BLENDS OF LIQUID CRYSTALLINE POLYMERS OF HYDROQUINONE POLY(ISO-TEREPHTHALATES) p-HYDROXYBENZOIC ACID POLYMERS AND ANOTHER LCP CONTAINING OXYBISBENZENE AND NAPHTHALENE DERIVATIVES

Abstract: This invention relates to a blend comprising a first LCP polyester polymer consisting essentially of units (I), (II), (III), and (IV), having a melting point under about 420 DEG C, p is approximately equal to r+q, r is from about 0.05 to about 0.9, q is from about 0.95 to about 0.1 and s is from about 0.05 to about 9, and a second LCP polyester polymer comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid, oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprise(s) at least about 5 mole percent of the units in said second LCP polyester.

Description: BLENDS OF LIQUID CRYSTALLINE POLYMERS OF HYDROQUINONE POLY SO-TEREPHIΗALATES) p-HYDROXYBENZOIC ACID POLYMERS AND ANOTHER LCP CONTAINING OXYBISBENZENE AND NAPHTHALENE DERIVATIVES This is a continuation-in-part of USSN 255,632, filed October 11, 1988. This invention relates to a blend comprising a first LCP polyester polymer consisting essentially of units (I), (13), (HI), and (IV). having a melting point under about 420 * C, p is approximately equal to r + q, r is from about 0.05 to about 0.9, q is from about 0.95 to about 0.1 and s is from about 0.05 to about 9, and a second LCP polyester polymer comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid, oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprised) at least about 5 mole percent of the units in said second LCP polyester. Wholly aromatic polyester resins have long been known. For instance, 4-hydroxybenzoic acid homopolymer and copolymers have been described in the past and are commercially available. Such polymers commonly are crystalline in nature and, when molten, frequendy exhibit orientation in the melt; however, they have relatively high melting points or possess a decomposition temperature which is below the melting point, which leads to great difficulty in processing. The homopolymer of p-hydroxybenzoic acid is a very high melting, insoluble material and, hence, very difficult to fabricate. Melting points as high as 610°C were quoted - see W . Jackson, The British Polymer Journal, December 1980, p. 155. In order to depress the high melting point of the homopolymer so as to make it melt fabricable, a variety of materials incorporating different types of comonomers were prepared over the years. One such material is, for example, the resin made from p-hydioxybenzoic acid, isophthalic and/or terephthalic acids and 4,4-biphenol as described in Corns et al., U.S. Patents Nos. 3,637,595 and 3,975,487. The polymer has outstanding high temperature properties and can be molded to give articles of high modulus and strength. It is offered commercially by Amoco Performance Products, Inc. under the trade name of Xydar ® . These LCPs usually contain a relatively high percent concentration of hydroxybenzoic acid to reduce the concentration of the expensive biphenol. The main drawback of the prior art p-hydroxybenzoic acid copolymers and LCP polyesters containing no p-hydroxybenzoic acid moieties is the relatively high cost associated with the use of an expensive comonomer, such as 4,4'-biphenol, substituted hydroquinones (e.g., phenylhydroquinone), naphthalene diols, naphthalene dicarboxylic acids, and hydroxy-naphthoic acids. Efforts to replace these expensive monomers with the significantly less expensive hydroquinone, which is disclosed as an equivalent of biphenol in the aforementioned U.S. Patents Nos. 3,637,595 and 3,975,487, were made by several research groups; however, none of these investigations were successful. Study of the prior art shows that replacement of 4,4'-biphenol with hydro¬ quinone leads to materials with inferior properties. The problem created by the introduction of hydroquinone is basically the following: at high terephthalate contents, high melting generally intractable polymers are obtained; tractability may be achieved at higher isophthalate levels, but the polyesters are relatively low melting and often display low second order glass transition temperatures which lead to low moduli and low heat distortion temperatures. For example, polyesters from p-hydroxybenzoic acid (PHB A) isophthalic acid (IA) and hydroquinone (HQ) were prepared by Deex, U.S. Patent No. 4,377,681. At mole ratios PHBA/IA HQ of 33.3/33.3/33.3 the material had a glass transition temperature of 110°C; when the above coreactants were used at ratios of 5025/25, a Tg of ll5°C was obtained. The high melting points of a series of p-hydroxybenzoic acid terephthalic acid/hydroquinone copolymers are graphically illustrated in Figure 2 of the paper by G.W. Calundann, Industrial Development ofThermotropic Polyesters in High Performance Polymers: Their Origin and Development, 233-249 (R.B. Seymour and G.S. Kirshenbaum, editors 1986). The publication shows clearly (in Figure 2) that hydroquinone polymers melt at considerably higher temperatures than their 4,4-biphenol counterparts. The T m of the lowest melting composition shown is about 420°C. Figure 4 of the same publication (p. 243) indicates how one research group was ableto depress the melting points of the subject polymers by incorporating naphthalene diols, naphthalene dicarboxylic acids, and hydroxy naphthoic acids into them. From a purely technical point of view, the latter approach was a success; however, the modified polymers were still expensive due to the high cost of the naphthalene-based monomers. The intractability of the hydroquinone-derived materials is discussed in Jackson et al., U.S. Patent No. 4,242,496. Column 2, lines 18-26, states: "U.S. Patent No. 3,637,595 discloses that aromatic liquid crystal polyesters prepared from terephthalic acid, hydroquinone and varying amounts of p-hydroxybenzoic acid melt in the general range of 800° to 900°F. Obviously, the melting point of these polymers is far too high and the thermal stability is insufficient to permit these polymers to be used in conventional melt-processing equipment" It is further stated (column 2, lines 33-40) that a solution to the above problem "was to incorporate a substituent on some of the aromatic rings of the polyester, preferably on the diol ring. For example, it is well known that use of chloro, methyl or ethyl hydroquinone lowers the melting point of the polyester. Although this approach can be used to lower the melting point, typically the mechanical properties are also substantially reduced." The patent goes on to propose the use of phenyl hydroquinone (an expensive comonomer) as the best way whereby the melting point can be reduced to obtain tractable resins, without adversely affecting the mechanical properties. As indicated earlier, polyesters forming oriented melts were made from a variety of substituted hydroquinones. See, for example, Lee et al., U.S. Patent No. 4,600,765; Hutchings et al., U.S. Patent Nos. 4,614,790 and 4,614,791; and Funakoshi et al., U.S. Patent No. 4,447,593. Readily processible polyesters made from p-hydroxybenzoic acid, isophthalic and optionally terephthalic acid, hydroquinone and 3,4'- and/or 4,4'-biphenol, 3,4'- and or 4,4 , -dihydroxydiphenyl ether, 3,4'- and/or 4,4'-dihydroxydiphenyl sulfide are the subject of Dicke et al., U.S. Patent No. 4,603,190. It should be recognized that once again an expensive monomer is necessary to obtain tractable melts. Similar situations are encountered in a host of other U.S. and foreign patents. See, for example: Portugall et al., European Patent Appln. No. EP-257,558; Hisgen et al., European Patent Appln. No. EP-257,598; Hisgen et al., German Patent Appln. No. DE-3,629,208; Hisgen et al., German Patent Appln. No. DE-3,629,210; and Okamoto et al., World Patent Application No. WO-88 00,955. As pointed out above, tractable materials result at high isophthalic acid levels but the products typically display undesirably low glass transition temperatures. Deex, U.S. Patent No. 4,377,681 states (column 1, lines 31-38): "For example, liquid crystal copolyesters have been prepared from the following fairly rigid molecular species: p-hydroxybenzoic acid, hydroquinone and isophthalic acid. However, when ratios of the monomers are selected to provide tractable polymers, the glass transition temperature is generally low and the high temperature mechanical properties are reduced." Attempts to increase the Tg of these products have been made. Thus, Deex, U.S. Patent No. 4,377,681, claims copolyesters prepared from p-hydroxybenzoic acid, isophthalic acid, hydroquinone and 2,2-bis(4-hydroxyphenyl) propane. The preferred compositions contain from about 20 to about 35 mole percent of p-hydroxybenzoic acid units, and from about 5 to about 12 mole percent of 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A) based on the total diphenol components. Glass transition temperatures of about 175 to about 190°C were observed in these polymers. These values represent an improvement when compared to the Tg's of the polyesters mentioned supra. However, they must be considered low as they lead to heat distortion temperatures (HDTs) which are, at best, of the order of about 120 to 140°C; moreover, the introduction of bisphenol-A lowers the degree of crystallinity and the rate of crystallization which we believe leads to lower HDTs. In addition, mold shrinkage of these copolymers is unsatisfactorily high. Further, the introduction of aliphatic moieties affects the melt stability of these materials. It has now been discovered ώat the addition of a first polyester polymer (a) comprising recurring moieties of dihydroxyarylene comprising hydroquinone, a nonvicinal benzene dicarboxylate (preferably terephthalic acid and mixtures of terephthalic acid and isophthalic acid) and p-oxybenzoate to a second polyester polymer (b) comprising recurring moieties of naphthalene based monomers, p-oxybenzoate, or substituted hydroquinone wherein said polymers and the moieties making up the