Title of Invention

A METHOD OF MAKING A FIBER AND A STAPLE BLEND COMPRISING THE SAME

Abstract

A method of making a fiber, wherein the fiber comprises a polyester, said method composing: 10 a) forming the polyester; b) spinning the polyester into a fiber; and c) drawing the spun fiber, wherein the polyester comprises terephthaloyl moieties; optionally, other aromatic diacid moieties; ethylene glycol moieties; isosorbide moieties; and, 15 optionally, one or more other diol moieties; wherein said polyester has an inherent viscosity of at least about 0.35 dL/g when measured as a 1 % (weight/volume) solution of said polyester in o-chlorophenol at a temperature of25°C.

Full Text

FORM 2 THE- PATENTS ACT 1970 [39 OF 1970] COMPLETE SPECIFICATION [See Section 10] E.I.DU PONT DE NEMOURS AND COMPANY, a Delaware corporation, of 1007 Market Street, Wilmington, Delaware 19898, United Stares of America, The following specification particularly describes the nature of the invention and the manner in which it is to be performed:- Field of the Disclosure This disclosure relates to a polyester fiber, methods of making the same, and articles made therefrom. In particular, this disclosure relates to a fiber of 5 polyester wherein the polyester has an isosorbide moiety, terephthaloyl moiety and ethylene glycol moiety, methods of making the same, and articles made therefrom. Background of the Disclosure Polyester fibers are produced in large quantities for use in a variety of applications. In particular, these fibers are desirable for use in textiles, 10 particularly in combination with natural fibers such as cotton and wool. Clothing, rugs and other items may be fashioned from these fibers. Further, polyester fibers are desirable for use in industrial applications due to their elasticity and strength. In particular, they are used to make articles such as tire cords and ropes. The term "fibers" as used herein is meant to include continuous 15 monofilaments, non-twisted or entangled multifilament yarns, staple yarns, spun yams and non-woven materials. Such fibers may be used to form uneven fabrics, knitted fabrics, fabric webs, or any other fiber-containing structures, such as tire cords. Synthetic fibers, such as nylon, acrylic, polyesters and others, are made by 20 spinning and drawing the polymer into a filament, which is then formed into a yarn by winding many filaments together. These fibers are often treated mechanically and/or chemically to impart desirable characteristics such as strength, elasticity, heat resistance, hand (feel of fabric) and the like as known in the art based on the desired end product to be fashioned from the fibers. WO 99/54534 PCT/US99/07015 The polymers currently used for fiber formation are generally based on completely man-made or synthetic molecules. In contrast, the diol 1,4:3,6-dianhydro-D-sorbitol, referred to hereinafter as isosorbide, the structure of which is illustrated below, is readily made from renewable resources, such as sugars and 5 starches. For example, isosorbide can be made from D-glucose by hydrogenation followed by acid-catalyzed dehydration. OH Isosorbide has been incorporated as a monomer into polyesters that also include terephthaloyl moieties. See, for example, R. Storbeck et al, Makromol. 10 Chem.. Vol. 194, pp. 53-64 (1993); R. Storbeck et al, Polvmer. Vol. 34, p. 5003 (1993). However, it is generally believed that secondary alcohols such as isosorbide have poor reactivity and are sensitive to acid-catalyzed reactions. See, for example, D. Braun et al., J. Prakt.Chem.. Vol. 334, pp. 298-310 (1992). As a result of the poor reactivity, polyesters made with an isosorbide monomer and 15 esters of terephthalic acid 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 moieties, ethylene glycol moieties, and terephthaloyl moieties have been reported only rarely. A copolymer containing 20 these three moieties, in which the mole ratio of ethylene glycol to isosorbide was about 90:10, was reported in published German Patent Application No. 1,263,981 WO 99/54534 PCT/US99/07015 (1968). The polymer was used as a minor component (about 10%) of a blend with polypropylene to improve the dyeabiliiy of polypropylene fiber. It was made by melt polymerization of dimethyl terephthalate, ethylene glycol, and isosorbide. but the conditions, which were described only in general terms in the publication, 5 would not have given a polymer having a high molecular weight. Copolymers of these same three monomers were described again recently, where it was observed that the glass transition temperature Tg of the copolymer increases with isosorbide monomer content up to about 200°C for the isosorbide terephthalate homopolymer. The polymer samples were made by reacting 10 terephthaloyl dichloride in solution with the diol monomers. This method yielded a copolymer with a molecular weight that is apparently higher than was obtained in the German Patent Application described above, but still relatively low when compared against other polyester polymers and copolymers. Further, these polymers were made by solution polymerization and were thus free of diethylene 15 glycol moieties as a product of polymerization. See R. Storbeck, Dissertation, Universitat Karlsruhe (1994); R. Storbeck, et al., J. Appl. Polymer Science. Vol. 59, pp. 