PROCESS FOR FORMING THERMALLY STABLE THERMOTROPIC LIQUID CRYSTALLINE POLYESTERS OF PREDETERMINING CHAIN LENGTH UTILIZING AROMATIC HYDROXYL MONOMER AND/OR AROMATIC AMINE MONOMER

Abstract: An improved polymerization process is provided for the formation of a polyester which is capable of forming an an­ isotropic melt phase and which optionally may include amide linkages. An approximately 0.25 to 4 percent molar excess of aromatic hydroxyl monomer and/or aromatic amine mon­ omer and/or an esterified and/or amidated derivative thereof is provided in the polymerization zone during the polymer­ ization reaction. Such monomer imparts dioxyaryl, diami­ noaryl, or oxyaminoaryl units to the interior of the resulting polymer chains and causes the polymer chains to terminate in hydroxyl end groups and/or in esterified derivative thereof and/or amino end groups and/or an amidated derivative thereof wherein the polymer chains achieve a predetermined average chain length through the depletion of other mono­ mers present in the polymerization zone. The resulting po­ lyester unlike the usual product of the prior art is substantially incapable of additional chain growth upon subsequent heat­ ing and accordingly may be relied upon to maintain a sub­ stantially constant viscosity during melt processing regardless of the duration of heating.

Description: It has been disclosed that certain polyesters may be formed which exhibit melt anisotropy. Such polymers commonly are referred to as being thermotropic liquid crystalline polymers. See, for instance, (a) Polyester X7G-A Self Reinforced Thermoplastic , by W. J. Jackson, Jr., H. F. Kuhfuss, and T. F. Gray, Jr., 30th Anniversary Technical Conference, 1975 Reinforced Plastics Composites Institute, The Society of the Plastics Industry, Inc., Section 17-D, Pages 1-4; (b) Belgian Patent Nos. 828,935 and 828,936; (c) Dutch Patent No. 7505551; (d) West German Nos. 2520819, 2520820, 2722120, 2834535, 2834536 and 2834537; (e) Japanese Nos. 43-223; 2132-116; 3017-692; and 3021-293; (f) U.S. Patent Nos. 3,991,013; 3,991,014; 4,057,597; 4,066,620; 4,067,852; 4,075,262; 4,083,829; 4,093,595; 4,118,372; 4,130,545; 4,130,702; 4,146,702; 4,153,779; 4,156,070; 4,159,365; 4,161,470; 4,169,933; 4,181,792; 4,183,895; 4,184,996; 4,188,476; 4,201,856; 4,219,461; 4,224,433; 4,226,970; 4,230,817; 4,232,143; 4,232,144; 4,238,598; 4,238,599; 4,238,600; 4,242,496; 4,245,082; 4,245,084; 4,247,514; 4,256,624; 4,265;802; 4,267,304; 4,269,965; 4,272,625; 4,279,803; 4,284,757; 4,285,852; 4,287,332; 4,294,955; 4,299,756; 4,311,824; 4,314,073; 4,318,841; 4,318,842; 4,330,457; 4,332,759; 4,333,907; 4,335,232; 4,337,190; 4,337,191; 4,339,375; 4,341,688; 4,346,208; 4,347,349; 4,351,917; 4,351,918; 4,355,132; 4,355,133; 4,355,134; 4,359,569; 4,360,658; 4,362,777; 4,370,466; 4,371,660; 4,374,288; 4,375,530; 4,381,389; 4,384,016; 4,393,191; 4,394,498; 4,395,307; 4,395,536; 4,408,022; 4,421,908; 4,429,060; 4,429,061; 4,429,100; 4,429,105; 4,431,770; and 4,434,262; (g) U.K. Application No. 2,002,404; (h) British Patent No. 1,568,541; and (i) European Patent Application Nos. 24,499 and 45,499. Amide groups and/or carbonate groups additionally may be present in the polyesters which exhibit melt anisotropy. The thermotropic liquid crystalline polymers of the prior art are formed by techniques whereby the requisite reactive groups which form ester groups along the polymer chain are carefully reacted so as to provide a stoichiometric balance of reactive groups. For instance, if a relatively volatile monomer, such as hydroquinone or hydroquinone diacetate, is employed as a reactant, an excess of this monomer sometimes is provided to compensate for the quantity of this reactant which is evolved and lost by volatilization through the use of the specific polymerization conditions selected. When the various ester-forming monomers are provided and react with each other under stoichiometrically balanced conditions, a polymer is produced having the random presence of the requisite ester-forming groups at the ends of the polymer chain. These end groups unless otherwise end capped in a further reaction step have the propensity upon subsequent thermal processing to react with each other and to cause the polymer chains to continue to grow in length. The thermal processing of such polymers to increase the molecular weight in the solid state is disclosed, for example, in U.S. Patent Nos. 3,975,487; 4,183,895; 4,247,514; and 4,424,184. The continued polymerization via a condensation reaction results in the simultaneous evolution or off-gassing of relatively small molecular by-products and an elevation in the melt viscosity of the resulting polymer upon any subsequent melt processing. Such increase in melt viscosity may require the selection of different melt processing conditions at different points in time as the average chain length increases. For instance, it may be desirable to modify the injection molding conditions when forming molded articles from the resulting anisotropic melt-forming polyester. Accordingly, the melt processing of such polymers