glycol and phosphoric acid (3.45 wt.% Phosphorus) is pumped into the reactor. This corresponds to approximately 50 ppm phosphorus (weight of phosphorus compared to the weight of terephthalic acid). The reactor is then placed under vacuum, while the reactor is heated to the polymerization temperature of 285 ° C. Distillation of water and excess diol is continued. A final vacuum of 1 Torr is reached in the next hour. Polymerization and distillation continue for an additional 2-3 hours, at which time the torque of the agitator reaches a predetermined level. The polymerization is stopped and the molten polymer is extruded from the reactor, cooled and minced. This polymer is almost identical to the polymer made in Example 1 before polymerization in the solid state. It has an inherent viscosity of approximately 0.5 dl / g. The monomeric composition of the polymer, determined by NMR of the proton, is as follows: terephthalic acid, 50%; isosorbide, 3%; ethylene glycol, 46 !; and diethylene glycol, 1 !. Its inherent viscosity is further increased from about 0.5 dl / g to about 0.7 dl / g, using the same solid state polymerization procedure, when used in example 1.

Example 3 7.48 kg of purified terephthalic acid are placed, 3. 55 kg of isosorbide and 1.70 kg of ethylene glycol, in a stirring stainless steel reactor, preheated to 70 ° C under a nitrogen purge at atmospheric pressure. The reactor is equipped with a packed distillation column. The composition of the monomer corresponds to the molar ratio of the terephthalic acid: ethylene glycol: isosorbide of 1: 0.61: 0.54. The reactor is heated to 285 ° C in the next 3 hours and the reaction mixture is maintained under a positive pressure of 345-414 kPa (50-60 psi). During this time, a water distillate is mainly collected from the packed column. After the melting temperature reaches at least 275 ° C, and terephthalic acid is essentially consumed, determined by clearing the reaction mixture, the pressure is released and 3.77 g of germanium oxide catalyst (IV) is added. ) to a solution of ethylene glycol (O.IOON of Ge02 ethylene glycol.) The reaction mixture is stirred for an additional 20 minutes.The pressure in the reactor is reduced to 1-2 mm of mercury over a period of 1 hour and a fraction is collected. Further, the reaction product, a viscous resin, is extruded in a water bath, cut into granules and dried in an oven.The resin has a vitreous transition temperature of 116 ° C and an inherent viscosity. 0.43 dl / g (measured at 25 ° C in a 1: (w / v) orthochlorophenol solution.) The monomeric composition of the polymer is measured by NMR as 49.5 μl of terephthalate, 30.3 μl of ethylene glycol residue, 2.0 μl. diethylene glycol residue and 18.2 % isosorbide residue, expressed as one mol% of the polymer.

Example 4 .68 kg of dimethyl terephthalate, 5.79 kg of isosorbide, 4.88 kg of ethylene glycol, 4.76 g of manganese acetate (II) are placed in a stirred reactor, stainless steel, under nitrogen purge at atmospheric pressure. The reactor is equipped with a filler distillation column. The composition of the monomer corresponds to a molar ratio of dimethyl terephthalate: ethylene glycol: isosorbide of 1: 1.43: 0.72. The reactor is heated to 230 ° C in the next three hours, to 240 during the next hour and to 265 during the next hour. During this time, a distillate consisting mainly of methanol is collected from the packed column. After the temperature reaches 284 ° C, polyphosphoric acid is added to the reactor. The amount of polyphosphoric acid is equivalent to 402 mg of phosphorus. 4.66 g of germanium oxide (IV) catalyst is added as a solution in ethylene glycol (O.IOON of Ge02 in ethylene glycol). The pressure inside the reactor is now reduced to .1 ml of mercury for a period of 2 hours. The reaction mixture is kept under vacuum for an additional 3 hours, and an additional distillation fraction is collected while the temperature is increased to 285 ° C. Subsequently, the reaction product, a viscous resin, is extruded in a water bath, cut into granules and dried in an oven. The resin has a glass transition temperature of 106 ° C and an inherent viscosity of 0.43 dl / g (measured at 25 ° C in a 1% (w / v) orthochlorophenol solution). The monomeric composition of the polymer is measured by NMR as 50.1% terephthalate, 33.5% ethylene glycol residue, 2.6% diethylene glycol residue and 12.9% isosorbide residue, expressed as moles. of the polymer.