polymers are present in specified proportions, yields alloys with improved processibiϋty, improved mechanical properties, and improved surface characteristics (such as reduced tendency to blister or better gloss). In some cases, the alloys have better properties than the individual polymers at reduced cost With some known exceptions, mixtures of polymeric materials are generally immiscible. That is, they consist of domains of chemically distinct phases. Usually, one component forms a continuous phase, while the other component forms roughly spherical domains as inclusions. Under some circumstances, bi-continuous structures are also obtainable. Mixing two arbitrarily chosen polymers usually results in inferior materials having no utility, since in the absence of adhesion between phases, the dispersed phase merely weakens the continuous phase. Some polymeric products, such as the wholly aromatic polyesters, exhibit an ordered structure in at least some regions of the polymer. This order can exist in one, two or three dimensions. The incorporation into blends of polymers exhibiting an ordered structure leads to an increased tendency of the blends to separate into phases. This is believed to be due to the fact that the order found in certain regions of the resin causes a fairly sharp boundary between the domains of the molecules of the component polymers. Hence, blends including such polymers would be expected to exhibit a significant reduction in properties. It should be noted, however, that many useful blends whose morphology and phase interaction are favorable, are known. Cottis, U.S. Patent No. 4,563,508, is directed to the improvement of molding compounds based on wholly aromatic polyesters by the addition of a minor amount of a flow modifier wherein at least 30 mole percent of the aromatic diol is biphenol. The flow modifier crystallizes poorly and improves the flow of the highly crystallized base polymer it is added to. The flow modifier does not enhance the end properties of the blend -composition. It is to be noted that the addition of the flow modifier decreases the HDT of the composition and does not increase the strength. Takayanagi et al., U.S. Patent No. 4,228,218, discloses a polymer composition comprising 20 percent or less, based upon the total weight of polymeric material, of a first rigid polymer with the balance being a second polymer composed substantially of flexible molecular chains. The first polymeric material is dispersed in the second polymeric material in a microscopic region of 1 μ or less. It is believed that wholly aromatic polyesters would be characterized by those skilled in the art as rigid molecules within the context of the above cited patent The patent does not disclose blends of two or more polymers having rigid chains. Blends of polymers exhibiting orientation in the melt with other polymers were investigated. Mixtures of liquid crystalline polyesters with poly(alkylene terephthalates), polycarbonates and polyarylates were described in Cincotta et al., U.S. Patent Nos. 4,408,022 and 4,451,611; Froix, U.S. Patent Nos. 4,489,190 and 4,460,735; and in Kiss, European Patent Application No. 169,947. Improved mechanical properties were found with these materials. The addition of a particular liquid crystal polymer to poly(butylene terephthalate) or other thermoplastic polymers was described as a method to obtain compositions with enhanced resistance to melt dripping during burning (see Kim et al., U.S. Patent No. 4,439,578). In several instances, e.g., in alloys of liquid crystalline polyesters with an aromatic sulfone polymer (Froix et al., U.S. Patent No. 4,460,736) with an aromatic poly(ester amide) (Kiss, U.S. Patent No. 4,567,227), and with poly(arylene sulfides) (Froix, U.S. Patent No. 4,276,397) improved mechanical characteristics and improved processibility (lower viscosity) of the non-anisotropic resin were noted. Better properties were also obtained by blending two particular liquid crystalline polyesters (see, for example, Froix, U.S. Patent No.4,267,289). Liquid crystalline materials, including polyesters, were used to decrease the viscosity and improve the processibility of a number of other resins, including fluorinated polyolefins (see Bailey et al., U.S. Patent No. 4,417,020; Cogswell et al., U.S. Patent Nos. 4,429,078 and 4,438,236; and George et al., U.S. Patent No. 4,650,836). In one instance (Bailey et al., U.S. Patent No. 4,508,891), it was claimed that the addition of an isotrqpic resin to an anisotropic resin leads to a decrease of anisotropy in the corresponding molded articles. The fracture-surface morphology of thermotropic 6-hydroxy-2-naphthoic acid- p-hydroxybenzoic acid cσpolymer blends with nylon 6, poly(butylene terephthalate), and polycarbonate prepared by screw injection molding, was studied by Beery et al. J. Mater . Sci. Lett. 1988. 7(10), pp. 1071-3. The morphology was found to be strongly dependent on the flow history and on the composition of the subject mixtures. A commonly assigned patent application entitled "Extrusion-Grade Compositions Comprising Mixtures of Wholly Aromatic Polyesters," Serial No. 060,038, filed on June 9, 1987, in the names of Field et al., now U.S Patent 4,851,480, hereby incorporated by reference, describes alloys of a first polyester comprising recurring moieties of 4,4'-biphenol, terephthalate, and p-oxybenzoate; with a second polyester comprising the same recurring moieties, but wherein the proportion of the p-oxybenzoate units is higher than in the first polyester. The application discloses that while each individual polyester is difficult to extrude into acceptable products, their alloys provide good extrusion grade compositions. Molding compositions comprised of the above first and second polyester, filler, and optionally a * polymeric flow modifier are claimed in commonly assigned U.S. Patent Application entitled "Molding Compositions Comprising Mixtures of Wholly Aromatic Polyesters and Fillers," Serial No. 060,114 filed on June 9, 1987 in the name of J.J. Duska, hereby incorporated by reference. Thus, it is known from the prior art that it is possible to alloy two polyesters, wherein said polyesters are based on identical monomers but differ in the relative proportion of the monomers, wherein each of said polyesters has unsatisfactory molding and extrusion characteristics and obtain good molding and extrusion grade compositions. No reference is known which is directed to the improvement of surface properties by blending two polymers having orientation in the melt A feature of the instant invention that is totally unexpected and highly remarkable is the fact that compatible blends showing good mechanical and surface properties are achieved by alloying two crystalline wholly aromatic copolyesters prepared from monomers having totally different structures, e.g., phenylene versus naphthalene or biphenylene or substituted phenylene. In any event as indicated earlier, alloys of materials having ordered structures would be expected to have reduced properties. Hence, the instant discovery was highly surprising and totally unexpected that commercial LCP polyester resins can be alloyed with cheaper LCP polyesters based on hydroquinone without sacrifice of properties. It is the general object of the present invention to provide novel, inexpensive, melt-processible alloys comprising hydroquinone poly(iso-terephthalates) containing residues of p-hydroxybenzoic acid polymers which form highly tractable oriented melt phase, and which are capable of melt extrusion to form quality, high performance fibers, films, three-dimensional molded articles, etc. It is a further object of the present invention to provide novel, melt-processible alloys comprising hydroquinone poly(iso- terephthalates) containing residues of p-hydroxybenzoic acid, polymers which form a melt phase below 400°C in the substantial absence of polymer degradation, unlike many other polymers which include relatively high concentrations of the 4-oxybenzoyl moiety. These and other objects, as well as the scope, nature and utilization of the invention will be apparent to those skilled in the art from the following detailed description. It was unexpectedly discovered that advantageous alloys can be formed comprising a first LCP polyester, consisting essentially of units (I), (II), (HI), and (IV) having a melting point under about 420 * C; and molecular weights in the range of from about 2,000 to about 200,000, p is approximately equal to r + q, r is from about 0.05 to about 0.9, q is from about 0.95 to about 0.1 and s is from about .05 to 9.0, and a second LCP polyester polymer comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprise at least about 5 mole percent of the units in said second LCP polyester. The firstJXP polyester useful in this invention forms a stable oriented melt phase at about 200 to about 420 * C preferably from about 250 to 380 * C; the melt phase is tractable and can be melt extruded with the second LCP polyester polymer to form quality, high performance fibers, films, molded objects, etc. Generally speaking, the first LCP polyester is based on relatively inexpensive monomers such as terephthalic acid, isophthalic acid, hydroquinone and hydroxybenzoic acid while the second LCP polyester comprises expensive monomers such as naphthalene diol, hydroxynaphthalene carboxylic acid, naphthalene dicarboxylic acid, oxybisbenzoic acid, biphenol and substituted hydroquinones such as phenyl, methyl, ethyl, t-butyl, styryl, or alpha-methyl styryl. With the exception of biphenol, each of the expensive monomer moieties in the second LCP polyester can impart orientation in the melt at a level of at least about 5% of the units in the polymer while biphenol is generally used with hydroxybenzoic acid or hydroxynaphthoic acid moieties. Hydroxybenzoic acid moieties also can impart orientation in the melt at a level of at least about 5% of the units of the polymer. Accordingly, the second