may require the continued or periodic monitoring of the molten polymer viscosity and the adjustment of melt processing conditions in an effort to yield uniform molded products if the molten polymer is provided at an elevated temperature for an extended period of time. Additionally, the melt devolatilization of previously formed thermotropic liquid crystalline polymers of the prior art is desirable to remove substantial quantities of void-forming volatile materials contained therein. However, if such devolatilization is practiced for a sufficient period of time to substantially remove such volatiles, a continued molecular weight increase also will occur. It is an object of the present invention to provide an improved process for forming a thermally stable thermotropic liquid crystalline polyester of predetermined chain length. It is an object of the present invention to provide an improved process for forming a thermally stable thermotropic liquid crystalline polyester which is particularly suited for melt processing to form substantially uniform molded articles on a consistent basis. It is an object of the present invention to provide an improved process for forming a thermotropic liquid crystalline polymer which will generate a significantly reduced amount of volatile by-products during further melt processing. It is an object of the present invention to provide an improved process for forming a thermotropic liquid crystalline polymer which is capable of undergoing vigorous melt devolatilization without concomitantly producing an excessive polymer chain growth and a significant change in the melt viscosity of the resulting polymer. It is an object of the present invention to provide a thermally stable polyester which is capable of forming a liquid crystalline melt phase without the need of employing a conventional end-capping reaction of a previously formed polymer. In EP-A-0,133,024 (claiming priority from United States Application No. 517,865) and United States Application No. 595,004, filed March 29, 1984, (now US-A-4,562,244), there are disclosed alternative routes for accomplishing the same objects as the present invention. The present invention now provides a process for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase and which optionally may include amide linkages through a polymerization reaction of ester-forming and optionally also amide-forming monomers to form a polymer having recurring moieties selected from the group consisting of the following where in each instance Ar comprises at least one aromatic ring: (a) and (b) a mixture of where Z is NH or NR where R is an alkyl group of 1 to 6 carbon atoms or an aryl group; in which there is provided in the polymerization zone during the polymerization reaction an approximately 0.25 to 4 percent molar excess of an aromatic monomer selected from the group consisting of the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (c) HO-Ar-OH, and/or an esterified derivative thereof, (d) H₂N-Ar-NH₂, and/or an amidated derivative thereof, (e) HO-Ar-NH₂, and/or an esterified and/or an amidated derivative thereof, and (f) mixtures of the foregoing, the polymerisation reaction being carried out until the depletion of the other monomers present in the polymerisation zone yields a polyester product that is substantially incapable of additional chain growth upon subsequent heating. A polyester formed in accordance with the process of the present invention is capable of forming an anisotropic melt phase, and is substantially incapable of further chain growth upon heating. Description of Preferred Embodiments As is known in polymer technology, a thermotropic liquid crystalline polymer exhibits optical anisotropy in the melt. The anisotropic character of the polymer melt may be confirmed by conventional polarized light techniques whereby crossed-polarizers are utilized. More specifically, the anisotropic nature of the melt phase may conveniently be confirmed by the use of a Leitz polarizing microscope at a magnification of 40X with the sample on a Leitz hot stage and under a nitrogen atmosphere. The amount of light transmitted changes when the sample is caused to flow; however, the sample is optically anisotropic even in the static state. On the contrary typical melt processable polymers do not transmit light to any substantial degree when examined under quiescent conditions and are isotropic in nature. The thermotropic liquid crystalline polyester which is formed by the process of the present invention, as described hereafter, is unlike the polymerization products of the prior art and is substantially incapable of further chain growth upon heating at its melt processing temperature. It possesses polymer chains which terminate substantially exclusively in (1) hydroxyl end groups and/or an esterified derivative thereof, (2) amino end groups and/or an amidated derivative thereof, or (3) mixtures of the foregoing. There is no use in its formation of an end-capping reaction of a previously formed polymer through the introduction of an end-capping reactant to the polymerization