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 stoving lacquers. The 20 polyesters are prepared with an alcohol and an acid. One of the many preferred alcohols is dianhydrosorbitol. However, the average molecular weight of the polyesters is from 1,000 to 10,000, and no polyester actually containing a dianhydrosorbitol moiety was made. U.S. Patent 5,179,143 describes a process for the preparation of compression 25 molded materials. Also, described therein are hydroxyl containing polyesters. These hydroxyl containing polyesters are listed to include polyhydric alcohols, including l,4:3,6-dianhydrosorbitol. Again, however, the highest molecular weights -4- - WO 99/54534 PCT/US99/0701S reported are relatively low, i.e. 400 to 10,000, and no polyester actually containing the l,4:3,6-dianhydrosorbitol moiety was made. Published PCT Application WO 97/14739 and WO 96/25449 describe cholesteric and nematic liquid crystalline polyesters that include isosorbide moieties 5 as monomer units. Such polyesters have relatively low molecular weight and are not isotropic. Summary of the Disclosure Contrary to the teachings and expectations that have been published in the prior art, isotropic, i.e., semi-crystalline and amorphous or nonliquid crystalline, 10 copolyestcrs containing terephthaloyl moieties, ethylene glycol moieties, isosorbide moieties and, optionally, diethylene glycol moieties, are readily synthesized in molecular weights that are suitable for making fabricated products such as fibers on an industrial scale. Further, fibers made from these polyesters offer improved strength, elasticity and abrasion resistance. In particular, such fibers show good 15 potential for use in textiles, and may be useful in industrial applications as well. The process conditions for producing the polyester fiber, particularly the amounts of monomers used in the polyester, are desirably chosen so that the final polymeric product used for manufacturing fibers contains thedesired amounts of the various monomer units, preferably with equimolar amounts of monomer units 20 derived from a diol and a diacid. Because of the volatility of some of the monomers. including isosorbide, and depending on the method of manufacture of the polyester, some of the monomers are desirably included in excess at the beginning of the polymerization reaction and removed as the reaction proceeds. This is particularly true of ethylene glycol and isosorbide. 25 The polyester may be formed by any method known in the art. Preferably, however, the polyester is formed by solvent or melt polymerization. The choice of WO 99/54534 PCT/US99/07015 -5- method may be determined by the desired amount of diethylene glycol in the final product. In a preferred embodiment, the number of terephthaloyl moieties in the polymer is in the range of about 25% to about 50 mole % (mole % of the total 5 polymer). The polymer may also include amounts of one or more other aromatic diacid moieties such as, for example, those derived from isophthalic acid, 2,5-furandicarboxylic acid. 2,5-thiophenedicarboxylic acid, 2,6-naphfhalenedi-carboxylic acid, 2.7-naphthalenedicarboxylic acid, and 4,4,-bibenzoic acid at combined levels up to about 25 mole % (mole % of the total polymer). 10 In a preferred embodiment, ethylene glycol monomer units are present in amounts of about 5 mole % to about 49.75 mole %. The polynier may also contain diethylene glycol moieties. Depending on the method of manufacture, the amount of diethylene glycol moieties is in the range of about 0.0 mole % to about 25 mole %. 15 In a preferred embodiment, isosorbide is present in the polymer in amounts in the range of about 0.25 mole % to about 40 mole %. One or more other diol monomer units may also be included in amounts up to a total of about 45 mole %. The polyester has an inherent viscosity, which is an indicator of molecular weight, of at least about 0.35 dL/g, as measured on a 1% (weight/volume) solution 20 of the polymer in o-chlorophenol at a temperature of 25°C. A higher inherent viscosity, such as at least about 0.40 dL/g, preferably at least about 0.50 dL/g. is desired for optimal fiber formation for use in commercial applications, such as textile manufacture. Further processing of the polyester may achieve inherent viscosities up to about 2.0 dL/g and even higher, which can be useful for the 25 formation of fibers for both commercial uses and industrial purposes, such as tire cords, cables and the like. The polyester fibers of the present invention are suitable for use in textile manufacture or other commercial applications, and for use in industrial applications. WO 99/54534 PCT/US99/070I5 -6- They may be woven or knitted to form fabrics, or may be provided in the form of continuous monofilaments, multifilament yarns or staple yams. Detailed Description of the Preferred Embodiments of the Disclosure The polyester fiber and a method of manufacturing the same are described in 5 detail below. In particular, the method of manufacturing a polyester comprising terephthaloyl moieties, ethylene glycol moieties and isosorbide moieties is described, as well as the process of forming fibers from such a polymer for use in commercial or industrial applications. In a preferred embodiment, ethylene glycol monomer units are present in the 10 polymer in amounts of about 33 mole % to about 49.9 mole %, preferably 37 mole % to about 45 mole %, although higher amounts may be included as necessary to achieve the desired results. The polymer composition may also contain diethylene glycol monomer units. Depending on the method of manufacture, the amount of diethylene glycol monomer units is in the range of from about 0.0 mole % to about 15 5.0 mole %, preferably 0.25 mole % to about 5 mole %, although higher amounts may be included as necessary to achieve the desired results. Diethylene glycol may be produced as a by-product of the polymerization process, or may be added directly to the composition to help accurately regulate the amount of diethylene glycol monomer units that are in the polymer. 20 In preferred embodiments, isosorbide moieties are present in the polymer in amounts in the range of from about 0.10 mole % to about 10 mole %, preferably from about 0.25 mole % to about 5.0 mole %, although higher amounts may be included as necessary to achieve the desired results. Isosorbide is most preferably present in the range of 1 mole% to 3 mole %. One or more other diol monomer 25 units may optionally be included in amounts up to a total of about 2.0 mole %, but preferably less than 1 mole %. The amount of other diols included may however be higher as necessary to achieve the desired results. Examples of the optional other WO 99/54534 PCT/US99/070I5 -7- diol units include aliphatic alkylene glycols having from 3-12 carbon atoms and having the empirical formula HO-CnH2n-OH, where n is an integer from 3-12, including branched diols such as 2,2-dimethyl-l,3-propanediol; cis or trans-1,4-cyclohexanedimethanol and mixtures of the cis and trans isomers; triethylene glycol; 5 2,2-bis[4-(2-hydroxyethoxy)phenyl] propane; l,l-bis[4-(2-hydroxy- cthoxy)phenyl]cyclohexane; 