LCP polyester must comprise at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, oxybisbenzoic acid and substituted hydroquinone in a concentration sufficient to provide at least about 5 mole percent of the units in said second LCP polyester to provide orientation in the melt Of course, the first polyester has a higher concentration of hydroquinone units than the second polyester. The concentration of second LCP polyester can range from about 0.01 to 99 parts by weight per each part by weight of first LCP polyester, preferably .3 to 99 parts by weight and most preferably 0.3 to 3. In general, the higher the concentration of first LCP, the lower the cost of the alloy. FIRST LCP POLYESTER In somewhat greater detail while the first polyester of this invention having a melting point under 420"C and a molecular weight of about 2,000 to 200,000 consists essentially of units (I), (II), (IH), and (TV) wherein p is approximately equal to q + r, q ranges from about 0.05 to about 0.9, r ranges from about 0.95 to about 0.1 and s ranges from about 0.05 to about 9.0, the preferred first polyesters of this invention have melting points from about 250 * C to about 380 * C, p is approximately equal to q + r, q ranges from about 0.05 to about 0.7, r ranges from about 0.3 to about 0.95 and s ranges from about 0.07 to about 1.5. Within the preferred range, there are two classes of polyesters which are the subject of application numbers (Case 29,723) and (Case 29,724) filed on even date, which are hereby incorporated by reference. One class of preferred LCP polyesters useful in this invention form a stable oriented melt phase at 340 to 400°C, preferably from 340 to 380°C; the melt phase is tractable and can be melt-extruded below its decoπφosition temperature to form quality, high performance fibers, films, molded articles, and the like. Fabricated products of these polymers alone show high strength as well as good retention of properties at high temperatures. Materials filled with 30 percent by weight of glass fibers have heat distortion temperatures of over 240 to about 280°C and higher, under a load of 264 psi. It is believed that the higher the amount of crystallinity of the polymer the higher the heat distortion temperature (HDT) will be. The crystallization temperatures of these copolymers are in the range of from 300 to 340°C preferably from 310 to 340°C; and their crystallization rates are at least 1,000 and up to 3,500 counts per minute, preferably from 1,500 to 2,000 counts per minute. This first class of preferred polymers have the following approximate monomer ranges based on moles: s » 0.25 to 0.55; q « 0.5 to 0.666; r » 0.334 to 0.5, and p * 1.0. A second class of preferred LCP polyesters useful in this invention form a stable oriented melt phase at about 250 to 360 * C, the melt phase is tractable, and the polymers display a significant improvement in moldability and can be melt-extruded below their decomposition temperatures to form quality, high performance fibers, films, molded articles, and the like. Fabricated products show good surface properties, high strength, and good retention of properties at high temperatures. Advantageously, materials filled with 30 percent by weight of glass have heat distortion temperatures of over 200 to about 240 * C and higher, under a load of 264 psi. It is believed that d e higher the amount of crystallinity of the polymer the higher the heat distortion temperature (HDT) will be, also die higher the melting point This second class of preferred LCP polyesters have the following approximate monomer ranges based on moles: s * 0.075 to 1.5, q » 0.05 to 0.58, r * 0.42 to 0.95, and p - 1.0. The. synthesis of the first LCP polyesters of the instant invention is described generally in Cords et al., U.S. Patent No. 3,637,595 entitled "P-Oxybenzoyl Copolyesters," and in Finestone, U.S. Patent No. 4,742,149 entitled "Production of Melt Consistent Aromatic Polyesters"; the disclosure of the aforementioned two patents is incorporated herein by reference. The bulk condensation of aromatic polyesters is described in the patent literature and broadly considered involves an alkanoylation step in which a suitable dicarboxylic acid, hydroxybenzoic acid and diol are reacted with an acid anhydride; a prepoly- merization step in which the reaction product of the first step is polycondensed to prepare a prepolymer, and the prepolymer is thereafter heated in a third step to produce a polycondensate of the desired degree of polymerization. Thus, in somewhat greater detail, the instant copolyesters are prepared by charging into the reactor the required amounts of isophthalic and terephthalic acids, p-hydroxybenzoic acid and hydroquinone. An anhydride of a lower monocarboxylic acid, preferably an anhydride of a to C 4 monocarboxylic acid, is added in at least stoichiometric amounts. It is most preferred to use acetic anhydride; its amount is preferably from about 5 to about 20 mole percent over that required for the acetylation of all of the hydroxyl groups. The acetylation reaction takes place at about 140°C for a period of time of from about 2 to about 6 hours. The reaction mixture is then heated to about 240 to 320°C at a rate of about 10 to 40°C per hour, and is kept at about 240 to 320°C for approximately a few minutes to about 4 additional hours. The low molecular weight polymer obtained is then solid state advanced to the required high molecular weight by heating to a temperature of from about 265 to about 340°C, for a period of time of from about one to about 24 hours. A preferred variant as described in Finestone, U.S. Patent No.4,742,149, comprises adding a salt particularly an alkaline earth metal salt or an alkali metal salt preferably potassium sulfate, during the preparation of the resin and particularly to the prepolymer melt prior to advancement of the final product to d e desired degree of polymerization. The incorporation of stabilizing amounts of phosphites, as described in Corns, U.S. Patent No. 4,639,504 is also advantageous. These polyesters commonly exhibit O or — CH 3 C OH end groups depending upon the synthesis route selected. As will be apparent to those skilled in the art die end groups optionally may be capped, e.g., acidic end groups may be capped with a variety of alcohols, and hydroxyl end groups may be capped with a variety of organic acids. For instance, end capping units such as phenyl ester or methyl ester O C 0 CH 3 optionally can be included at the end of the polymer chains. The polymers can be annealed below their melting points for a period of time or the polymers may be oxidatively crosslinked to at least some degree, if desired, by heating in an oxygen-containing atmosphere (e.g., in air) while in bulk form or as a previously shaped article at a temperature below their melting points for a limited period of time (e.g., for a few minutes). The polyesters of the present invention tend to be substantially insoluble in all common polyester solvents such as hexafluoroisopropanol and o-chlσrophenol, and accc-idingly are not susceptible to solution processing. They can surprisingly be readily processed by known melt processing techniques as discussed hereafter. The polyesters of the present invention commonly exhibit weight average molecular weights of about 2,000 to about 200,000. These polyesters alone can be melt processed in the substantial absence of polymer degradation to form a variety of relatively stiff shaped articles, e.g., molded three-dimensional articles, fibers, films, tapes, etc. The polyesters are suitable for molding applications and may be molded via standard injection molding techniques commonly utilized when forming molded articles. Unlike die polyesters commonly encountered in the prior art it is not essential that more severe injection molding conditions (e.g., higher temperatures), compression molding, impact molding, or plasma spraying techniques be utilized. Fibers or films may be melt extruded. In some instances, as described in Cottis et al., U.S. Patent No. 4,563,508, melt fabrication may be facilitated by adding flow aids. These polymers can contain up to 10 mole percent (based on total reactants) of carbonate linkages and/or aromatic comonomers other than (I)-(IV), such as biphenol, provided that the use of said carbonate linkages and/or comonomers does not unfavorably affect die very attractive properties of the instant copolyesters. SECOND LCP POLYESTERS As indicated above the first LCP polyesters are blended with a second different LCP polyester comprising at least one moiety selected from d e group consisting of hydroxybenzoic acid, hydroxynaphdialene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid, oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprises at least about 5 mole percent of the units in said second LCP polyester. The preferred second LCP polyesters consist essentially of one or more units H, J, K, L, and M having a molecular weight of about 2,000 to 200,000, wherein R is at least one member selected from the group consisting of naphthalene and phenyl, alkyl (t-butyl), aralkyl (styryl or alpha-methyl styryl) or chloro substituted phenylene, Rj is at least one member selected from the group consisting of phenylene and naphdialene, R2 is at least one member selected from the group consisting of naphthalene and oxybiphenyl, R3 is at least one member selected from the group consisting of p-phenylene and m- phenylene, R4 is at least one member selected from die group consisting of phenylene, biphenylene and oxybiphenyl, h +j + k + 1 + m is approximately equal to l, h +j + k = 0.05 to 1, h + m is approximately equal to k + 1 and from about 0.05 to 1.0 units (preferably at least 0.15 units) in the polyester comprise at least one member selected from die group consisting of naphthalene, phenyl, alkyl (t-butyl), aralkyl (styryl or alpha-methyl styryl) or chloro substituted phenylene, oxybiphenyl and biphenylene. Unless stated to the