zone at the conclusion of the polymerization. The polymer chains terminate in functional groups which ore substantially incapable of a further polymerization reaction between the adjoining polymer chains. When such polymer is heated in an inert atmosphere (e.g. nitrogen or argon) for 30 minutes while at a temperature of 340°C., its weight average molecular weight preferably increases no more than 15 percent. Polyester-forming monomers are selected which are capable of imparting recurring moieties of the structure to the polymer chain where Ar may be the same or different and comprises at least one aromatic ring. In a preferred embodiment Ar is 1,4-phenylene or 2,6-naphthalene. Accordingly the moiety is a 4-oxybenzoyl moiety or a 6-oxy-2-naphthoyl moiety in such instances. The polyester may include a plurality of different recurring moieties where Ar is different in each and where each moiety satisfies the above general formula, such as a combination of 1,4-phenylene and 2,6-naphthalene. Such monomers are inherently stoichiometrically balanced since they contain precisely the correct quantity of ester-forming reactant groups. The aromatic ring or rings present optionally may include substitution of at least some of the hydrogen atoms present thereon. Such substitution may be selected from an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, halogen (e.g. Cl, Br, I), phenyl, and mixtures of the foregoing. Particularly preferred moieties may be derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. Representative ring substituted moieties include 2-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 2-phenyl-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 6-hydroxy-4,7-dichloro-2-chloro-2-naphthoic acid, etc. Other non-ring substituted moieties may be derived from 3-hydroxybenzoic acid and 4-hydroxybiphenyl-4'-carboxylic acid, etc. Alternatively, a mixture of polyester-forming and amide-forming monomers may be selected which are capable of imparting recurring moieties of the structures to the polymer chain where Ar may be the same or different and comprises at least one aromatic ring, and Z is NH or NR, where R is an alkyl group of 1 to 6 carbon atoms or an aryl group. These monomers are inherently stoichiometrically balanced since they contain precisely the correct quantity of ester-forming or amide-forming reactant groups. The resulting polyester may include three or more different recurring moieties so long as the above general formulas are satisfied. Monomers which impart moieties of the first expressed structure are previously described. When selecting monomers which impart moieties of the second expressed structure, Ar is 1,4-phenylene in a preferred embodiment. Also, when selecting monomers which impart moieties which satisfy the second expressed structure the aromatic ring or rings present optionally may include substitution of at least some of the hydrogen atoms present thereon as discussed in connection with the first described moiety. Examples of monomers from which this moiety may be derived include p-aminobenzoic acid, p-N-methylaminobenzoic acid, m-aminobenzoic acid, 3-methyl-4-aminobenzoic acid, 2-chloro-4-aminobenzoic acid, 4-amino-1-naphthoic acid, 4-N-methylamino-1-naphthoic acid, 4-amino-4'-carboxydiphenyl, 4-amino-4'-carboxydiphenyl ether, 4-amino-4'-carboxydiphenyl sulfone, 4-amino-4'-carboxydiphenyl sulfide, p-aminocinnamic acid, etc. Particularly preferred moieties may be derived from p-aminobenzoic acid. Highly satisfactory polyesters which may be produced in a modified form in accordance with the concept of the present invention are disclosed in commonly assigned United States Patent Nos. 4,161,470 and 4,351,917. In accordance with the concept of the present invention all ester-forming and amide-forming monomers are added to the polymerization zone in carefully measured quantities so that during the course of the polymerization there is provided a 0.25 to 4 percent molar excess of an aromatic monomer selected from the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (1) HO-Ar-OH, and/or an esterified derivative thereof, (2) H₂N-Ar-NH₂, and/or an amidated derivative thereof, (3) HO-Ar-NH₂, and/or an esterified and/or an amidated derivative thereof, and (4) mixtures of the foregoing. Such aromatic monomer during the polymerization reaction imparts units to the interior of the polymer chains which are selected from dioxyaryl units, diaminoaryl units, oxyaminoaryl units, and mixtures of the foregoing. Also, the resulting polymer chains are caused to end in groups selected from the following: (1) hydroxyl end groups and/or an esterified derivative thereof, (2) amino end groups and/or an amidated derivative thereof, and (3) mixtures of the foregoing. Representative aromatic diols which may serve as the aromatic monomer which is provided in a molar excess include the following: In a particularly preferred embodiment Ar is 2,6-naphthalene, or 4,4'-biphenyl. The polyester may include a plurality of different recurring moieties where Ar is different in each and where each moiety satisfies