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene; 1,4:3,6-dianhydromannitol; l,4:3,6-dianhydroiditol; and 1,4-anhydroerythritol. Tcrephthaloyl moieties in the polyester may range from 25-50 mole %, but are preferably in the range of from about 40-50 mole %, although higher amounts 10 may be included as necessary to achieve the desired results. Other aromatic diacid moieties in the polymer, if desired, may include, for example, those derived from isophthalic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 4,4'-bibenzoic acid, at combined levels up to about 10 mole %, preferably between 0.01 and 5 mole 15 % of the total polymer, although higher amounts may be included as necessary to achieve the desired results. It is preferable that equimolar amounts of diacid monomer units and diol monomer units are present in the polymer in order to achieve a high molecular weight and high inherent viscosity, which provide a lower shrinkage rate and higher 20 glass transition temperature (T„) than, for example, poly(ethylene terephthalate). The polyester formed has an inherent viscosity, which is an indicator of molecular weight, of at least about 0.35 dL/g, as measured on a 1 % (weight/volume) solution of the polymer in o-chlorophenol at a temperature of 25°C. Preferably, the inherent viscosity is at least about 0.45 dL/g. Most preferably, an inherent viscosity of about 25 0.5 - 1.5 is desired. The molecular weight is normally not measured directly. Instead, the inherent viscosity of the polymer in solution or the melt viscosity is used as an indicator of molecular weight. For the present polymers, the inherent viscosity is WO 99/54534 PCT/US99/070I5 -8- measured by the method described previously, with a molecular weight corresponding to an inherent viscosity of about 0.35 dL/g or more. Higher molecular weights corresponding to inherent viscosities of at least about 0.45 dL/g are preferred for commercial applications, and molecular weights corresponding to 5 inherent viscosities of about 0.8 dL/g to 2.0 dL/g, and even higher are desired for industrial uses. Generally, the inherent viscosity/molecular weight relationship can be fitted to the linear equation: log (IV) = 0.586 x log(Mw) - 2.9672. The inherent viscosities arc a better indicator of molecular weight for comparisons 10 of samples and are used as the indicator of molecular weight herein. The polyesters used to make the fibers of the invention can be made by any of several methods. The product compositions vary somewhat depending on the method used, particularly in the amount of diethylene glycol residue that is present in the polymer. These methods include the reaction of the diol monomers with the 15 acid chlorides of terephthalic acid and any other acids that may be present. The reaction of terephthaloyl dichloride with isosorbide and ethylene glycol is readily carried out by combining the monomers in a solvent (e.g., 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, pp. 1199 -1202 20 (1996). Other well-known variations using terephthaloyl dichloride may also be used (e.g., interfacial polymerization), or the monomers may 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 about the same as the ratio of reacting monomers. 25 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 diacids generally will be used to obtain a high molecular weight polymer. WO 99/54534 PCT/US99/07015 -9- The polymers can also be made by a melt polymerization process, in which the acid component is either terephthalic acid or dimethyl terephthlate, and also may include the free acid or dimethyl ester of any other aromatic diacids that may be desired in the polyester polymer composition. The diacids or dimethyl esters are 5 heated with the diols (ethylene glycol, isosorbide, optional diols) in the presence of a catalyst to a high enough temperature that the monomers combine to form esters and diesters, then oligomers, and finally polymers. The polymeric product at the end of the polymerization process is a molten polymer. The diol monomers (e.g., ethylene glycol and isosorbide) are volatile and distill from the reactor as the polymerization 10 proceeds. Therefore, an excess of these diols is desirably charged to 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 efficiency of monomer recovery and recycle. Such modifications in the amounts of monomers and the like in accordance with the characteristics of a reactor are readily 15 made by practitioners in the art. Further, skilled practitioners can readily determine the amount of each component desirably charged to any particular reactor to form the polymer of the invention. The above described melt polymerization process is the preferred method of making the polymer and is described in detail in copending commonly assigned U.S. 20 Application No. 09/064.844 (Attorney Docket No. 032358-001), incorporated herein by reference. The meU polymerization processes using dimethyl terephthalate and terephthalic acid are also summarized below. Dimethyl Terephthalate Process In this process, which is carried out in two stages, terephthalic acid and the 25 optional diacid monomers, if present, are used as their dimethyl ester derivatives. The diols (e.g., ethylene glycol and isosorbide) are mixed with the dimethyl ester of the aromatic diacid (e.g., dimethyl terephthalate) in the presence of an ester WO 99/54534 PCT/US99/07015 -10- interchange catalyst, which causes exchange of the ethylene glycol for the methyl group of the dimethyl esters through a transesterification reaction. This results in the formation of methanol, which distills out of the reaction flask, and bis (2-hydroxyethylterephthalate). Because of the stoichiometry of this reaction, somewhat 5 more than two moles of ethylene glycol arc desirably added as reactants for the ester interchange reaction. Catalysts that bring about ester interchange include salts (usually acetates) of the following metals: Li, Ca, Mg, Mn. Zn, Pb, and combinations thereof, Ti(OR)4, where R is an alky! group having 2-12 carbon atoms, and PbO. The catalyst 10 components are generally included in an amount of about 10 ppm to about 100 ppm. Preferred catalysts for ester interchange include Mn(OAc)2. Co(OAc)-,, and Zn(OAc)2, where OAc is the