contrary, each of the phenyl and phenylene groups are preferably para and die naphthalene groups are drawn infra. Suitable second LCP polyester useful in this invention include: a second polyester comprising units (IX), (X), and (XI): -j- wherein e is approximately equal to f; e is one; and g is in die range of from about 1.5 to about 5, preferably in the range of from about 2 to about 4, based on die number of moles of monomer corresponding to units (TX); where die molecular weight of said polyester is in the range of from about 2,000 to about 200,000; said second polyesters when admixed witii the first LCP yield blends tiiat are easy to melt fabricate, display vastly improved moldability and physical properties, yield parts pleasing to the eye; land, surprisingly, show a reduced tendency to blister on molding. A totally unexpected and surprising feature of die instant blends is diat botii tiieir moldability and die surface characteristics of the molded objects obtained from d em, are often better than the corresponding properties of many of the individual polyesters. In addition, die materials display improved mechanical properties over tiiose of the constituent polymers. Heat distortion temperatures, bodi on neat or on 30 percent by weight glass fiber filled compositions often range from at least 200 * C to as high as 350' C and higher under a load 264 psi, particularly when alloyed with preferred class 1 polyesters. Another second polyester comprises unit (V), (VI), (VII), and (Vπi): where a is approximately equal to b + c; b is in the range of from about 0 _5 to about 0.8; c is in die range of from about 0.5 to about 0.2; and d is in die range of from about 1 to about 7, preferably from about 2 to about 4, based on d e total number of moles of monomer corresponding to units (V) where said polyester has molecular weights in the range of from about 2,000 to about 200,000, said second polyesters when admixed with the first LCP yield blends tiiat are easy to melt fabricate and yield injection molded parts that surprisingly show a significandy decreased tendency to blister. In addition, die materials display improved mechanical properties over tiiose of the constituent polymers, as well as improved processibility, composites with preferred class 1 polyester containing about 30 weight percent of glass fibers, have heat distortion temperatures (HDTs) of at least 240°C, when measured under a load of 264 psi. An additional second polyester polymer comprises at least 1 unit : X ! - Ar - X 2 (XΠD wherein Ar comprises at least one member selected from die group consisting of: X 1 and X 2 are independendy oxy or carbonyl optionally in conjunction with units: Xi -Ar -X- 2 (xvm) wherein Xι and X 2 are as previously defined, and die Ar group of the second polyester can also comprise a divalent radical comprising at least one phenylene group such as phenylene, biphenylene and oxybiphenyl, having molecular weight of from about 2,000 to about 200,000. The instant blends with die preferred class 1 polyester are generally easier to melt fabricate, display improved moldability and yield parts pleasing to the eye with good surface characteristics. Unexpectedly, die materials usually have improved mechanical properties diat are quite often superior to the properties of die two constituent polymers. Heat distortion temperatures, both on neat and on 30 percent by weight glass filled blend compositions, are at least 175°C and may be as high as 300°C and even higher, when measured under a load of 264 psi. Especially preferred second polyesters are the copolyesters which are disclosed in U.S. Patent Nos.4,161,470; 4,184,996; and 4,256,624, herein incorporated by reference. The polyester disclosed in U.S. Patent No.4,161,470 is a melt processible wholly aromatic polyester which is capable of forming an anisotropic melt phase at a temperature below approximately 350°C apart from the blend. The polyester consists essentially of d e recurring moieties (XIX) and (XX) which may include substitution of at least some of die hydrogen atoms present upon an aromatic ring: 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, and mixtures of me foregoing. The wholly aromatic polyester there disclosed comprises approximately 10 90 mole percent of moiety (XTX) and approximately 90 to 10 mole percent of moiety (XX). The polyester disclosed in U.S. Patent No. 4,184,996 is a melt processible wholly aromatic polyester which is capable of forming an anisotropic melt phase at a temperature below approximately 325°C apart from the blend. The polyester consists essentially of the recurring moieties (XX), (XXI), and (XXQ): ( XX ) ( XXI ) (xxπ ) The wholly aromatic polyester there disclosed comprises approximately 30 to 70 mole percent of moiety (XX). The polyester preferably comprises approximately 40 to 60 mole percent of moiety (XX); approximately 20 to 30 mole percent of moiety (XXI); and approximately 20 to 30 mole percent of moiety (XXII). Each of die moieties of die polyester is free of ring substitution. The polyester disclosed in U.S. Patent No.4,256,624 is a melt processible wholly aromatic polyester capable of forming an anisotropic melt phase at a temperature below approximately 400°C apart from me blend. The polyester consists essentially of die recurring moieties (XIX), (XXm) and (XXTV) which may include substitution of at least some of d e hydrogen atoms present upon an aromatic ring: (XK ) (xxm) ( XXIV ) wherein Ar is as previously defined; witii 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, a phenyl group and mixtures of the foregoing. The polyester comprises approximately 10 to 90 mole percent of moiety (XIX), approximately 5 to 45 mole percent of moiety (XXDI), and approximately 5 to 45 mole percent of moiety (XXIV). Any of the LCP polyesters based on substituted hydroquinones discussed above can be used as die second LCP polyester such as poly phenyl substituted phenylene terephtiialates of U.S. Patent No. 4,159,365. The phenomenon of blistering is known. Blisters may occur near a surface or in the bulk of the sample. Here, we are mainly concerned with surface blisters; note, however, diat small internal blisters or voids may also be detrimental to material performance. Moldings based on polymers that show orientation in die melt display skin-core effects. Hence, phenomena observed in these systems are often analogous to those encountered in coatings and composites. In composites, for example, blistering and delamination occur especially between two layers of different composition. In coatings, blistering is known to be a localized delamination at an interface; it depends on die diffusion of chemicals such as water and degradation by-products. The difference in die diermal expansion coefficient between a coating and d e substrate can create stresses and may weaken die interface. A blister may then form with less pressure difference, due to volatiles, than in cases where these stresses are absent In summary thus, blistering is due to a surface layer delamination and can be caused eitiier by trapped volatiles or by built-in stresses. Most probably bodi factors are at work. Two types of blistering are encountered with polymeric materials: (1) molding blisters and (2) oven blisters. Blisters which occur during molding generally indicate die presence of degraded material. Quite often parts having acceptable surface characteristics are obtained upon molding. However, when tiiese parts are treated at high temperatures for a certain period of time, blisters ("oven blisters") often appear. These do not necessarily indicate d e presence of degraded material as a result of molding. It is of paramount importance that molding of the polymer does not yield parts having a blistered surface. It should be noted tiiat the configuration of a part is also quite often a factor in mold blistering. In any event if molding blisters are detected upon visual examination, the part will generally blister to a considerably greater extent when exposed to heat treatment Thus, the particular molding compound is most probably of inadequate quality. If, on die otiier hand, a good looking molding part is obtained, there is no assurance as to what the results of "oven testing" will be. For high temperature applications, it is imperative tiiat oven blistering be also either absent or significandy minimized. The oven test and die method of blister rating are described in the Experimental. The blends of the instant invention show a considerably decreased tendency to blister — both during molding and in the oven test Molding compounds may be formed from the subject copolyesters and blends by incorporating therein fillers such as talc, wollastonite or titanium dioxide; and/or reinforcing agents, e.g„ glass fibers. One attractive application of die novel copolyesters of the instant invention is, for example, in ovenware. Both die neat polymers or composites as disclosed by Duska et al., U.S. Patent No.4,626,557 are useful in this application. Molding compounds of interest in ovenware are described in commonly assigned U.S. Patent application entided "Novel Plastic Ovenware Compositions," Serial No. 255,753. Articles may also be molded from a molding compound which includes, as one component, the blend of die present invention. Such a molding compound incorporates into the blend of die present invention approximately 1 to 80 percent preferably approximately 10 to 70 percent by weight based upon die total weight of the molding compound, of a solid filler and/or reinforcing agent Representative fibers which may serve as reinforcing media include glass fibers, asbestos, graphitic carbon fibers, amorphous carbon fibers, synthetic polymeric fibers, aluminum fibers, aluminum silicate fibers, oxide of aluminum fibers, titanium fibers, magnesium fibers, rock wool fibers, steel fibers, tungsten fibers, etc. Representative filler materials include calcium silicate, silica, clays, talc, mica, carbon black, titanium