the above general formula for an aromatic diol. The aromatic ring or rings present optionally may include substitution of at least some of the hydrogen atoms present thereon as discussed in connection with the earlier described monomers. Examples of aromatic monomers which include ring substitution are those derived from phenylhydroquinone, methylhydroquinone, chlorohydroquinone, etc. Particularly preferred aromatic monomers may be simply derived from 2,6-dihydroxynaphthalene, and 4,4'-biphenol. Representatives aromatic diamines which may serve as the aromatic monomer which is provided in a molar excess are p-phenylenediamine, N-methyl-p-phenylenediamine, N,N'-dimethyl-p-phenylenediamine, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-ethylenedianiline, 4,4'-diaminodiphenyl sulfone, 2,5-diaminotoluene, 4,4'-diaminodiphenyoxy-ethane, etc. Representatives aromatic hydroxyamino compounds which may serve as the aromatic monomer which is provided in a molar excess are p-aminophenol, p-N-methylaminophenol, m-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenyl methane, 4-amino-4'-hydroxydiphenyl ethane, 4-amino-4'-hydroxydiphenyl sulfone, 4-amino-4'-hydroxydiphenyl sulfide, etc. Any hydroxy groups present upon the aromatic monomer which is provided in a molar excess optionally may be esterified. Also, any amino groups present upon such aromatic monomer optionally may be amidated. They preferably are provided as lower acyl esters or amides of 2 to 4 carbon atoms. Preferably the acetate esters or acetamides of such aromatic monomer which would otherwise include hydroxyl and/or amine groups are provided. Examples of such aromatic monomers or 2,6-naphthalene diacetate, 4,4'-diacetoxybiphenyl, 1,4-phenyleneacetamide, p-acetoxyacetanilide, etc. In a preferred embodiment the aromatic monomer which is provided during the course of the polymerization reaction in a molar excess is introduced in a molar excess of 0.5 to 4 percent. It is essential that this molar excess of aromatic monomer (as defined) be provided during the polymerization reaction in excess of the other monomer quantities which are sufficient to provide a stoichiometric balance between all carboxylic acid reactive groups (and/or an esterified derivative thereof) and the hydroxyl reactive groups (and/or an esterified derivative thereof) plus any amine reactive groups (and/or an amidated derivative thereof). During the course of the polymerization reaction in accordance with the process of the present invention dioxyaryl units, diaminoaryl units, oxyaminoaryl units, or mixtures thereof derived from such molar excess of such aromatic monomer are incorporated into the interior of the polymer chains of the resulting polymer and cause the polymer chains to terminate in hydroxy end groups and/or an esterified derivative thereof, amino end groups and/or an amidated derivative thereof, or mixtures of these. As the polymerization reaction progresses the other monomers present in the polymerization zone are fully depleted. The average polymer chain length achieved is directly controlled by the molar excess quantity the aromatic monomer (as defined) provided in the polymerization zone during the course of the polymerization reaction. As the molar excess quantity of the aromatic monomer increases within the range specified, the average polymer chain length decreases. As the molar excess quantity of the aromatic monomer decreases within the range specified, the average polymer chain length increases. A polymer product of predetermined average chain length is produced by the process of the present invention through the selection of the specific molar excess utilized. Such average chain length may be conveniently evidenced by the inherent viscosity of the resulting polymer. In all instances the polymer chains of the resulting thermotropic liquid crystalline polyester terminate in the groups indicated. Such product is thermally stable in the sense that it cannot undergo substantial additional polymerization with the concomitant evolution of condensation reaction by-products since the like end groups are substantially incapable of additional polymer chain growth upon subsequent heating. The polyester of the present invention may be formed by a variety of ester-forming techniques whereby the organic monomer compounds are reacted. For instance, the functional groups of the organic monomer compounds may be carboxylic acid groups, hydroxyl groups, ester groups (e.g. acyloxy groups), amine groups, amide groups (e.g. acylamide groups), acid halides, etc. The organic monomer compounds may be reacted in the absence of a heat exchange fluid via a melt acidolysis procedure. They accordingly, may be heated initially to form a largely melt solution of the reactants. The polymer product sometimes is suspended therein as solid polymer particles. A vacuum may be applied to facilitate removal of volatiles formed during the final stage of the condensation (e.g., acetic acid or water) and to otherwise expedite the polymerization. In U.S. Patent No. 4,067,852 of Gordon W. Calundann, entitled "Melt Processable Thermotropic Wholly Aromatic Polyester Containing Polyoxybenzoyl Units" is described a slurry polymerization process which may be employed to form the polyester of the present invention wherein the solid product is suspended in a heat exchange medium. When employing either the melt acidolysis procedure or the slurry procedure of U.S. Patent No. 4,067,852 the primary monomer reactants from which the polymer moieties are derived which would otherwise include a hydroxyl and/or an amine group preferably also are preliminarily esterified and/or amidated. They preferably are provided as lower acyl esters or amides of 2 to 4 carbon atoms. Preferably the acetate esters or acetamides of such monomers which would otherwise include a hydroxyl group and/or an amine group are provided. Examples of such reactants are 6-acetoxy-2-naphthoic acid, 4-acetoxybenzoic acid, 4-acetamidobenzoic acid, etc. Representative catalysts which optionally may be employed in either the melt acidolysis procedure or in the procedure of U.S. Patent No. 4,067,852 include dialkyl tin oxide (e.g., dibutyl tin oxide), diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alkoxides, alkali and alkaline earth metal salts of carboxylic acids, the gaseous acid catalysts such as Lewis acids (e.g., BF₃), hydrogen halides (e.g., HCl), etc. The quantity of catalyst utilized typically is 0.001 to 1 percent by weight based upon the total monomer weight, and most commonly 0.01 to 0.2 percent by weight. The polymerization procedures of U.S. Patent Nos. 4,393,191 and 4,429,105, and of United States Application Serial No. 583,643, filed February 27, 1984 (now U.S. Patent No. 4,574,066) of John D. Gibbon et al entitled "Improved Process for the Expeditious Formation of a High Strength Shaped Article of Poly(6-Oxy-2-Naphthoate-4-Oxybenzoate)" , also are suitable for use when carrying out the process of the present invention. In a particularly preferred embodiment a polyester of U.S. Patent No. 4,161,470 is produced in a modified form in accordance with the concept of the present invention. It has been found that in such embodiment where a process is carried out for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase through a polymerization reaction of ester-forming monomers to form a polymer which consists essentially of moieties I and II wherein: wherein said polyester comprises 10 to 90 mole percent (e.g. 25 to 45 mole percent) of moiety I, and 10 to 90 mole percent (e.g. 55 to 75 mole percent) of moiety II; that improved results are achieved by providing in the polymerization zone during the polymerization reaction a 0.25 to 4 percent molar excess of an aromatic monomer of the formula: and/or an esterified derivative thereof, which during the polymerization reaction imparts dioxyaryl units to the interior of the polymer chains and causes the polymer chains to end in hydroxy end groups and/or an esterified derivative thereof, wherein the polymer chains achieve a predetermined average chain length through the depletion of other monomers present in the polymerization zone to yield a polyester product which is substantially incapable of additional chain growth upon subsequent heating. In a further particularly preferred embodiment a polyester of U.S. Patent No. 4,351,917 which includes amide linkages is produced in a modified form in accordance with the concept of the present invention. It has been found that in such embodiment that a product can be formed in modified form which consists essentially of moieties I, II, and optionally III, which optionally may include substitution of at least some of the hydrogen atoms present upon an aromatic ring wherein: I is II is where Ar comprises at least one aromatic ring and where Z is NH or NR where R is an alkyl group of 1 to 6 carbon atoms or an aryl group, and III is wherein at least some of the hydrogen atoms present upon the rings optionally may be replaced by substitution selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, halogen, phenyl, and mixtures thereof, and wherein moiety I is present in a concentration of 10 to 90 mole percent, moiety II is present in a concentration of 5 to 45 mole percent, and moiety III is present in a concentration of 0 to 45 mole percent, with the total concentrations of moieties I and III being within the range of 55 to 95 mole percent, and which additionally incorporates an 0.25 to 4 percent of units derived from the aromatic monomer which is provided in molar excess. The thermotropic liquid crystalline polyesters of the present invention commonly form an anisotropic melt at a temperature below 400°C., and preferably at temperature below 350°C. The polymeric product of the present invention tends to be substantially insoluble at ambient temperature in all common polyester solvents, such as hexafluoroisopropanol and o-chlorophenol, and accordingly is not susceptible to solution processing. It can be readily processed by common melt processing techniques. Most compositions are soluble in pentafluorophenol to at least a slight degree. The polyester of the present