abbreviation for acetate, and combinations thereof. The polycondensation catalyst used in the second stage of the reaction, preferably Sb(III) oxide, may be added initially or at the start of the polycondensation stage. A 15 catalyst that has been used with particularly good success is based on salts of Mn(II) and Co(II), used in the amount of about 50 to about 100 ppm each. These are preferably used in the form of Mn(II) acetate tetrahydrate and Co(II) acetate tetrahydrate, although other salts of the same metals may also be used. Ester interchange is desirably brought about by heating and stirring the 20 mixture of reactants under an inert atmosphere (e.g., nitrogen) at atmospheric pressure from room temperature to a temperature high enough to induce the ester interchange (about 150°C). Methanol is formed as a by-product and distills out of the reactor. The reaction is gradually heated to about 250°C until methanol evolution stops. The end of methanol evolution can be recognized by a drop in the 25 overhead temperature of the reaction vessel. A small amount of an additive having a boiling point of 170-240 °C may be added to the ester interchange to aid in the heat transfer within the reaction medium and to help retain volatile components in the vessel that may sublime into the packed WO 99/54534 PCT/US99/07015 -11- column. The additive must be inert and not react with alcohols or dimethyl terephthalate at temperatures below 300°C. Preferably, the additive has a boiling point greater than 170°C, more preferably wirfiin the range of 170°C to 240°C\ and is used in an amount between about 0.05 and 10 wt %, more preferably between 5 about 0.25 and 1 wt % of the reaction mixture. A preferred additive is tetrahydronaphthalene. Other examples include diphenyl ether, diphenyl sulfone and benzophenonc. Other such solvents are described in U.S. Patent 4,294.956, the contents of which are hereby incorporated by reference. The second stage of the reaction is commenced by adding a 10 polycondensation catalyst if it was not added at the beginning of the process, and a sequestering agent for the transesterification catalyst. Polyphosphoric acid is an example of a sequestering agent and is normally added in an amount of about 10 to about 100 ppm of phosphorous per gram of dimethyl terephthalate. An example of a polycondensation catalyst is antimony (III) oxide, which may be used at a level of 15 100 to about 400 ppm. The polycondensation reaction is typically carried out at a temperature from about 250°C to 285°C. During this time, ethylene glycol distills out of the reaction due to condensation of the bis(2-hydroxyethyl) terephthalate to form polymer and by-product ethylene glycol, which is collected as a distillate. 20 The polycondensation reaction described above is preferably carried out under vacuum, which can be applied while the reactor is being heated to the temperature of the polycondensation reaction after polyphosphoric acid and Sb(III) oxide have been added. Alternatively, vacuum can be applied after the polycondensation reaction temperature reaches 280°C - 285°C. In either case, the 25 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 pre-determined level. This is observed as an increase in the torque needed for the stirring motor to maintain WO 99/54534 PCT/US99/07015 -12- stirring. An inherent viscosity of at least 0.5 dL/g, and generally up to about 0.65 dL/g or greater, can be achieved by this melt polymerization process without further efforts at raising molecular weight. For certain composition ranges, the molecular weight can be increased further by solid state polymerization, described 5 below. Terephthalic Acid Process The terephthalic acid process is similar to the dimethyl terephthalate process except that the initial esterification reaction that leads to bis(2-hydroxy-ethylterephthalate) and other low molecular weight esters is carried out at a slightly 10 elevated pressure (autogenous pressure, about 25 to 50 psig). Instead of a two-fold excess of diols, a smaller excess (about 10% to about 60%) of diols (ethylene glycol, isosorbide and other diols, if any) is used. The intermediate esterification product is a mixture of oligomers, since not enough diol is present to generate a diester of terephthalic acid. The catalysts are also different. No added catalyst is necessary in 15 the esterification reaction. A polycondensation catalyst (e.g., Sb(III) or Ti(IV) salts) is still desirable to achieve a high molecular weight polymer. The catalyst that is needed to achieve 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 20 that are useful for making a high molecular weight polymer directly from terephthalic acid and the diols include the acetate or other alkanoate salts of Co(II) and Sb(III), oxides of Sb(III) and Ge(IV), and Ti(OR)4 (where R is an alkyl group having 2 to 12 carbon atoms), as well as glycol solubilized metal oxides. The use of these and other catalysts in the preparation of polyesters is well-known in the art. 25 The reaction may be carried out in discrete steps, but this is not necessary. In practice on a large scale, it may be carried out in steps as the reactants and intermediate products are pumped from reactor to reactor at increasing temperatures. WO 99/54534 PCT/US99/07015 -13- ln a batch process, the reactants and catalyst may be charged to a reactor at room temperature and then gradually heated to about 285°C as the polymer forms. The pressure is vented in the range of about 200°C to about 250°C, and a vacuum is then desirably applied. 