Example 5 The following monomers and additives are added to a 19 1 (5 gallon) reactor, constructed of 316 stainless steel which is equipped with a reflux column, packed with Pall 316 stainless steel rings and a water cooled condenser: dimethyl terephthalate , 11.65 kg; isosorbide, 4,384 kg; ethylene glycol, 3,724 kg; manganese acetate. (II), 7.02 g; antimony oxide, 4.18 g; and 1, 2, 3, -tetrahydronaphthalene, 125 ml. A nitrogen purge is placed in the reactor and the contents are heated to 250 ° C in the next 180 minutes; and then at 275 ° C for the next 60 minutes. During the heating, a distillate consisting mainly of methanol is collected. When the reaction mixture reaches 270 ° C, polyphosphoric acid is added in an amount equivalent to 25.4 mg of phosphorus. After reaching 275 ° C, the pressure inside the reactor is reduced to 1-2 mm of mercury over a period of 240 minutes. The reaction mixture is maintained at this pressure for 240 minutes and an additional distillate fraction is collected while increasing the temperature to 285 ° C. When the melt viscosity reaches a predetermined level, measured by the torque required to maintain a constant stirrer speed of 50 rpm, the reactor is filled with nitrogen to a pressure of 414 kPa (60 psi) and the polymer extrudes other Instead of a die with a diameter of 3.2 mm (0.125 inches) in a water channel. The polymer chain is cut into granules and dried in an oven at 100 ° C for 10 hours. It is found that the polymer has a vitreous transition of 117 ° C when measured at a heating rate of 10 ° C per minute. The inherent viscosity, measured in o-chlorophenol at 25 ° C, is 0.41 dl / g. The polymer composition, determined by proton NMR spectrometry, is 50.6% portions of terephthalic acid, 17.6% portions of isosorbide, 29.9% portions of ethylene glycol and 1.9% portions of diethylene glycol.

Example 6 The following polymerization reagents are added in a Hastalloy B polymerization reactor with a maximum capacity of 189 1 (50 gallons) which is placed with a reflux column cooled with Hastalloy B water of 15 cm (6") packed with stainless steel rings, a mixer of stainless steel impeller, a condenser cooled with water and a derivation: 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 - This corresponds to 85 ppm of manganese (weight of the metal as a fraction of the weight of dimethyl terephthalate), 90 ppm of cobalt and 35 ppm of antimony. The stirrer reactor (50 rpm) is purged with a stream of nitrogen while the temperature is increased to 250 ° C over a period of 4 hours. The reactor is coated and a system of a hot oil cycle, controlled in terms of 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 P 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. Then vacuum is gradually applied using a vacuum pump with a multiple vacuum with a 20 horsepower fan. 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, is terminated 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 chain that, when cooled by immersion and a cold water channel, can be 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 proton NMR, is about 6% isosorbide, 42% ethylene glycol, 2% diethylene glycol and 50%! of 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.

Ahem 7 The second example is prepared in a manner similar to that of Example 6, except that a smaller reactor is used (maximum capacity of 19 1 (5 gallons)). Equivalent ratios of the reactants also change in order to prepare a polymer with higher isosorbide content. Therefore, 10680 g of dimethyl terephthalate, 5787 g of isosorbide and 4881 g of ethylene glycol are charged to the reactor, which corresponds to a molar ratio of 1: 0.72: 1.43, 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 the metal as a fraction of the weight of dimethyl terephthalate) and 300 ppm of germanium. Germanium oxide is added in the form of a solution in ethylene glycol (O.IOON of Ge02 in ethylene glycol). A solution of polyphosphoric acid in ethylene glycol is added in a similar manner as in the above, and in this case 9.6 ml, which has a concentration of 3.45 g of P per 100 ml of polyphosphoric acid solution, is used. The polymerization is carried out in a manner similar to the above, however, the resulting finished resin does not obtain the same inherent viscosity within the given time. In this case, the I.V. of the 0.42 dl / g solution. It is also observed that the monomeric unit composition of the polymer, determined by NMR of the proton, is about 13! of isosorbide, 34! of ethylene glycol, 3% diethylene glycol and 50% terephthalic acid, all expressed as moles% of the polymer. The degree of incorporation of isosorbide is somewhat lower in this case than in the previously observed one, but it reflects the efficiency of the different reactors instead of the polymer that is manufactured.

