CA2000485A1 - Blends of liquid crystalline polymers of hydroquinone poly (iso-terephthalates) p-hydroxybenzoic acid polymers and another lcp containing oxybisbenzene and naphthalene derivatives - Google Patents

Abstract

ABSTRACT

This invention relates to a blend comprising a first LCP polyester polymer consisting essentially of units (I), (II), (III), and (IV).

( I ) (II)

Description

~ t 2tiC~ 85 BLENDS OF LIQUID CRYSTALLINE POLYMERS
OF HYDROQUINONE POLY(ISaTEREPHTHAIATES) p-HYDROXYBENZOIC ACID POLYMERS AND ANOT~IER
LCP CONTAIN~G 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 consisdng essendally of units (1), (II), (III), and (IV).
~~~ ~oC~3C03~
( I ) (II) ~~r ~Iv~S ]
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 consisdng 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.
Wholly aromatic polyester resins have long been known. For instance, 4 hydroxybenzoic acid homopolymer and copolymers have been described in the pastand are c~cially available. Such polyrners commonly are crystalline in nature and, when molten, frequently 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 610C were quoted - see W.J. Jackson, The British Polymer Journal, December 1980, p. 155.
In order to depress the high rnelting point of the homopolyrner so as to rnake it melt fabricable, a variety of materials incorporating different types of comonomers were prepared over the years.

2C~ 485 One such material is, for example, the resin made from p-hydroxybenzoic acid, isophthalic and~or terephthalic acids and 4,4'-biphenol as described in Cottis 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 Perform~ance Products, Inc. under the trade name of Xydar~. These LCPs usually contain a relatively high percent concentration ofhydroxybenzoic æid to reduce the concentration of the expensive biphenol.
The main drawback of the prior art p-hydroxybenzoic æid copolymers and LCP
polyesters containing no p-hydroxybenzoic æid moieties is the reladvely 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 hydro~quinone, which is disclosed as an equivalent of biphenol in the aforemendoned U.S. Patents Nos. 3,637,595 and 3,975,487, were made by several research groups; however, none of these invesdgadons were successful.
Study of the prior art shows that replacement of 4,4'-biphenol with hydro-quinone leads to materials with inferior properdes. The problem created by the introdwtion of hydroquinone is basically the following: at high terephthalate contents, high meldng generally intractable polymers are obtained; tractability may be achieved at higher isophthalate levels, but the polyesters are reladvely low melting and often display low second order glass transitdon temperatures which lead to low moduli and low heat distordon temperatures. For example, polyesters from p-hydroxybenzoic acid (PHBA) isophthalic acid aA) and hydroquinone aIQ) were prepared by Deex, U.S. Patent No.

4,377,681. At mok rados PHBAIIA/HQ of 33.3/33.3/33.3 the material had a glass transitdon temperature of 110C; when the above coreactants were used atratios of sol2sns, a Tg of 115C was obtaine~
The high melting points of a series of p-hydroxybenzoic acid/terephthalic acidlhydroquinone copolymers are graphically illustrated in Figure 2 of the paper by G.W. C~undann, Industrial Development of Thermotropic Polyesters in High Performance Polymers: Their Origin and Development, 233-249 (R.B. Seymour and G.S. Kirshenbaum, editors 1986). The publicatdon shows clearly (in Figure 2) that hydroquinone polymers melt at considerably higher temperatures than their 4,4'-biphenol counterparts. The Tm of the lowest melting composidon shown is about 420C. Figure 4 of the same publication (p. 243) indicates how one research group was able to depress the melting points of the subject polymers by incoqporating naphthalene diols, naphthalene dicarboxylic acids, and hydroxy naphthoic acids into them. From a purely technical point of view, the latter approach was a success;

2~0Q485 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 Jacksonet al., U.S. Patent No. 4,242,496. Column 2, lines 18-26, states:
"U.S. Patent No. 3,637,59S discloses that aromatic liquid crystal polyesters plepared from terephthalic acid, hydroquinone and va~ying amounts of p-hydroxybenzoic acid melt in the general range of 800 to 900F. Obviously, the melting point of these polymers is far too high and the the~mal stability is insufficient to permit these polymers to be ussd in conventiona1 melt-processing equipment."

It is furthcr stated (column 2, lines 33-40) that a solution to the above problem "was to inc~porate 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 hyd~quinone lowers the melting point of the polyester. Although this approach can be used to lower the melting point, typicaUy 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 rcsins, without adversely affecting the mechanical properties. As indicated earli, polyestcrs forming oriented melts were made from a variety of substituted hydroquinones. See, for cxamplc, Lee et al., U.S. Patent No. 4,6û0,765; 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 proccssible polyesters madc from p-hydroxybenzoic acid, isophthalic and optionally tcrcphthalic acid, hydroquinone and 3,4'- and/or 4,4'-biphcnol, 3,4- andlor 4,4'-dihydroxydiphenyl ether, 3,4'- and/or 4,4' dihydroxydiphcnyl sulfide are the subject of Dicke et al., U.S. Patent No.
4,603,190. It should be recognizsd 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. Sec, for example: Portugall et al., European Patent Appln. No.
EP-257,S58; Hisgen et al., European Patent Appln. No. EP-257,S98; Hisgen et al.,Gennan 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. W~88/û0,955.