invention commonly exhibits a weight average molecular weight of 4,000 to 50,000, and preferably 4,000 to 30,000. Such molecular weight may be determined by standard gel permeation chromatography. For instance, in a typical test 150 microliters of a 0.1 percent by weight polymer solution in a solvent consisting of a 1:1 mixture on a volume basis of pentafluorophenol and hexafluoroisopropanol are introduced into the gel permeation chromatography equipment consisting of a main control unit (e.g. Waters liquid chromatograph Model No. 201), four columns containing porous silica particles (e.g. DuPont SE4000, DuPont SE1000, DuPont SE100, and Waters 60 Angstrom Microporasil), and a laser light scattering unit (e.g. Chromatix KMX6) at ambient temperature. Typical melt processable anisotropic melt-forming polymers commonly show a retention time distribution in the range of 20 to 50 minutes. The polyester additionally commonly exhibits an inherent viscosity (i.e., I.V.) of at least 0.6 dl./g. and preferably at least 0.8 dl./g. (e.g., approximately 0.8 to 10.0 dl./g. or more) when dissolved in a concentration of 0.1 percent by weight in pentafluorophenol at 60°C. In a particularly preferred embodiment the polyester of the present invention exhibits an inherent viscosity in the range of 0.8 to 8.0 dl./g. when dissolved in a concentration of 0.1 percent by weight in pentafluorophenol at 60°C. Alternatively, the inherent viscosity of the polyester may be determined while dissolved in a 1:1 solution of pentafluorophenol/hexafluoroisopropanol in a concentration of 0.1 percent (W/V) at 25°C. This alternate technique offers the possibility of automation while operating at room temperature; however, it tends to yield numerical values which are higher than those obtained with a 0.1 percent solution in pentafluorophenol at 60°C. For instance, such values with the mixed solvent may be on the order of approximately 10 percent higher than those obtained with pentafluorophenol at 60°C. The polyester of the present invention preferably also exhibits a melt viscosity in the range of 10 to 10,000 poise (1 to 1,000 Pa.s), preferably 20 to 3,000 poise (2 to 300 Pa.s), at 300°C. and a shear rate of 100 sec.⁻¹. Such melt viscosity may be determined by standard techniques using an Instron capillary rheometer having a capillary which measures 4 inches (101.6 mm) in length and has an inner diameter of 30 mils (0.762 mm). The polymeric product of the present invention is capable of withstanding vigorous melt devolatilization following its formation to eliminate entrained gaseous by-products from the preceding polymerization reaction. Suitable vigorous devolatilization processing conditions can, for instance, be carried out for 10 minutes or more at a temperature above the polymer melting temperature (e.g. at 320°C. or above) while under a reduced pressure of 1 Torr (133.3 Pa) with vigorous agitation. The moleclar weight of the polymer does not change to any substantial degree during such procedure nor does it change to any substantial degree during any subsequent melt processing step even if prolonged. The substantially complete removal of such gaseous by-product as well as the substantial non-generation of the same during subsequent melt processing facilitates the formation of quality molded articles in the substantial absence of deleterious voids caused by off-gassing. Accordingly, quality molded articles may be consistently formed from the product of the present invention on a reliable and readily reproducible basis. The product of the present invention because of its thermal stability is particularly suited for the formation of molded articles on a reliable and readily reproducible basis. The product is capable of undergoing vigorous melt devolatilization. The following examples are presented as specific illustrations of the claimed invention. It should be understood, however, that the invention is not limited to the specific details set forth in the examples. EXAMPLE 1 It was desired to produce a thermally stable polyester which is capable of forming an anisotropic melt phase, and has a predetermined average chain length which is evidenced by a relatively high weight average molecular weight. To a 300 ml. three-neck round bottom flask equipped with a sealed paddle stirrer, gas inlet tube, and distillation head connected to a condenser were added at room temperature (i.e. approximately 25°C.) the following: (a) 31.21 grams of 6-acetoxy-2-naphthoic acid (0.136 mole), (b) 65.90 grams of 4-acetoxybenzoic acid (0.366 mole), (c) 0.43 grams of 2,6-naphthalene diacetate (0.002 mole), and (d) 0.006 gram of potassium acetate catalyst. It can be calculated that a molar excess of 0.4 percent of 2,6-naphthalene diacetate monomer was provided in the flask. More specifically, the 6-acetoxy-2-naphthoic acid and 4-acetoxybenzoic acid reactants were inherently stoichiometrically balanced since each provided the required carboxylic acid and acetoxy ester-forming reactant groups in an identical quantity. Accordingly, the 2,6-naphthalene diacetate served as the aromatic