5 Esterification to form bis(2-hydroxyethylterephthaIate) esters and oligomers takes place at elevated temperatures (between room temperature and about 220°C to 265°C under autogenous pressure), and the polymer is made at temperatures in the range of about 275°C to about 285°C under a high vacuum (less than 10 Torr, preferably less than 1 Torr). The vacuum is needed to remove residual ethylene 10 glycol, isosorbide and water vapor from the reaction to raise 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 achieved by the direct polymerization process, without subsequent solid state polymerization. The progress of the polymerization can be followed by the melt viscosity, which is easily observed by the torque that is 15 required to maintain stirring of the molten polymer at a constant rpm. Solid State Polymerization Polymers can not be made by the melt condensation process described above having an inherent viscosity of about 0.65 dL/g or greater without further treatment. Compositions of ethylene glycol, isosorbide, and terephthalic acid having isosorbide 20 in an amount of about 0.25% to about 10% on a mole basis may have their molecular weight increased further by solid state polymerization. The product made by melt polymerization, after extruding, cooling, and pelletizing, is essentially non¬crystalline. The material can be made semi-crystalline by heating it to a temperature in the range of about 115°C to about 140°C for an extended period of time (about 2 25 to about 12 hours). This induces crystallization so that the product can then be heated to a much higher temperature to raise the molecular weight. The process WO 99/54534 PCT7US99/07015 -14- works best for low levels of isosorbide, from about 0.25 mole % to about 3 mole %, because the polyester crystallizes more easily with low levels of isosorbide. The polymer may also be crystallized prior to solid state polymerization by treatment with a relatively poor solvent for polyesters, such as acetone, which 5 induces crystallization. Such solvents reduce the glass transition temperature T(„), allowing 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 hereby incorporated by reference. The crystallized polymer is subjected to solid state polymerization by placing 10 the pclletized or pulverized polymer into a stream of an inert gas, usually nitrogen, or under a vacuum of 1 Torr, at an elevated temperature, above 140°C but below the melting temperature of the polymer, for a period of about two to 16 hours. Solid state polymerization is generally carried out at a temperature in the range of about 190° to about 210°C for a period of about two to about 16 hours. Good results are 15 obtained by heating the polymer to from about 195° to about 198°C for about 10 hours. This solid state polymerization may raise the inherent viscosity to about 0.8 dL/g or higher. Fiber Production The monomer composition of the polyester polymer is desirably chosen to 20 result in a partially crystalline polymer. This crystallinity is desirable for the formation of fibers, providing strength and elasticity. As first produced, the polyester is mostly amorphous in structure. In preferred embodiments, the polyester polymer readily crystallizes on reheating and/or extension of the polymer. In the process of the invention, fibers are made from the polymer by any 25 process known in the art. Generally, however, melt spinning is preferred for polyester fibers. WO 99/54534 PCT/US99/07015 -15- Melt spinning, which is most commonly used for polyesters such as poly(ethylene terephthalate), comprises heating the polymer to form a molten liquid, or melting the polymer against a heated surface. The molten polymer is forced through a spinneret with a plurality of fine holes. Upon contact with air or a non- 5 reactive gas stream after passing through the spinneret, the polymer solution from each spinneret solidifies into filaments. The filaments are gathered together downstream from the spinneret by a convergence guide, and may be taken up by a roller or a plurality of rollers. This process allows filaments of various sizes and cross sections to be formed, including filaments having a round, elliptical, square. 10 rectangular, lobed or dog-boned cross section, for example. Following the extrusion and uptake of the fiber, the fiber is usually drawn, thereby increasing the crystallization and maximizing desirable properties such as orientation along the longitudinal axis, which increases elasticity, and strength. The drawing may be done in combination with takeup by using a series of rollers, some 15 of which are generally heated, as known in the art, or may be done as a separate stage in the process of fiber formation. The polymer may be spun at speeds of from about 600 to 6000 meters per minute or higher, depending on the desired fiber size. For textile applications, a fiber with a denier per filament of from about 0.1 to about 100'ls desired. 20 Preferably, the denier is about 0.5 to 20, more preferably 0.7 to 10. However, for industrial applications the fiber should be from about 0.5 to 100 denier per filament, preferably about 1.0 to 10.0, most preferably 3.0 to 5.0 denier per filament. The required size and strength of a fiber is application specific, however, and the appropriate size of the fiber can readily be determined by one of ordinary skill in the 25 art for any given application. The resulting filamentary material is amenable to further processing through the use of additional processing equipment, or it may be used directly in applications requiring a continuous filament textile yam. If desired, the filamentary material WO 99/54534 PCT/US99/07015 -16- subsequently may be converted from a flat yarn to a textured yarn through known false twist texturing conditions or other processes known in the art. In particular, ii is desirable to increase the surface area of the fiber to provide a softer feel and to enhance the ability of the fibers to breathe, thereby providing better insulation and 5 water retention in the case of textiles, for example. The fibers may therefore be crimped or twisted by the false twist method, air jet, edge crimp, gear crimp or stuffer box, for example. Alternatively, the fibers may be cut into shorter lengths, called staple, which may be processed into a yarn. A skilled artisan can determine the best method of crimping or twisting based on the desired application and the 10 composition of the fiber. After formation, the fibers are finished by any method appropriate to the desired final use. In the case of textiles, this may include dyeing, sizing or addition of chemical agents such as antistatic agents, flame retardants, UV light stabilizers, antioxidants, pigments, dyes, stain resistants, antimicrobial agents and the like, 15 which are appropriate to adjust the look and hand of the fibers. For industrial applications, the fibers may be treated to impart additional