dioxide, wollastonite, polytetrafluoroethylene, graphite, alumina trihydrate, sodium aluminum carbonate, barium ferrite, etc. The molding compounds are useful in a variety of applications including high temperature applications, for example, in cookware and electrical articles, and the like. It has been found in accordance with this invention that a uniform and pleasing appearance can be imparted to ovenware articles and any undesirable bubbling can be suppressed or minimized by die inclusion of talc in the oxybenzoyl compositions from which they are molded. The talc contains a minimum amount of materials decomposable at elevated temperatures, e.g., up to about 800°C, such as magnesium carbonate. Among such talcs are talcs which are of high purity, are selectively combined from various ores or have been calcined or subjected to acid treatment These talcs which are employed according to die present invention are characterized by a low weight loss on ignition, a low iron content analyzed as iron oxide, and a closely controlled particle size. The weight loss on ignition of the suitable talcs is not more tiian 6 percent or less at 950°C and is 2 percent or less at 800°C. The iron content analyzed as iron oxide will not be more dian about 1 percent and tiiat of die particularly preferred talcs will not be more than about 0.6 percent and may be less. In addition, die particle size distribution of the talc must preferably be such that about 90 to 95 percent of the particles are less than about 40 microns. Experiments and tests carried out have demonstrated quite conclusively tiiat it is essential to use such talc in order to realize the objectives of die present invention. The use of otiier forms of talc does not provide satisfactory properties in the finished molding product However, such other forms of talc can be employed in conjunction with die specified talcs in amounts of from about 0.05 percent to about 20 percent of the required forms of talc. The talcs containing the minimum amounts of decomposable material will be presented in amounts of from about 1 percent to about 60 percent based on the total composition weight with the preferred range being from about 35 percent to about 55 percent Rutile titanium dioxide can also be employed in conjunction with the talc material, including mixtures of highly refined talcs and otiier talc. The rutile titanium dioxide will be present in a proportion of from about 2 percent to about 20 percent based on die weight of the total composition. The preferred range is from about 2 percent to about 15 percent In the molding compositions of the present invention, die resins will generally comprise from about 35 percent to about 85 percent and die total inerts from about 65 percent to about 15 percent For optimum results, the inerts will comprise from about 40 percent to about 55 percent of the molding compositions. The inerts will comprise up to about 55 percent of highly refined talc and from about 0 to about 10 percent of titanium dioxide. The compositions of die present invention can be prepared by extrusion in accordance with generally known practice. For example, a twin screw extruder can be employed with addition of die polymer, selected talc, and titanium dioxide at die feed throat and with addition of die glass roving at both d e vent and feed tiiroat The compositions so prepared can then be injection molded according to general practice using techniques familiar to the injection molding field. Examples The following examples serve to give specific illustrations of the practice of this invention but they are not intended in any way to limit the scope of this invention. The examples and comparative examples are plotted on die triangular phase diagram. Experimental Procedures The following procedures were used to obtain the data given in the examples. A. X-ray Mcasure aφnts 1. Apparatus X-ray diffraction data were obtained using a Philips XRG-3000 X-ray generator equipped with a vertical diffractometer, a long, fine focus copper X-ray tube, a Paar HTK-10 high temperature diffractometer attachment and a Paar HTK-heat controller. Diffractometer position is controlled by computer, which also measures and records radiation count rate produced by sample crystallinity and sample temperature. (a) Determination of the Polymer Melting Point A sample of the polymer is submitted to a preliminary X-ray diffraction scan between 15 and 25 degrees two-theta angle by increasing the temperature by increments of 60°C within a temperature range from about 200 to about 480°C. This allows determination of the approximate temperature at which the peak located at approximately 19.7 degrees two-theta (4.50 A d-spacing) reaches its minimum value, i.e., an approximate melting point A second-degree polynomial equation is derived from die above data; this polynomial equation now allows to follow die peak angle as the sample temperature is varied. The temperature at which the peak height reaches a minimum (i.e., touches the baseline), is considered to be the melting point The polymer sample is now heated and cooled at a rate of 100°C per minute between the previously mentioned temperature limits, and its melting point is deter¬ mined Since the melting point of a crystalline material often changes on heating and cooling (due to recrystallization, further polymerization, etc.), the sample is cooled and reheated. This allows determination of the melting point on the second heating cycle. Generally, the second cycle yields a melting point which remains approximately constant if additional heating or cooling cycles are performed. Therefore, the value obtained in the second heating cycle is taken as the polymer melting point (b) The crystalline melting point is measured by following the intensity of the X-ray diffraction of die most intensive peak as a function of temperature. The most intensive diffraction peak is located at a spacing of about 4.5 A. Based on literature data [J. Polymer Sci., Polym. Chem. Ed., H, 2207 (1976); J. Polymer Sci., Polym. Chem. Ed., 21, 2249 (1983)], the subject peak has been tentatively assigned to die distance between the polymer chains. The point at which die intensity reaches a minimum is considered for the polymer melt temperature. The rate of temperature change is 100 * C per minute. The onset of crystallization is measured while the sample is cooled at 100°C per minute. The temperature at which the peak emerges from die baseline during die second cooling cycle is considered as die onset of crystallization. (C) CrvRta11i7atir>n Rate At every temperature below die sample melting point, the intensity of X-ray diffraction of a crystalline material can be expressed as counts per second (or any unit of time). The increase in the number of counts per unit of time while die sample is being cooled at a certain rate (100°C per minute) is therefore proportional to the rate of crystallization. A temperature interval starting at the onset of crystallization and 40°C below tiiat temperature was arbitrarily chosen. Rates of crystallization are expressed as the increase in counts per minute for a sample cooled witiiin these temperature limits during the second cooling cycle. B. DMA Flexural Modulus The measurement is performed using a Dupont Dynamic Mechanical Analyzer (DMA), Model 982 in conjunction with a thermal analyzer, Model 1090. The DMA measures changes in the viscoelastic properties of materials as a function of time and temperature. Tests are conducted at a heating rate of 5°C per minute. When d e run is complete, the stored data is analyzed; die storage modulus (very similar to the flexural modulus) and d e loss modulus are calculated and plotted as a function of temperature. The modulus is expressed in GPa's and die temperature in degrees Centigrade. Conversion into psi's is performed using the equation: Modulus (psi) = Modulus (GPa) x (1.45*105) C. Compressive Flow (CF) The term "Compressive Flow" (CF) as used in this application is a measure of the flow of a weighed sample when pressed on a Carver press at 5,000 pounds. It is also an indirect measure of the polymer molecular weight die higher the CF value at a given temperature, the lower is die molecular weight of the wholly aromatic polyester. CF is measured from the area of a disc obtained from a sample of powdered material of given weight usually 0.5 to 1.0 grams which has been pressed between two parallel plates. In carrying out the determination of this characteristic, a sample is pressed between two sheets of aluminum foil which in turn are backed by chromium-plated steel plates 6" x 6" x 1/4". A Carver 2112-X Model No. 150-C hydraulic press modified for 800°F is used to press the sample. The particular temperature of the press is that indicated in each sample run. The sample material is allowed to stand for 5 minutes between the plates at holding pressure in order that die temperature of die material can equilibrate with die press temperature. A load of 5,000 pounds is then applied for 2 minutes. The CF is then calculated on the following basis. The area of the pressed molding compound is measured by cutting an aluminum sandwich out of die sample pressed between the two aluminum foil sheets. The aluminum foil has a known area weight relationship called d e foil factor. The area is normalized for the pressure of the applied load and tiiat number is multiplied by 100 to give a number greater than 1. The compressive flow is tiien calculated by means of the following equation: CF = X 100 Applied Load (Kg) X wt of sample D. Blister Rating Samples to be tested are preconditioned at 20 to 25°C, 50 ± 5 percent relative humidity for 48 hours. Test sample lot normally includes five tensile bars (1/8" thick), five HDT bars (5" x 1/2" x 1/4" thick) and five flex bars (5" x 1/2" x 1/8" thick). The samples are carefully inspected and any existing cracks and/or blisters are circled. The samples are then annealed in an oven which has been equilibrated