monomer which was provided in a stoichiometric excess beyond the stoichiometric balance which existed with respect to the other monomers present. The flask and its contents were throughly purged of oxygen by evacuating and refilling with dry argon, and were heated in a hot oil bath under a slow stream of argon. The contents of the flask were initially heated to 240°C. over a period of approximately 1 hour, and to 340°C. over a period of another 100 minutes, and were maintained at 340°C. for 15 minutes while at substantially atmospheric pressure. Finally, the flask was evacuated to a pressure of approximately 0.2 mm. of Hg (26.7 Pa) and heated at 340°C. under such reduced pressure conditions for another 45 minutes. The vacuum was then broken, and the resulting polymer was recovered following cooling. The chains of the resulting polymer included dioxyaryl units derived from 2,6-naphthalene diacetate at interior locations along the length of the polymer chains and terminated in acetate ester end groups. When the polymer is heated in either the melt or in the solid phase, no further polymerization or chain growth is observed. The inherent viscosity (I.V.) of the polymer product is found to be approximately 10.6 dl./g. as determined in a pentafluorophenol solution of 0.1 percent by weight concentration at 60°C. in accordance with the equation: where c = concentration of solution (0.1 percent by weight), and ηrel = relative viscosity. The weight average molecular weight of the polymer product was approximately 47,000. When the polymer was subjected to differential scanning calorimetry (20°C./min. heating rate), it exhibited a melt endotherm peak at 286°C. The polymer melt was optically anisotropic. EXAMPLE 2 Example 1 was substantially repeated with the exception that it was desired to produce a thermally stable polyester which is capable of forming an anisotropic melt phase, and has a predetermined average chain length which is evidenced by a relatively low weight average molecular weight. To the flask were added the following: (a) 27.63 grams of 6-acetoxy-2-naphthoic acid (0.120 mole), (b) 65.76 grams of 4-acetoxybenzoic acid (0.365 mole), (c) 3.66 grams of 2,6-naphthalene diacetate (0 015 mole), and (d) 0.006 gram of potassium acetate catalyst. It can be calculated that a molar excess of 3.1 percent of 2,6-naphthalene diacetate monomer was provided in the flask. The inherent viscosity (I.V.) of the polymer product is found to be approximately 1.45 dl./g. as determined in a pentafluorophenol solution of 0.1 percent by weight concentration at 60°C. The weight average molecular weight of the polymer product was approximately 6,500. When the polymer was subjected to differential scanning calorimetry (20°C./min. heating rate), it exhibited a melt endotherm peak at 283°C. EXAMPLE 3 Example 1 was substantially repeated with the exception that it was desired to produce a thermally stable polyester which is capable of forming an anisotropic melt phase, and has a predetermined average chain length which is evidenced by a weight average molecular weight value intermediate that of Examples 1 and 2. To the flask were added the following: (a) 25.32 grams of 6-acetoxy-2-naphthoic acid (0.110 mole), (b) 65.75 grams of 4-acetoxybenzoic acid (0.365 mole), (c) 1.22 grams 2,6-naphthalene diacetate (0.005 mole), and (d) 0.012 gram of potassium acetate catalyst. It can be calculated that a molar excess of 1.05 percent of 2,6-naphthalene diacetate monomer was provided in the flask. The inherent viscosity (I.V.) of the polymer product is found to be 3.2 dl./g. as determined in a pentafluorophenol solution of 0.1 percent by weight concentration at 60°C. The weight average molecular weight of the polymer product was approximately 16,500. When the polymer was subjected to differential scanning calorimetry (20°C./min. heating rate), it exhibited a melt endotherm peak at 285°C. EXAMPLE 4 It was desired to produce a thermally stable polyester which is capable of forming an anisotropic melt phase and has a predetermined average chain length which is evidenced by a relatively high weight average molecular weight while providing a molar excess of a different aromatic monomer than employed in Examples 1, 2, and 3. The reaction conditions were substantially the same as those employed in Example 1. To the flask were added the following: (a) 31.15 grams of 6-acetoxy-2-naphthoic acid (0.135 mole), (b) 65.76 grams of 4-acetoxybenzoic acid (0.365 mole), (c) 0.676 gram of 4,4'-diacetoxybiphenyl (0.025 mole), and (d) 0.006 gram of potassium acetate catalyst. It can be calculated that a molar excess of 0.5 percent of 4,4'-diacetoxybiphenyl monomer was provided in the flask. The inherent viscosity (I.V.) of the polymer product is found to be approximately 8.91 dl./g. as determined in a pentafluorophenol solution of 0.1 percent by weight concentration at 60°C. The weight average molecular weight of the polymer was approximately 40,000. When the polymer was subjected to differential scanning calorimetry (20°C./min. heating rate), it exhibited a melt endotherm at 285°C.