Example 8 The third example is prepared in a manner similar to the first, except that a larger **** 378 1 (100 gallon) reactor 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 the 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. The granulated polymer is loaded in a drum dryer and, under a stream of nitrogen, it is heated at 115 ° C for a period of 4 hours and then kept 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 the solid state polymerization.

Example 9 This polymer is prepared in a manner similar to that of Example 8, 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 approximately 3 moles! of isosorbide content.

Example 10 This example describes a combination of polymers containing isosorbide with nucleating agents and glass fiber. The purpose of the nucleating agents is to increase the crystallinity and thereby improve the thermal resistance (heat deflection temperature) of the combinations. The polymer of examples 6, 7 and 9 are bonded by combination with the sodium bicarbonate nucleating agent (Aldrich) and a type of OCF 183 glass fiber (PPG, Pittsburg, PA) using a Leistritz brand extruder (model MC 1866 / GL, Leistritz AG). The combinations are then injection molded into test parts using an Arburg molding machine as described in example 5. The molded parts (example 10a-c) are heat treated in an oven at 130 ° C for 30 minutes. The compositions and results are summarized below. Table - 4d - - 4§ - It should be understood that the modalities described in the foregoing are only illustrative and that modifications to them may occur to a person skilled in the art. Accordingly, this invention does not consider as limited by the modalities as 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 (45)

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

1. A method for making a polyester polymer, characterized in that it comprises: (1) combining in a reactor, a monomer comprising a terephthaloyl portion; optionally one or more additional monomers containing an aromatic diacid moiety; a monomer comprising a portion of ethylene glycol; a monomer comprising a portion of isosorbide; optionally, one or more additional monomers comprising a diol portion; and optionally, a monomer comprising a diethylene glycol portion, with a condensation catalyst suitable for condensing aromatic diacids and glycols; and (2) heating the monomers and the catalyst at a temperature sufficient to polymerize the monomers in a polyester polymer having at least terephthaloyl moieties, ethylene glycol moieties and isosorbide moieties; wherein the heating continues for a sufficient time to provide an isotropic polyester having - 5 - an inherent viscosity of at least about 0.35 dl / g when measured as a 1! (weight (volume) of the polyester in o-chlorophenol at a temperature of 25 ° C.

2 . The method according to claim 1, characterized in that the process further includes agitation of the monomers during heating and the concurrent removal of by-products by distillation or evaporation, or both.

3. The method according to claim 1, characterized in that the monomer comprising a terephthaloyl portion is terephthalic acid.

4. The method in accordance with the claim

3, characterized in that the water and monomer that has not reacted are removed while the monomers polymerize.

5. The method according to claim 1, characterized in that the monomer comprising a terephthaloyl portion is dimethyl terephthalate.

6. The method according to claim 5, characterized in that the methanol and monomer that has not reacted are removed, while the monomers polymerize.

7. The method according to claim 1, characterized in that the process further comprises adding an additive to the process to help retain volatile components.

8. The method according to claim 7, characterized in that the additive is tetrahydronaphthalene.

9. The method according to claim 1, characterized in that one additional optional diols are selected from the group consisting of aliphatic alkylene glycols and 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, -cyclohexanedimethanol and mixtures thereof; 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.

10. The method according to claim 1, characterized in that one or more optional additional aromatic diacids are selected from the group consisting of isophthalic acid, 2,5-furanodicarboxylic acid, 2,5-thiophenecarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, and 4,4'-benzoic acid.

11. The method according to claim 1, characterized in that the monomers are included in such amounts that the terephthaloyl moieties are present in an amount of about 40 moles! at approximately 50 moles! of the polyester, one or more additional aromatic diacid portions are present in an amount of up to about 10 mole% of the polyester, the ethylene glycol moieties 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 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 different diol portions are present in an amount of up to about 15 mol% of the polyester.

12. The method according to claim 11, characterized in that the monomers are included in such amounts that the terephthaloyl moieties are present in an amount of about 45 moles! at approximately 50 moles! of the polyester, one or more optional additional aromatic diacid portions are present in an amount of up to about 5 mole% of the polyester, the ethylene glycol moieties are present in an amount of about 10 mole% to about 49.5 mole! 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 polyester, and other diol portions are present in an amount up to about 10 moles! of polyester.

13. The method according to the claim

1, characterized in that it also comprises increasing the molecular weight of the polyester by polymerization in the solid state.