desired characteristics such as strength, elasticity or shrinkage, for example. The continuous filament fiber of the invention may be used either as produced or texturized for use in a variety of applications such as textile fabrics for 20 apparel and home furnishings, for example. High tenacity fiber can be used in industrial applications such as high strength fabrics, tarpaulins, sail cloth, sewing threads and rubber reinforcement for tires and V-belts, for example. The staple fiber of the invention may be used to form a blend with natural fibers, especially cotton and wool. In particular, the polyester is a chemically 25 resistant fiber which is generally resistant to mold, mildew, and other problems inherent to natural fibers. The polyester fiber further provides strength and abrasion resistance and lowers the cost of material. Therefore, it is ideal for use in textiles WO 99/54534 PCT7US99/07015 -17- and other commercial applications, such as for use in fabrics for apparel, home furnishings and carpets. Further, the polyester polymer of the invention may be used with anotiicr synthetic polymer to form a heterogenous fiber, thereby providing a fiber with 5 improved properties. Polymers which may be used include those listed in copending application Serial Nos. 09/064.826 (Attorney Docket No. 032358-005) and 09/064.720 (Attorney Docket No. 032358-008). The heterogeneous fiber may be formed in any suitable manner, such as side-by-side, sheath-core and matrix designs. as known in the art. 10 The polyester polymer of the invention may also be used to form a blend which may be used to produce a fiber having improved properties. Examples of polymers which may be blended with the polyester polymer of the invention are those found for example in co-pending application Serial Nos. 09/064.826 (Attorney Docket No. 032358-005) and 09/064.720 (Attorney Docket No. 032358-008). 15 Further, the fiber may itself be made by any method known in the art using isosorbide-containing polyesters such as those described in copending application Serial Nos. 09/064.826 (Attorney Docket No. 032358-005) and 09/064.720 (Attorney Docket No. 032358-008). The fiber of the invention, its manufacture and properties are further 20 illustrated by the following non-limiting examples. Examples The polymer molecular weights are estimated based on inherent viscosity (I.V.), which is measured for a 1% solution (wt/volume) of polymer in o-chlorophenol at a temperature of 25°C. The levels of catalyst components are 25 expressed as parts per million (ppm), based on a comparison of the weight of the metal with the weight of either the dimethyl terephthalate or terephthalic acid, depending on which monomer is used. WO 99/54534 PCTVUS99/070I5 -18- Example 1 A) Polymerization The following polymerization reactants are added to a 4-liter polymerization flask fitted with a jacketed Vigreux column approximately 14 inches long and 5/8 5 inch in diameter with air cooling, a mechanical stirrer, and a water-cooled condenser: dimethyl terephthalate (780.lg), isosorbide (62.6g), and ethylene glycol (504.7g), which corresponds to a mole ratio of 1: 0.106: 2.13. A catalyst of Mn(II) acetate tetrahydrate (0.296g), Co(ll) acetate tetrahydrate (0.297g), and Sb(III) oxide (0.308g) is also charged. This corresponds to 85 ppm manganese (weight of metal 10 as a fraction of the weight of dimethyl terephthalate), 90 ppm cobalt, and 330 ppm antimony. The flask is purged with a stream of nitrogen while the temperature is raised to 250°C over a period of two hours, using a fluidized sand bath as a heating medium. Methanol is continuously collected as the reaction is heated above approximately 150°C. By noting when the temperature drops at the top of the 15 Vigreux column, it is possible to determine the end of methanol evolution, indicating the finish of the first step of the reaction, which is the transesterification of the diols and dimethyl terephthalate. At this point, 91 ppm of phosphorous is added in the form of a polyphosphoric acid solution in ethylene glycol. In this case, 0.244g of polyphosphoric acid mixed with approximately 1 ml'-of ethylene glycol is 20 used. Also at this time, the nitrogen purge is stopped. Heating is continued while a vacuum is gradually applied. The attainment of full vacuum, preferably less than 1 Torr, takes approximately 1 hour. During this hour, the reaction mixture is heated to 285°C. Also during this time, ethylene glycol distills off, and a low molecular weight polymer forms. The molten polymer is heated under vacuum at 285°C for 25 about 2 hours, or until the polymer achieves sufficient melt viscosity, as determined by an increase in torque of the stirrer. When sufficient viscosity is achieved, the polymerization is stopped, and the flask is removed from the sand bath. WO 99/54534 PCTYUS99/070I5 -19- The cooled polymer is removed from the flask and ground. The solution inherent viscosity (I.V.) of the material is 0.44 dL/g. The monomer unit composition of the polymer, determined by proton NMR, is about 3% isosorbide, 44% ethylene gylcol, 3% diethylene glycol, and 50% terephthalic acid, all 5 expressed as a mole % of the polymer, as shown in Table 1. It is noteworthy that the amount of isosorbide in the polymer is approximately half of the amount that was charged, when compared with the amount of terephthalic acid. Unreacted isosorbide was found in the distillates, especially in the ethylene glycol. The amount of isosorbide in the polymer by this process thus is very dependent on the 10 efficiency of the distillation or other separation methods that are used in the process. A skilled practitioner can readily establish specific process details according to the characteristics of the reactor, distillation columns and other equipment used. B) Fiber Making The above produced polymer was ground and dried at 130°C overnight in a 15 vacuum oven. Rods were made from the polymer by first placing it in a mold which was then heated under gentle pressure from a plunger. The pressure was provided by a hydraulic press. When the polymer began to soften, more pressure (500-1000 2 lbs/in ) was applied to compress the polymer into a hard rod. The ingress of moisture was reduced by encasing