Claims: A process for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase and which optionally may include amide linkages through a polymerization reaction of ester-forming and optionally also amide-forming monomers to form a polymer having recurring moieties selected from the group consisting of the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (a) and (b) a mixture of where Z is NH or NR where R is an alkyl group of 1 to 6 carbon atoms or an aryl group; characterised by providing in the polymerization zone during the polymerization reaction a 0.25 to 4 percent molar excess of an aromatic monomer selected from the group consisting of the following where in each instance Ar may be the same or different and comprises at least one aromatic ring: (c) HO-Ar-OH, and/or an esterified derivative thereof, (d) H₂N-Ar-NH₂, and/or an amidated derivative thereof, (e) HO-Ar-NH₂, and/or an esterified and/or an amidated derivative thereof, and (f) mixtures of the foregoing, the polymerisation reaction being carried out until the depletion of the other monomers present in the polymerisation zone yields a polyester product that is substantially incapable of additional chain growth upon subsequent heating. A process in accordance with Claim 1 wherein said polymerization reaction is carried out in the melt. A process in accordance with Claim 1 wherein said polymerization reaction is carried out while the monomers are suspended as a slurry. A process in accordance with Claim 1, 2 or 3, wherein any monomer present in the polymerization zone which would otherwise include a hydroxyl group and/or an amine group is provided as a lower acyl ester and/or amide of 2 to 4 carbon atoms. A process in accordance with Claim 1, 2 or 3, wherein any monomer present in the reaction zone which would otherwise include a hydroxyl group and/or an amine group is provided as an acetate ester and/or an acetamide. A process in accordance with any of Claims 1 to 5 wherein said aromatic monomer which is provided in said molar excess is provided in the polymerization zone in a molar excess of 0.5 to 4 percent. A process in accordance with any of Claims 1 to 6 wherein said polyester product exhibits an inherent viscosity of 0.8 to 10.0 dl./g. when dissolved in a concentration of 0.1 percent by weight in pentafluorophenol at 60°C. A process in accordance with any of Claims 1 to 7, wherein said polyester product consists essentially of moieties I and II which optionally may include substitution of at least some of the hydrogen atoms present upon an aromatic ring, wherein: I is and II is with said optional substitution if present being selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, halogen, phenyl, and mixtures of the foregoing, and wherein said polyester comprises 10 to 90 mole percent of moiety I, and 10 to 90 mole percent of moiety II, and which additionally incorporates 0.25 to 4 percent of said units derived from said aromatic monomer which is provided in molar excess. A process in accordance with any of Claims 1 to 7 wherein said product consists essentially of moieties I, II and optionally III, which optionally may include substitution of at least some of the hydrogen atoms present upon an aromatic ring wherein: I is II is where Ar comprises at least one aromatic ring and where Z is NH or NR where R is an alkyl group of 1 to 6 carbon atoms or an aryl group, and III is wherein at least some of the hydrogen atoms present upon the rings optionally may be replaced by substitution selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, halogen, phenyl, and mixtures thereof, and wherein moiety I is present in a concentration of 10 to 90 mole percent, moiety II is present in a concentration of 5 to 45 mole percent, and moiety III is present in a concentration of 0 to 45 mole percent, with the total concentrations of moieties I and III being within the range of 55 to 95 mole percent, and which additionally incorporates 0.25 to 4 percent of said units derived from said aromatic monomer which is provided in molar excess. A process in accordance with any of claims 1 to 7 for the formation within a polymerization zone of a polyester which is capable of forming an anisotropic melt phase through a polymerization reaction of ester-forming monomers to form a polymer which consists essentially of moieties I and II wherein: I is and II is wherein said polyester comprises 25 to 45 mole percent of moiety I, and 55 to 75 mole percent of moiety II, which process comprises providing in the polymerization zone during said polymerization reaction a 0.25 to 4 percent molar excess of an aromatic monomer of the formula: HO-Ar-OH, and/or an esterified derivative thereof. A process in accordance with Claim 10 wherein the oxy portions of the ester-forming monomers which form moieties I and II are provided in said polymerization zone as lower acyl esters of 2 to 4 carbon atoms. A process in accordance with Claim 10 wherein the oxy portions of the ester-forming monomers which form moieties I and II are provided in said polymerization zone as acetate esters. A process in accordance with Claim 10, 11 or 12 wherein the aromatic monomer which is provided in a molar excess is 2,6-dihydroxynaphthalene and/or an esterified derivative thereof. A process in accordance with Claim 10, 11 or 12 wherein the aromatic monomer which is provided in a molar excess is p,p'-biphenol and/or an esterified derivative thereof. A process in accordance with any of Claims 10 to 14 wherein the aromatic monomer which is provided in said molar excess is provided in said polymerization zone as a lower acyl ester of 2 to 4 carbon atoms. A process in accordance with any of Claims 10 to 14 wherein the aromatic monomer which is provided in said molar excess is provided in said polymerization zone as an acetate ester.

Inventors: YOON, HYUN-NAM
Applicants: CELANESE CORPORATION
Application year: 1985
Main classification: C08G63
IPC codes: C08G63, C08G69, C09K19