at 232°C (450°F) for a period of 4 hours. They are then removed, cooled and inspected. Rating codes follow: 0 - no new blisters; 1 - very slight blistering (one or two very small blisters) 2 - slight blistering (three to six small blisters); 3 - moderate blistering (a few large blisters and or many small blisters); and 4 - heavy blistering (many large or small blisters covering more than half of of the specimen surface). The numerical blister rating is calculated using the equation: R = l/n ∑ . Xi 2 i = 1 where R = numerical blister rating (0-16); n = number of samples tested; X j = blister rating sample i (0-4). In the above calculation, die individual ratings for the entire set of test samples (tensile bars, HDT bars, flex bars) are generally treated as a single population. The ratings vary widiin die range of 0 (no blistering) to 16 (severe blistering, worst case). E. Determination of the Fiber Rating Fiber ratings were obtained using a hot bar apparatus with a temperature range from 270 to 415°C. A 2 to 5 gram sample of polymer is thinly and evenly sprinkled on d e upper portion of die hot bar using a spatula and is allowed to melt Using a large pair of tweezers, grab a small portion of material from the melted pool and slowly draw a fiber at a steady speed. The following rating system is used: 0 - Material does not melt or does not draw a fiber 1 - Material draws a short fiber with poor strength 2 - Material draws an intermediate lengdi fiber with intermediate level of tenacity or material draws a long fiber with poor strength 3 - Material draws a long fiber witii good strength L - An additional rating of L is added to the rating of 0-3 if a low melt temperature occurs which indicates low molecular weight A - An additional rating of A is added if the melted material is clear which indicates die material is amorphous in the melt state F. VES VPS or vapor phase soldering is an assembly technique used to solder components to a printed circuit board. This technique involves heating a fluid to its boiling point so that a vapor is produced tiiat is above the melting temperature of standard solder. The printed circuit assembly is placed into the vapor blanket The vapor condenses onto the printed circuit assembly and causes the solder to reflow. VPS Procedure 1. Samples were processed as received and preconditioned for 7-day intervals at 75% Relative Humidity/Room Temperature. 2. The vapor phase unit used was Model No.912 II manufactured by HTC. 3. The primary vapor was FC-70 Fluσrinert an inert fluorochemical manufactured by 3M Company. The vapor was at a temperature of 428°F (220°C). 4. The secondary vapor was Genesolv D, a trichlortrifluσroethane manufactured by Allied Chemical Company. The vapor was maintained at a temperature of approximately 117°F (47°C). 5. The samples were lowered dirough the secondary vapor into the primary vapor and allowed to dwell for 4 minutes. 6. During the removal cycle, the samples were allowed to dwell for 30 seconds in the Genesolv D vapor and then removed totally. 7. Samples were examined for blistering. If no blistering is evident, tiien the samples are considered passed. If blisters are evident die sample has failed. G. Miscellaneous The flexural strength of the experimental samples was measured according to the procedure of ASTM D-790-84A; and HDT (DTUL) data were obtained using the method as described in ASTM D648. Tensile strength were measured in accord with ASTM D-638. Polymerizations pxam lg P-l This is an example of the synthesis of a novel polyester based on terephtiialic acid, isophdialic acid, p-hydroxybenzoic acid, and hydroquinone in the nominal mole ratio of 0.6:0.4:0.5: 1. The following ingredients were combined in the manner described. Items A through F were charged to a 15-gallon, oil heated vessel equipped with an anchor type stirrer, reflux condenser, after condenser, injection por and distillate receiver. After purging widi nitrogen, die contents were heated with stirring to 141°C and held under reflux at that temperature for 3 hours. Distillation was then started while increasing the temperature over a 4.8 hour period to 285°C. Item G was tiien injected into the vessel. After an additional 15 minutes die contents of the vessel were transferred to a sigma blade mixer that had been preheated to 320°C. After mixing for 4 hours at this temperature under an atmosphere of nitrogen, the mixer was cooled to near room temperature where the contents were removed as a granular solid. The melting point of die polymer (X-ray) was 359°C; its crystallization temperature was 336°C with a crystallization rate of 2,400. A sample of the polymer was melted, extruded and pelletized with a twin screw extruder. The pellets were molded into test specimens. The resulting testing showed superior high temperature performance with a heat distortion temperature of 250°C and a flexural modulus of 570,000 psi as measured at 250°C by DMA. A molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens. The heat distortion temperature of the obtained composite was 264°C and its flexural modulus (by DMA) was 520,000 psi as measured at 250°C. (ASTM-D-4065) Example P-2 The ingredients were the same as in Example P-l with die exception that die amount of item F was 14.16 grams, and tiiat item G was not used in the preparation. The equipment was the same as in example 1 and die operating procedure is described below. After purging with nitrogen, the contents were heated with stirring to 141°C and held under reflux at that temperature for 3 hours. Distillation was then started with increasing the temperature over a 3.6 hour period to 250°C. The reaction mixture was then stirred for 1 hour at 250-260°C. The contents of die vessel were transferred to a sigma blade mixer which had been preheated to about 250°C. The material was mixed while the temperature was increased to 300°C and mixing was continued for a total of 5 hours at that temperature. A molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens. The heat distortion temperature of the obtained composite was 250°C and its flexural modulus (by DMA) was 420,000 psi as measured at 250°C. (ASTM-D-4065) Example P-3 The ingredients were die same as in Example P-2 with the exception of item F the amount of which was 7.08 grams; also, 16.00 grams of triphenyl phosphite were added prior to transfer of die reaction mixture to the sigma blade mixer. Otherwise, the procedure was the same as in Example P-2. The melting point of the polymer (X-ray) was 359°C; its crystallization temperature was 329°C with a crystallization rate of 2,500. A molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens. The heat distortion temperature of die obtained composite was 268°C and its flexural modulus (by DMA) was 480,000 psi as measured at 25Q°C. (ASTM-D-4065) Example P-4 This is an example of the syndiesis of a novel polyester based on terephdialic acid, isophthalic aεdd p-hydroxybenzoic acid and hydroquinone in the nominal mole ratio of 0.6:0.4:0.75:1. The following ingredients were combined in the manner described: These ingredients were processed as described in Example P-l. The melting point of the polymer (X-ray) was 353°C; its crystallization temperature was 331°C with a crystallization rate of 2,100. A molding composition containing 70 weight percent of the above polymer and 30 weight percent of milled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens. The heat distortion temperature of d e obtained composite was 240°C. Additional polymers were examined in Tables IV and VI. The polymers of Tables IV and VI were prepared using the mole percentage of monomers delineated in the table and reacting there in the same manner as P-l to P-4. Fr7rømptø P--7 ' This is an example of die synthesis of a novel polyester based on terephdialic acid, isophthalic acid, p-hydroxybenzoic acid, and hydroquinone in the nominal mole ratio of .4142 .5858 .4285/1.015. The following ingredients were combined in the manner described. Items A through F were charged to a 15-gallon, oil heated vessel equipped with an anchor type stirrer, reflux condenser, after condenser, injection port, and distillate receiver. After purging with nitrogen, die contents were heated witii stirring to 141 * C and held under reflux at diat temperature for 3 hours. Distillation was then started while increasing the temperature 20'C hr to 259 * C. Item G was then injected into the vessel. After the reactor reached 263 * C die contents of the vessel were transferred to a sigma blade mixer that had been preheated to 300"C. After mixing for 5 hours at this temperature under an atmosphere of nitrogen, the mixer was cooled to near room temperature where the contents were removed as a granular solid. The melting point of the polymer (X-ray) was 268 * C; its crystallization temperature was 248 * C with a crystallization rate of 186. A sample of the polymer was blended with glass, melted, extruded and pelletized with a twin screw extruder. The pellets were molded into test specimens. The resulting testing showed superior high temperature performance with a heat distortion temperature of 238 * C. Example P-6 This example describes die preparation of a polyester in the laboratory. It is to be noted tiiat the preferred method is described in Example P-7 and die following . wherein the polymers were produced in scaled-up size in the pilot plant There a continuous method of in situ polymerization was utilized which is more demonstrative of scale-up production and economies. Unfortunately in scale-up production, physical and mechanical operating parameters can be varied as compared to laboratory production. The polyester had die molar composition: terephthalic acid isophthalic acid/p-hydroxybenzoic acid/hydroquinone 0.5/0.5/1.0/1.0 (see Cottis et al., U.S. Patent No. 3,637,595; example no. 10, noted as designation"x" on Figure 1). A 5 liter resin flask equipped with a stirrer, condenser system designed both for reflux and distillation, and