the equipment in a Lucite box which was 20 continuously purged by a flow of dry nitrogen. Spinning was immediately carried out on a single filament spinning machine. The polymer in rod form was melted by pressing it against a heated "grid" which was conical in shape with a hole at the apex. The machine temperatures were slowly raised until the melted polymer started to flow through this hole. In the present 25 example, this occurred at 287°C. The polymer was then filtered through a bed of 80/120 shattered metal, and finally emerged from the single hole spinneret capillary, 0.020" diameter and 0.030" long. The throughput was 0.30 grams per minute (gpm), WO 99/54534 PCT/US99/070I5 -20- and the fiber, which was to be drawn, was taken up at 50 meters per minute (mpm). These conditions were found to give low orientation single filaments of about 69 denier per filament (dpf)- A temperature scan was made to produce the optimum spun fiber for subsequent drawing. A fiber sample was also made at the maximum 5 take up speed possible in order to obtain a feel for draw down and to measure the spun fiber properties. In the present case that speed was 2500 mpm. Single filament drawing was performed on modular draw units with hot shoes between each roll. The fiber was drawn in two stages using the second stage to develop the maximum fiber tenacity and crystallinity. The hot shoe temperatures 10 used in the present example were 90°C and 160°C. In this way, a single filament was collected and small samples cut from the last roll. A sample was tested for its tensile properties using ASTM test method D3822. The tests were conducted on a three inch gauge length at 60% strain, and the results are exhibited in Table 1. Examples 2-13 15 The conditions used to spin and draw similar fibers 2-13 from other polymer compositions of the invention, as well as the resulting tensile properties, are also presented in Table 1. Further, comparative examples using compositions of po!y(ethylene terephthalate) are presented in Table 1. These polymer fibers were produced and spun in the same manner as Example 1 using the conditions set forth 20 in Table 1. Table 2 provides additional data regarding birefringence and orientation of the drawn fibers of Examples 1A and B, 2A, 3A, 4A, 8B, 9A and B, 10A, 11A and Comparative Examples 1 and 2, which are poly(ethylene terephthalate). The birefringence of the fibers was measured by x-ray scattering with a Leitz Orthoplane 25 Polarized Light Microscope with a Berek tilt type microscope. The orientation of the fibers was measured by X-ray scattering from the crystalline phase with a Rigaku Rotating Type generator having a two dimensional (2D) position sensitive WO 99/54534 PCT/US99/07015 -21- detector using Ka radiation. The measurement of birefringence divided by orientation is a measure of the normalized birefringence of the fiber independent of the draw ratio and orientation. It is to be understood that the above described embodiments are illustrative 5 only and that modification throughout may occur to one skilled in the art. Accordingly, this invention is not to be regarded as limited to the embodiments disclosed herein. PCT/US99/070I5 -22- TABLE1 Spun fiber properties Example V.ISOS Charged to Reaction Extrusion Temp CO Take-up Speed (mpm) DPF Tenacity (gpd) Elongation (%) Modulus (gpd) Comp. 1A 0 287 75 66 0.5 3 22 Como. 1B 287 2900 0.6 2.5 117 43 1A 5% 287 50 69 0.5 3.5 18 1B 287 75 73 0.5 3.5 18 1C 287 2500 0.8 2.1 113 28 2A 6% 288 50 68 0.5 3.4 20 2B 288 3000 0.7 1.9 71 34 3A- 7% 287 75 70 0.5 3.2 20 3B 287 2500 0.9 2.4 84 31 4A 10% 237 75 68 0.5 3.6 20 4B 287 2550 0.8 2.3 58 32 5A 6% 277 25 78 0.5 3.6 19 53 277 2500 0.9 2 94 32 6A 6% 277 25 67 0.5 174 19 6B 278 1500 1.4 2 77 44 7A 6% 278 50 62 0.5 3.2 19 78 277 1400 1.6 1.7 . ' 62 35 Comp. 2A 0 277 25 52 0.5 3.6 19 ComD. 2B 277 2000 1 2.1 132 33 8A 12% 261 25 74 0.5 3.3 19 8B 261 50 72 0.5 3.4 20 8C 260 75 75 0.5 3.2 20 80 260 1400 1.35 2 70 38 9A 18.3% 250 30 9B 250 120 10A 24.5% 281 25 65 0.5 75 18 10B 281 50 74 0.7 342 18 10C 281 75 70 0.8 351 18 11A 36% 267 25 76 0.5 285 19 11B 267 50 72 0.5 258 18 12A 36% 243 25 78 0.6 281 21 12B 243 50 75 0.7 331 22 • 12C 243 75 73 0.7 324 22 12D 243 1000 1.8 2.6 50 28 13A 36% 292 25 151 0.6 167 21 13B ] 293 50 33.4 0.6 136 24 13C 293 75 48.2 0.6 139 21 13D 294 425 4.4 1.34 48 21 SUBSTITUTE SHEET (RULE 26) WO 99/54534 PCT/US99/070I5 -23- TABLE 1 (Cont'd) Drawn fiber properties Resin Analysis Example Draw Ratio DPF renacity (9Pd) Elong¬ation (%) Mod¬ulus (9Pd) Hot shoe temp (°C) 1 2 Shrinkage Snset 5 Imp [ t-) °C) % Tmp CO ! HNMR mol% dL/9) SOS EG DEG Comp. 1A 7.3 9.6 9 7.8 154 90 160 66.3 7.17 80 245 .54 — 49.3 0.7 Como. 1B 1A 7.1 9.3 7.2 8.3 110 90 160 83.1 5.96 86 234 0.44 3.2 43.95 2.9 1B 7.1 10.6 6.6 7.5 126 90 160 1C 2A 7.5 9.3 6.7 7.4 125 90 160 87.6 4.68 89 225 0.51 4.3 43.3 2.3 2B 3A 7.3 9.6 6.6 7.2 133 90 160 90.1 5.39 91 224 0.53 4.45 42.7 2.85 3B 4A 7.5 9.3 4.9 6.4 103 90 160 90.1 4.41 93 N.A. 0.49 7.25 39.1 3.65 4B 5A 7.6 9.9 7.7 8.4 126 100 180 5B 6A 7.6 9.5 7.7 8.0 123 100 180 89 0.55 6B 7A 7.4 8 9.1 8.5 137 100 180 89 0.49 4.2 42.65 3.25 7B Comp. 2A 7.4 10.4 8.6 8.3 131 100 180 80 245 0.81 Comp. 2B 8A 7 10.3 6.4 8.0 129 90 130 74.7 10 95 N.A. 0.6 5.5 42.9 1.1 8B 6.8 10.9 6.5 7.6 126 90 130 8C 6.6 11.5 6.5 7.8 123 90 130 8D 9A 6.3 16.7 2 42 36 115 none 97 0.4 93 8.1 10.2 2.5 21.4 65 115 120 .. 