14. The method according to claim 13, characterized in that the solid state polymerization comprises: a) crystallizing the polyester by heating the polyester at a temperature in the range of about 115 ° C to about 140 ° C or treating the polyester with a solvent which reduces the glass transition temperature of the polyester allowed for crystallization; and b) heating the polyester under vacuum or in a stream of inert gas at an elevated temperature above about 140 ° C, but below the melting temperature of the copolyester to provide a copolyester having an increased inherent viscosity.

15. The method according to claim 14, characterized in that the heating step (b) is carried out at a temperature of about 195 ° to about 198 ° C for about 10 hours.

16. The method according to claim 13, characterized in that the inherent viscosity increases by at least about 0.8 dl / g.

17. The method according to claim 13, characterized in that the polyester comprises from about 0.25 moles! up to approximately 10 moles! of portions of isosorbide.

18. An isotropic polyester, characterized in that it comprises portions of terephthaloyl, 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 solution of 1! (weight / volume) of the polyester in o-chlorophenol at a temperature of 25 ° C.

19. The isotropic polyester, according to claim 18, characterized in that the polyester comprises approximately 40! at approximately 50! of the terephthaloyl portions and a total of up to about 10 moles! of one or more optional additional aromatic diacid portions.

- 20 - The isotropic polyester, according to claim 19, characterized in that the terephthaloyl moieties are derived from terephthalic acid or dimethyl terephthalate.

21. The isotropic polyester, according to claim 19, characterized in that the ethylene glycol portions 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 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 up to about 15 moles! of polyester.

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

23. The isotropic polyester according to claim 18, characterized in that one or more optional additional aromatic diacids are selected from the group consisting of isophthalic acid, 2,5-furanodicarboxylic acid, 2,5-thiopheneca oxbole, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 4,4'-benzoic acid.

^ 24. The isotropic polyester, according to claim 18, characterized in that the terephthaloyl moieties are present in an amount of about 45 moles! at approximately 50 moles! of the polyester, one or more 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, 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 polyester, and other diol portions are present in an amount up to about 10 moles! of polyester.

25. The isotropic polyester according to claim 24, characterized in that other diol portions are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol or mixtures thereof.

26. The isotropic polyester according to claim 25, characterized in that optional additional aromatic diacid portions are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid or mixtures thereof.

27. The isotropic polyester, according to claim 18, characterized in that the polyester has an inherent viscosity of at least 0.40 dl / g.

28. The isotropic polyester, according to claim 18, characterized in that the terephthalate portions are present in an amount of about 45 moles! at approximately 50 moles! of polyester; one or more additional aromatic diacid portions are present in an amount of up to about 5 moles! of the polyester, and are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid or mixtures thereof; portions of ethylene glycol are present in an amount of about 38 moles! at approximately 49.5 moles! of polyester; Diethylene glycol portions are present in an amount of approximately 0.25 moles! to approximately 5 moles! of polyester, the isosorbide portions are present in an amount of about 0.25 moles! to approximately 5 moles! of polyester; and the other optional additional diol portions are present in an amount of up to about 2 moles! of the polyester and are portions of cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol portions, or mixtures thereof; wherein the polyester has an inherent viscosity of at least about 0.45 dl / g.

29. The isotropic polyester, according to claim 18, characterized in that the terephthaloyl moieties are present in an amount of about 45 moles! at approximately 50 moles! of polyester; one or more optional additional aromatic diacid portions are present in an amount of up to about 5 moles! of the polyester, and are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, acid, -bibenzoic acid or mixtures thereof; portions of ethylene glycol are present in an amount of about 10 moles! at approximately 49.5 moles! of polyester; Diethylene glycol portions are present in an amount of approximately 0.25 moles! to approximately 5 moles! of polyester; the isosorbide portions are present in an amount of approximately 6 moles! to approximately 30 moles! of polyester; and other diol portions are present in an amount of up to about 10 moles! of the polyester and are portions of cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol portions, or mixtures thereof.

- 6l - 30. The isotropic polyester, according to claim 18, characterized in that it further comprises an additive wherein the additive is a plasticizer, pigment, flame retardant, reinforcing agent, thermal stabilizer, ultraviolet light stabilizer, impact modifier or flow improver

31. The isotropic polyester, according to claim 30, characterized in that the additive is glass fibers.

32. An isotropic polyester, characterized in that it comprises portions of terephthaloyl; optionally, other portions of aromatic diacid; portions of diethylene glycol; optionally, portions of diethylene glycol; isosorbide portions 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 solution of 1! (weight / volume) of the polymer in o-chlorophenol at a temperature of 25 ° C.