a heating mantle was charged with the following: 1,092.5 g of p-hydroxybenzoic acid; 657.1 g of terephthalic acid; 657.1 g of isophthalic acid; 871.0 g of hydroquinone; and 2,786.0 g of acetic anhydride. The above mixture was heated at reflux for a period of 3 hours; vigorous stirring was maintained diroughout the reaction. At die end of die reflux period collec¬ tion of distillate was started. The reaction mass was then heated at a rate of about 30°C per hour to 311°C at which point 98.2 percent of the theoretical distillate was collected. The molten material was poured into an aluminum pan and allowed to cool to room temperature. The solid was pulverized and ground to pass a 2 millimeter screen. The powder was placed in a drum and was heated in a nitrogen stream, while rotating, to a temperature of 330°C; and held at tiiat temperature for two hours. The product was removed from the drum after cooling. The melting point of the polymer (X-ray) was 325°C; its crystallization temperature (onset of crystallization) and crystallization rate (both measured via X-ray techniques) were 299°C and 2,242, respectively. A portion of die product was pelletized and injection molded into test specimens. The neat polymer had a HDT of 226°C, a flex strength of 16,000 psi, a flex modulus of 1.85 X 10 6 psi and a blister rating of 16. Another portion of the product was compounded widi milled glass fiber to prepare a pelletized material containing 30 percent glass. Injection molding yielded test specimens which were very brittle. Therefore, to run HDT analyses, 1/8" Flex Bars were used. The HDT was 233°C. Exapφfc P-7 This example describes die preparation of a polyester having the mole ratio of 0.5/0.5/1.0/1.015. The following ingredients were combined in the manner described: ______ l_m_______ A Terephthalic acid B Isophthalic acid C p-Hydroxybenzoic acid D Hydroquinone E Acetic anhydride F Magnesium acetate tetrahydrate G Triphenyl phosphite Items A through F were charged to a 15-gallon, oil heated vessel equipped with an anchor type stirrer, reflux condenser, after condenser, injection port, and distillate receiver. After purging widi nitrogen, the contents were heated with stirring to 141°C and held under reflux at that temperature for 3 hours. Distillation was tiien started while increasing the temperature 30° /hour to 273°C Item G was then injected into die vessel. After die reactor reached 277°C the contents of the vessel were transferred to a sigma blade mixer that had been preheated to 285°C. After mixing for 5 hours at this temperature under an atmosphere of nitrogen, the mixer was cooled to near room temperature where the contents were removed as a granular solid. The melting point of the polymer (X-ray) was 349°C; its crystallization temperature was 331°C with a crystallization rate of 1667. A sample of the polymer was blended with glass, melted, extruded, and pelletized with a twin screw extruder. The pellets were molded into test specimens. The resulting testing showed lower temperature performance widi a 264 psi heat distortion temperature of only 214°C Blends Preparative Examples Example B- Preparation of polyester having the following molar composition: 0.25 moles isophdialic acid/0.75 moles terephdialic acid/3.0 moles p-hydroxybenzoic acid/1.0 mole 4,4-biphenol. A mixture of: 184 lbs of terephthalic acid; 61 lbs of isophdialic acid; 612 lbs of low ash p-hydroxybenzoic acid; 275 1bs of4,4'-biphenol; 868 lbs of acetic anhydride; and 40.1 grams (88.5 ppm) of magnesium acetate tetrahydrate was placed in a 325 gallon rectOT and heated with stirring until distillation started. The rector was held at this temperature for 3 hours. Distillation was started and die temperature increased until 400 pounds of distillate had been collected. The contents were pressured into a 200 gallon reactor and die temperature was increased at a rate of 30°C per hour until die contents reached 313°C. Then the contents were poured into a mechanical mixer and mixed at 290 to 300°C for 5 hours. Six batches of polymers were made with compressive flows at 330°C from 55 to 74, and polymer had very good color. ExampkB-2 Preparation of polyester having the following molar composition: 1 mole terephthalic acid 3.7 moles p-hydroxybenzoic acid/1 mole 4,4-biphenol. The following ingredients were combined in the manner described: Item Ingredient A Terephthalic acid B p-Hydroxybenzoic acid C 4,4'-Biphenol D Acetic anhydride E Potassium sulfate F Pentaerythritol diphosphite Items A through E were charged into die rector and heated to 307°C over a period of 10 hours with distillation of acetic acid. Item F was men added and heating was continued for 6 minutes to a melt temperature of 310°C. The contents of the vessel were transferred to a sigma blade mixer that had been preheated to 335°C. The temperature was raised to 350°C and mixing was continued at 350°C for 9.5 hours under an atmosphere of nitrogen. The mixer was cooled to near room temperature where the contents were removed as a granular solid having a compressive flow of 52. Example B-3 The naphthalene-based polyester used in the instant blends was Vectra® A950, produced by die Hoechst-Celanese Corporation and composed of about 73 mole •percent 4-oxybenzoyl moieties (XX) and 27 mole percent of 6-oxy-2-naphthoyl moieties (XDQ: Preparation of Polyester Blends Gsπsal Polyesters prepared as described in preparative examples 1 and 2 were formulated into a 30 percent glass filled composition, compounded and pelletized. The blends contained as a percentage of the resins phase, either 0, 10, 21 or 40 weight percent of polymer (b). The formulations were compounded and pelletized on a 25 mm diameter Berstorff twin screw extruder. The barrel profile temperature for compounding was: Barrel zone 1 = 320 to 325°C Barrel zone 2 = 355 to 362°C Barrel zone 3 = 355 to 376°C Barrel zone 4 = 365 to 395°C Barrel zone 5 = 380 to 400 C C Barrel zone 6 = 370 to 380°C Barrel zone 7 = 360 to 370°C Die = 355 to 380°C The screw rpm was 170 to 175; the output was 12 to 15 pounds per hour. The above materials were molded on a 75 ton, 3 ounce Newbury injection molding machine. The barrel profile was: Rear zone about 377°C Front zone about 382°C Nozzle about 388°C The mold temperature was set at 121°C and the injection pressure was in the range of 1,000 to 1,360 psi. The molding machine screw rpm was about 330. The formulations of Table VII were compounded and pelletized on a 25 mm diameter Berstorff twin screw extruder. The barrel profile temperature for compounding was: Barrel zone 1 = 293 to 320°C Barrel zone 2 = 360 to 376°C Barrel zone 3 = 375 to 400°C Barrel zone 4 = 395 to 405°C Barrel zone 5 = 390 to 400°C Barrel zone 6 = 370 to 385°C Barrel zone 7 = 375 to 387°C Die = 370 to 387°C The screw rpm was 175 with an output of about 10 to 13 pounds per hour. The above materials were molded on a 75 ton, 3 ounce Newbury injection molding machine having the following barrel temperature profile: Rear zone about 377°C Front zone about 382°C Nozzle about 388°C The mold temperature was set at 120°C for composition no.7 and at 66°C for all other compositions. The injection pressure was 1,000 psi and die molding machine screw rpm was about 330. Blends of Table XI (test nos. 21-32): Barrel zone 1 = 150 to 176°C Barrel zone 2 = 270 to 345°C Barrel zone 3 = 285 to 365°C Barrel zone 4 = 275 to 370°C Barrel zone 5 = 270 to 370°C Barrel zone 6 = 280 to 365°C Barrel zone 7 = 275 to 360°C Die = 270 to 355°C Blends of Table XI (test nos. 33-40): Barrel zone 1 = 185 to 301°C Barrel zone 2 = 370 to 385°C Barrel zone 3 = 385 to 400°C Barrel zone 4 = 390 to 400°C Barrel zone 5 = 385 to 390°C Barrel zone 6 = 375 to 380°C Barrel zone 7 = 370 to 376°C Die = 370 to 374°C Blends of Table XI (test nos.41-44): Barrel zone 1 = 320°C Barrel zone 2 = 355 to 360°C Barrel zone 3 = 370 to 375°C Barrel zone 4 = 390 to 395°C Barrel zone 5 = 390°C Barrel zone 6 = 370°C Barrel zone 7 = 370 to 376°C Die = 350 to 375°C The screw rpm was in the range of 120 to 175 for all the blends; the output was about 10 to 13 pounds per hour. The above materials were molded on a 75 ton 3 ounce Newbury injection molding machine having the following barrel temperature profile: Blends of Table XI (test nos. 21-32): Rear zone = 376 to 337°C Front zone = 271 to 337°C Nozzle = 282 to 348°C Blends of Table XI (test nos. 33-40): Rear zone = 337 to 388°C Front zone = 332 to 382°C Nozzle = 343 to 393°C Blends of Table XI (test nos. 41-44): Rear zone = 299 to 371°C Front zone = 288 to 377°C Nozzle = 299 to 382°C The mold temperature was set at 66°C for compositions 21 to 32 and 36; it was 99°C for no.44 and 120°C in all other examples. The injection pressure was: 1,000 psi in examples: 21,27,28,29,30,31,32,35,36,37 and 38; 1,400 psi in all other examples. The molding machine screw rpm was set at 330. Examinations of die table shows that die blends can generally be fabricated at lower temperatures than the corresponding controls; tiierefore there is less chance of decomposition and concurrently less blistering. Summary of Tables Tables I - V: Properties of Neat and Glass-Filled Polymers Tables I - m Additional materials that were prepared are listed in Tables I, π, and HI. Table I lists the polyesters useful in this invention which by themselves have desirable properties. Table H lists borderline resins. Table HI lists polymers whose properties are relatively poor. Table IV: Polymers Runs 1 to 26 in Table IV do not correspond to same run numbers in Tables I, H, and HI. Table V: Polvmer Fiber Rating Runs 1 to 79 in Table V do not correspond to the same number runs in Tables I, H, m,.and IV. Tfth ff -Vfl - XHI: Blends of Polyesters (a) and (b) and tiieir properties The blends have lower injection molding temperatures than die base polymer showing they can be fabricated at lower temperatures. The data clearly show that the blends display improved mechanical properties - see, for example, Table VH flexural