10A 6.9 11 4.3 12.9 68 100 130 107 0.56 10B 6.7 11.7 4.3 12.9 70 100 130 10C 6.2 10.7 4.3 13.3 62 |100 130 11A 6.2 12.8 1.7 51 24 130 140 118 0.46 11B 5.9 12.4 2.5 20 41 130 135 12A 5.5 13.9 1.5 8 45 120 none 110 0.43 13.9 32.3 3.4 12B 7 11.4 1.8 27 35 130 none 12C 7.8 9.3 1.8 11 42 130 none 12D 13A 5 35.1 1.6 28 31 160 none , 141 0.46 26.6 21.4 1.6 13B 2.8 15.4 1.2 30 29 16Q none i 13C 2.9 24.8 1.3 28 29 160 nont i 13D SUBSTITUTE SHEET (RULE 26) TABLE 2 tw £» EXAMPLE isosorbide mole% charged mass fraction isos draw ratio birefringence orientation biref/orien mod(gpd) tenacity elong% Comp Ex 1* 0 0.478 7.3 0.2 0.982 0.203666 154 9 7.8 Ex 1A 5 7.188 7.1 0.185 0.981 0.188583 110 7.2 8.3 Ex IB 5 7.188 7.1 0.186 0.977 0.190379 126 6.6 7.5 Ex2A 6 8.5084 7.5 0.184 0.976 0.188525 125 6.7 7.4 Ex3A 7 9.8216 7.3 0.177 0.971 0.182286 133 6.6 7.2 Ex4A 10 13.718 7.5 0.151 0.967 0.156153 103 4.9 6.4 Ex8B 12 16.2796 6.8 0.162 0.955 0.169 126 6.5 7.6 Ex9A 18 23.7916 6.0 0.064 0.509 0.125737 36 2 42 Ex9B 18 23.7916 8.0 0.073 0.843 0.086 65 2.5 21.4 10A 24.5 6.5 0.129 0.97 0.132 66 4.1 13 I1A 36 6.0 0.084 0.49 0.171429 32 2.1 35 -3 o *PET o ^« o ytQ-WSttt— PCT/US99/0701S 1 he fiber accordfeg4e- Claim 1, having an initial modulus of from about 20 to 150 gpd. The Claim 1, having a denier per filament of from about 0.5 to 20. Ftietiber Claim 1, having a cross section selected from the group consisting of circular, elliptical, square, rectangular, crescent-shaped, rnjjjtj-lobed and dog-boned. A method of making a fiber, wherein the fiber comprises a polyester, said method composing: 10 a) forming the polyester; b) spinning the polyester into a fiber; and c) drawing the spun fiber, wherein the polyester comprises terephthaloyl moieties; optionally, other aromatic diacid moieties; ethylene glycol moieties; isosorbide moieties; and, 15 optionally, one or more other diol moieties; wherein said polyester has an inherent viscosity of at least about 0.35 dL/g when measured as a 1 % (weight/volume) solution of said polyester in o-chlorophenol at a temperature of25°C. The method according to- wherein forming the polyester comprises: (a) combining in a reactor a monomer comprising a terephthaloyl moiety; optionally, one or more other monomers containing an aromatic diacid moiety; a monomer comprising an ethylene glycol moiety; a monomer comprising an isosorbide moiety; and optionally, one or more other monomers comprising a diol moiety with a condensation catalyst suitable for condensing aromatic diacids and 25 glycols; and SUBSTITUTE SHEET (RULE 26) -28- (b) heating said monomers and said catalyst to a temperature sufficient to polymerize said monomers into a polyester polymer having at least a terephthaloyl moiety, ethylene glycol moiety and isosorbide moiety, wherein said heating is continued for a sufficient time to yield a 5 polyester having an inherent viscosity of at least about 0.35 dL/g when measured as a 1 % (weight/volume) solution of said polyester in o-chlorophenol at a temperature of 25°C. The method according to Claim V&. wherein heating said monomers further includes stirring said monomers with the concurrent removal of by-products by distillation and/or evaporation. The method according to Claim \& wherein said monomer comprising a terephthaloyl moiety is terephthalic acid. The method aecording to Claim w wherein water and unreacted monomer are removed while said monomers polymerize. The method according-to Claim \&wherein said monomer comprising a terephthaloyl moiety is dimethyl terephthalate. The method according to Claim lift wherein methanol and unreacted monomer are removed while said monomers polymerize. J2£r The method according to Claim ^wherein said one or more 20 optional other diol moieties are derived from aliphatic alkylene glycols or branched aliphatic glycols having from 3-12 carbon atoms and having the empirical formula HO-CnH2n-OH, where n is an integer from 3-12; cis or trans-1,4- SUBSTITUTE SHEET (RULE 26) cyclohexanedimethanol or mixtures thereof; triethylene glycol; 2,2-bis[4-(2-hydroxyethoxy)phenyl] propane; l,l-bis[4-(2-hydroxyethoxy) phenyl] cyclohexane; or9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene. y -23. The methodic-cording to Claim 1# wherein said optional other 5 aromatic diacid moieties are derived from isophthalic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,6-naphthalenedi-carboxylic acid, 2,7-naphthalenedicarboxylic acid, or 4,4'-bibenzoic acid. The method according to Claim l&, wherein said terephthaloyl moieties are present in an amount of about 40 to 50 mole % of said polyester, said 10 optional other aromatic diacid moieties are present in an amount up to about 10 mo % of said polyester, said ethylene glycol moieties are present in an amount of abou 33 to 49.9 mole % of the polyester, said isosorbide moieties are present in an amount of about 0.25 to 10.0 mole % of said polyester, and said one or more other diol moieties are present in an amount up to about 2.0 mole % of said polyester. 15 The method a6cofdingto Claim Vd wherein said one or more other diol moieties are diethylene glycol moieties in an amount of up to about 5.0 mole % of said polyester. The method according^ Claim tefftmfter comprising increasing the molecular weight of said polyester by solid state polymerization. 20 The method accordiag-tfr-Claim 26fwherein said solid state polymerization comprises: (a) crystallizing said polyester by heating said polyester to a temperature in the range of about 115°C to about 140°C; and SUBSTITUTE SHEET (RULE 26) (b) heating said polyester under vacuum or in a stream of inert gas at an elevated temperature above 140°C but below the melting temperature of said polyester to yield a polyester having an increased inherent viscosity. The method .according to Claim 2^fwherein said heating step (b) is carried out at a temperature of about 195° to 198°C for about 10 hours. /5 -19. The method-aecording to Claim 27 wherein said increased inherent viscosity is at least about 0.65 dL/g. The method according te Claim 15wherein spinning the polyester into fiber comprises: a) melting said polyester; b) extruding said molten polyester through a spinning orifice; and c) cooling said extnided polyester, thereby forming a fiber. The method according te Claim 15,wherein drawing the spun fiber comprises: 15 a) heating the spun fiber; b) exerting tension on the heated spun fiber, thereby stretching the heated spun fiber; and A staple blend, comprising the fiber jafQaiffi ■! and at least one other c) collecting and cooling the stretched fiber. 20 fiber selected from the srouD consisting of synthetic fibers, cotton fiber and wool "An artirle rnmpnsing thp. staple b>nd of Claim 35- ^3- SUBSTITUTE SHEET (RULE 26) »4T AJI dilit.li; made fium llit flb£rp1 Claim 1. ^-^n The article according-te Claim 34, wherein the article is selected from atexute-febiic, high strength industrial fabric, sewing threads, and cording for rubber reinforcement. The anicle, wherein the fiber size is from SUBSTITUTE SHEET (RULE 26)

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