33. The isotropic polyester, according to claim 32, characterized in that the polyester comprises approximately 40! at approximately 50! of the terephthaloyl portions and up to a total of approximately 10 moles! of - e? -One or more additional aromatic diacid portions optional.

34. The isotropic polyester, according to claim 33, characterized in that the terephthaloyl moieties are derived from terephthalic acid or dimethyl terephthalate.

35. The isotropic polyester, according to claim 33, characterized in that the ethylene glycol portions are present in an amount of about 10 moles! at approximately 49.5 moles! of the polyester, the portions of the ethylene glycol are present in an amount of about 0.25 moles! to approximately 10 moles! of the polyester, the isosorbide portions are present in an amount from about 0.25 mol% to about 40 mol% of the polyester and one or more additional diol portions are present in an amount of up to about 15 mol% of the polyester.

36. The isotropic polyester, according to claim 32, characterized in that one or more diol portions are derived from aliphatic alkylene glycols or branched aliphatic glycols having 3-12 carbon atoms and having the empirical formula, HO-CnH2n-OH, in where n is an integer of 3-12; cis or trans-1,4-cyclohexanedimethanol and 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,: 3, 6-dianhydroiditol; or 1,4-anhydroerythritol.

37. The isotropic polyester, according to claim 32, 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, 2, 7-naphthalenedicarboxylic acid, and 4, '-benzoic acid.

38. The isotropic polyester, according to claim 32, characterized in that the terephthaloyl moieties are present in an amount from about 45 mole% to about 50 mole! of the polyester, one or more 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 the polyester, the isosorbide portions are present in an amount of about 0.25 moles! to approximately 30 moles! of polyester, and other diol portions are present in an amount up to about 10 moles! of polyester.

39. The isotropic polyester, according to claim 38, characterized in that the other diol portions are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol or mixtures thereof.

40. The isotropic polyester according to claim 39, characterized in that optional additional aromatic diacid portions are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid or mixtures thereof.

41. The isotropic polyester, according to claim 32, characterized in that the polyester has an inherent viscosity of at least about 0.65 dl / g.

42. The isotropic polyester, according to claim 32, characterized in that the terephthaloyl moieties are present in an amount of about 45 moles! at approximately 50 moles! of polyester; one or more additional aromatic diacid portions are present in an amount of up to -63 -about 5 moles! of the polyester, and are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid or mixtures thereof; portions of ethylene glycol are present in an amount of about 38 moles! at approximately 49.5 moles! of the polyester; Diethylene glycol portions are present in an amount of approximately 0.25 moles! to approximately 5 moles! of polyester, the isosorbide portions are present in an amount of about 0.25 moles! to approximately 5 moles! of polyester; and the other optional additional diol portions are present in an amount of up to about 2 moles! of the polyester and are portions of cis-1, -cyclohexanedimethanol, portions of trans-1, -cyclohexanedimethanol, or mixtures thereof; wherein the polyester has an inherent viscosity of at least about 0.45 dl / g.

43. The isotropic polyester, according to claim 32, characterized in that the terephthaloyl moieties are present in an amount of about 45 moles! at approximately 50 moles! of polyester; one or more optional additional aromatic diacid portions are present in an amount of up to about 5 moles! of the polyester, and are derived from phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid or mixtures thereof; portions of ethylene glycol are present in an amount of about 10 moles! at approximately 44 moles! of polyester; Diethylene glycol portions are present in an amount of approximately 0.25 moles! to approximately 5 moles! of polyester; the isosorbide portions are present in an amount of approximately 6 moles! to approximately 30 moles! of polyester; and the other diol portions are present in an amount of up to about 10 moles! of the polyester and are derived from cis-1,4-cyclohexanedimethanol, trans-1, -cyclohexanedimethanol, or mixtures thereof, wherein the polyester has an inherent viscosity of at least about 0.65 dl / g.

44. The isotropic polyester, according to claim 32, further comprising an additive wherein the additive is a plasticizer, pigment, flame retardant, reinforcing agent, thermal stabilizer, ultraviolet light stabilizer, impact modifier or flow improver.

45. The isotropic polyester, according to claim 44, characterized in that the additive is glass fibers.