strengdis, test nos. 3 through 6. Overall, a significant and unexpected improvement in surface properties (blister rating) is also observed. The high HDTs of the novel blends are noteworthy, they are intermediate between tiiose of the constituent polymers of the blends. This in turn could be interpreted as a result of compatibility for the instant highly crystalline polyesters. DMA modulus data show that stiffness is maintained up to quite high temperatures, making the present materials useful at elevated temperatures. In conclusion, therefore, the blends of this invention possess a combination of toughness, surface, and high temperature properties that could not be anticipated beforehand. TABLE I (a) The polymers were prepared via mediods similar to diat used in Example 7. In all of the examples, p is one. (b) Counts per minute. Remarks ( d ) Poor processibility HDT=219 * C Neat polymer fused at 450 * C with decomposition (smoke) when compounding was attempte 387 347 2810 361 335 2700 Same as Example 8 11 334 300 1794 12 389 341 3200 13 362 291 2000 14 333 311 1510 15 381 344 3860 16 400 351 2500 17 334 294 2110 18 366 304 820 19 387 309 430 (a) Prepared in a manner similar to that of Example 6, except where otherwise indicated. (b) Prepared in a manner similar to that of Example P- 1. (c) In all examples p is equal to one. (d) HDT measured on 30 percent by weight milled glass filled compositions. (e) Counts per minute. TABLE HI (Continued) PROPERTIES Example Composition* 0 * No. (a) Remarks (d) 72 0.20 0.80 0.75 73 0.00 1.00 0.75 74 0.462 0.538 0.538 75 1.00 0.00 0.50 76 0.30 0.70 0.50 77 0.00 1.00 0.50 78 0.80 0.20 0.25 79 0.70 0.30 0.25 80 0.50 0.50 0.25 81 0.30 0.70 0.25 82 0.00 1.00 0.25 83 0.61 0.39 0.22 84 0.41 0.59 0.18 85 0.70 0.30 0.10 86 0.50 0.50 0.10 87 0.30 0.70 0.10 88 0.80 0.20 0.00 89 0.70 0.30 0.00 90 0.10 0.90 0.00 (a) Polymers were prepared in a manner similar to that of Example 6, except where noted. (b) Prepared as described in Example P- 1. (c) In all Examples p is equal to 1. (d) Measured on a 37 weight percent talc filled composition. (e) Measured on a 30 weight percent milled glass filled composition. (0 Counts per minute. TABLE Vπ BLENDS OF POLYESTERS (a) and (b) (!) Henry and Frick, untreated 3016 (1/16") glass fiber. ( 2 ) Based on OC497 glass roving (Owens-Coming). TABLE Vπi 1 Blister rating: 0 = best; 16 = worst. 2 Value at 30°G TABLE DC TABIJEX ROOMTEMPERATUREIZODDATA OFBLENDSOFPOLYESTERSOFTABLEVH TλB E BLENDS OF POLYESTERS (!) Henry and Frick, 1/16" milled glass fiber. _____ι___w PROPERTIES OF BLENDS OF TABLE XI BLENDS A 0.45 moles terephthalic acid 0.55 moles isophthalic acid 0.50 moles p-hydroxybenzoic acid 1.0 moles hydroquinone B: 0.75 moles terephthalic acid 0.25 moles isophthalic acid 3.0 p-hydroxybenzoic acid 1.0 biphenol

Claims: WE CLAIM 1. A blend comprising a first LCP polyester polymer consisting essentially of units (I), (II), (El), and (TV). having a melting point under about 420'C, p is approximately equal r + q, r is from about 0.05 to about 0.9, q is from about 0.95 to about 0.1 and s is firom about 0.05 to 9, and a second LCP polyester polymer comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydroxy naphthalene, naphthalene dicarboxylic acid, oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprise(s) at least about 5 mole percent of the units in said second LCP polyester. 2. The blend of Claim 1 , wherein the second LCP polyester can range from about .3 to 99 parts by weight per each part by weight of first LCP polyester. . The blend of Claim 1 , wherein die first LCP polyester forms a stable oriented melt phase at about 340 to 400 * C, s » 0.25 to?55, q » .5 to .66, r *.334 to 0.5, and p - 1.0. 4. The blend of Claim 1 , where die first LCP polyester filled with 30% by weight glass has an HDT of at least about 240 * C. 5. The blend of Claim 1 , wherein the first LCP polyester forms a stable oriented melt phase at about 250 to 360'C, s » 0.075 to 1.5, q - 0.05 to 0.58 r - 0.42 to 0.95, and p - 1.0. 6. The blend of Claim 1 , wherein the first LCP polyester filled with 30% by weight glass has an HDT of at least about 200'C. 7. The blend of Claim 1 , wherein the first LCP polyester contains up to 10 mole percent biphenol moieties. 8. The blend of Claim 1, wherein the first LCP polyester contains more hydroquinone moieties than the second LCP polyester. 9. An alloy comprising a first LCP polyester polymer consisting essentially of units (I), (IT), (d), and (IV). having a melting point under about 420 * C, p is approximately equal to r + q, r is from .05 to .9, q is from 0.95 to .1 and s is from about .05 to 9 and a second LCP polyester consisting essentially of one or more units H, J, K, L, and M: having a molecular weight of about 2,000 to 200,000, wherein R is at least one member selected from die group consisting of naphthalene and phenyl substituted phenylene, alkyl substituted phenylene, aralkyl substituted phenylene and chloro substituted phenylene, Rj is at least one member selected from the group consisting of phenylene and naphthalene, R2 is at least one member selected from the group consisting of naphthalene and oxybiphenyl, R3 is at least one member selected from the group consisting of p-phenylene and m-phenylene, R4 is at least one member selected from the group consisting of phenylene, biphenylene and oxybiphenyl, h +j + k + 1 + m is approximately equal to l, h +j + k = 0.05 to 1, h + m is approximately equal to k + 1 and from about 0.05 to 1.0 units in the polyester comprise at least one member selected from the group consisting of naphthalene, phenyl substituted phenylene, alkyl substituted phenylene, aralkyl substituted phenylene, chlorophenylene oxybiphenyl and biphenylene. 10. The alloy of Claim 9, wherein the first LCP polyester contains more hydroquinone moieties than the second LCP polyester. 11. The alloy of Claim 10, wherein the second LCP polyester comprises recurring units (V), (VI), (VII) and (VIII): ( V ) ( VI ) where a is approximately equal to b + c; b is in the range of from about 0.5 to about 1.0; c is in the range of from about 0.50 to about 0; d is in the range of from about 1 to about 7 per unit of a. 12. The alloy of Claim 10, wherein the second LCP polyester comprises at least one unit X Ar - X 2 (XIII) wherein Ar comprises at least one member selected from the group consisting of X and X2 are independently related from the group consisting of oxy and carbonyl. 13. The alloy of Claim 12, wherein the second LCP polyester consists essentially of the recurring units (XK) and (XX) which may be substituted by one or more Ci to C4 alkyl groups, Ci to C4 alkoxy groups or halogen atoms; and wherein said second polyester comprises from about 10 to about 90 mole percent of units (XTX) and from about 90 to about lO'mole percent of units (XX). 14. The alloy of Claim 12, wherein the second LCP polyester consists essentially of die recurring units (XX), (XXI), (XXII): and wherein said second polyester comprises from about 40 to about 60 mole percent of units (XX); firom about 20 to about 30 mole percent of units (XXI); and from about 20 to about 30 mole percent of units (XXII). 15. The alloy of Claim 12, wherein die second LCP polyester consists essentially of the recurring units (XIX), (XXIII), and (XXIV) which may be substituted by one or more Ci and C4 alkyl groups, C\ to C4 alkoxy groups, halogen atoms, or phenyl groups; wherein the group Ar is as previously defined; and wherein said second polyester comprises from about 10 to about 90 mole percent of units (XD ); from about 5 to about 45 mole percent of units (XXm); and from about 5 to about 45 mole percent of units (XXIV). 16. The alloy of Claim 10, wherein the first LCP polyester form a stable oriented melt phase at about 340 to 400 * C, s * 0.25 to 0.55, q » 0.5 to 0.66 and r = 0.334 to 0.5. 17. The alloy of Claim 16, wherein the second LCP polyester comprises recurring units (V), (VI), (VII), and (VIII): ( V ) ( VI ) where a is approximately equal to b + c; b is in the range of from about 0.5 to about 1.0; c is in the range of from about 0.5 to about 0; d is in die range of from about 1 to about 7 per unit of a. 18. The alloy of Claim 17, wherein b is from .5 to .8, c is from .5 to .2 and d is from 2 to 4 per unit of a. 19. The alloy of Claim 17, wherein a and b are approximately equal to 1, c = o and d ranges from about 1.5 to 7 per unit of a. 20. The alloy of Claim 16, wherein the second LCP polyester comprises at least oneΛinit X ! - Ar - X 2 wherein Ar comprises at least one member selected from the group consisting of: Xl and X2 are independently selected from the group consisting of carbonyl and oxy. 21. The alloy of Claim 10, wherein the first LCP polyester forms a stable oriented melt phase at about 250 to 360 * C, s - 0.075 to 1.5, q » 0.05 to .58 and r - 0.42 to 0.95. 22. The alloy of Claim 21 , wherein the second LCP polyester comprises recurring units (V), (VI), (VII), and (VIII). ( V ) ( VI ) wherein a is approximately equal to b + c, b is in the range from about 0.5 to 1.0, c is in die range of from about 0.5 to about 0, d is in the range of from about 1 to about 7 per unit of a. 23. The alloy of Claim 22 wherein b is from .5 to .8, c is from .5 to .2 and d is from 2 to 4 per unit of a. 24. The alloy of Claim 22 wherein a and b are approximately equal to 1, c = o and d ranges from about 1.5 to 7 per unit of a. 25. The alloy of Claim 21 , wherein the second LCP polyester comprises at least one unit X Ar - X 2 wherein Ar comprises at least one member selected from the group consisting of: X\ and X2 are independendy selected from the group consisting of carbonyl and oxy.

Inventors: FRAYER PAUL DAVID, HUSPENI PAUL JOSEPH, LAYTON RICHARD, MATZNER MARKUS, STERN BRIAN ALLEN, FRAYER, PAUL, DAVID, HUSPENI, PAUL, JOSEPH, LAYTON, RICHARD, MATZNER, MARKUS, STERN, BRIAN, ALLEN
Applicants: AMOCO CORP, AMOCO CORPORATION
Application year: 1989
Main classification: C08L67
IPC codes: C08G63, C08K7, C08L67