As pointed out above, tractable materials result at high isophthalic acid levels but the products typically display undesirably low glass transidon temperatures. Deex, U.S. Patent No. 4,377,681 states (column 1, lines 31-38):

Z~Q485 "For exampk, 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 nomers 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-Ws(4-hydroxyphenyl) propane. The preferred compositions contain from about 20 to about 35 mole percent of p-hydroxybenzoic acid units, and f~om about 5 to about 12 mole percent of 2,2-bis(~hydroxyphenyl)propane (bisphenol-A) based on the tota1 diphenol components. Glass transition temperatures of about 175 to about 190C 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 (HDrs) which are, at best, of the order of about 120 to 140C; moreover, the introduction of bisphenol-A lowers the degree of crystallinity and the rate of crystallization which we believe leads to lower HDT's. In addition, mold shrinkage of these copolymers isunsatisfactorily high. Further, the introduction of aliphadc moieties affects the melt stability of these materials.
It has now been discovered that 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-oxybenwate, or substituted hydroquinone wherein said polymers and the moieties making up the polymers are present in specified proportions, yields alloys with improved p~ccssibility, improved mechanical properties, and improved surface characteristics (such as reduced tendency to blister or better gloss). In some cases, the alloys have bett 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 cornponent forms roughly spherical domains as inclusions. Under some circumstances, bi-continuous StlUCDS are also obtainable. Mixing two arbi~arily chosen polymers usl~ally results in inferior materials having no utility, since in the absence of adhesion be~ween 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 2~0Q4~35 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 interacdon are favorabb, are known.
Cotds, U.S. Patent No. 4,563,508, is directed to the improvement of molding compow~s based on wholly aromade polyesters by the addidon of a minot amount of a flow modifier wherein at least 30 mole pereent of the a~made diol is biphenol. The flow modifier e ystallizes poorly and improves the flow of the highly erystallized base polymer it is added to.
The flow tnodifier 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 inerease the strength.
Takayanagi et al., U.S. Patent No. 4,228,218, discloses a polymer composition comprising 20 percent or bss, based upon the to~al weight of polymeric mate~ial, of a first rigid po1ymer with the balanae behg a second polymer composed substantially of flexible molecular chahs. The first polymerie material is dispersed h the second polymeric rnaterial in a mieroseopic region of 1 llm or less. It is believed that wholly aromadc polyesters would be characte~ized by those skilled in the art as rigid molecules within the context of the above cited patent. The patent does not diselose blends of two or more polymers having rigid chains.
Blends of polymers exhibidhg orientadon in the melt with other polymers were hvestigated. Mixtures of liquid erystallhe polyesters with poly(alkylene terephthalates), polyeasbonates and polyatylates were described in Cineotta et al., U.S. Patent Nos. 4,408,022 and 4,451,611; Froix, U.S. Patent Nos. 4,489,190 and 4,46û,735; and in Kiss, European Patent Applieation No. 169,947. Improved mechanieal propetdes were found with these materials. The addition of a partieular liquid erystal polymcr to poly(butylene terephthalate) or other thermoplastic polymers was described as a method to obtain compositions with enhanced resistanee to melt dripping during burning (see Kim et al., U.S. Patent No. 4,439,578). In seve~al instanees, e.g., in alloys of liquid crystalline polyesters with an aromadc sulfone polymer (Froix et al., U.S. Patent No. 4,460,736) with an atomatdc 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 characterisdcs and improved processibiliq (lower viscosi~y) of the non-anisotropic resin were note~ Better properdes were also obtained by blending two pardcular 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 processibiliq of a number of other resins, including fluorinated polyolefins xal00485 (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 addidon of an isotropic resin to an anisotropic resin leads to a decrease of anisotropy in the co~responding molded ardcles.
The fracture-surface morphology of thermotropic 6-hydroxy-2-naphthoic acid-p-hydroxybenzoic acid copolymer blends with nylon 6, poly(butybne terephthalate), and polycarbonate prepared by screw injecdon molding, was studied by Beery et al. J. Mater .
Sci. Lett..l2~, 7(10), pp. 1071-3. The morphology was found to be strongly dependent on the flow history and on the composidon of the subject mixtures.
A commor~y assigned patent applicadon endded ' Extrusion~rade Compositions Comprising Mixtures of Wholly Aromatic Polyesters," Serial No. 060,038, filed on June 9, 1987, in dhe 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, terephdlalate, and p-oxybenzoate; widh a socond polyester comprising the same recurring rnoieties, but wherein d e p~oportion 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 acceptabb p~ducts, their alloys provide good extrusion grade compositions. Molding composidons comprisod of the above first and second polyester, filler, and opdonally a polymeric flow modifier are clairnod in cornmonly assigned U.S. Patent Application endtled "Molding Cornposidons Comprising Mixtures of Wholly Aromadc 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 Icnown from the pri art that it is possible to alloy two polyesters, wherein said polyesters are basod on i~iÇi~l monomers but differ in the relative proportion of the monomers, wherein each of said polyesters has unsadsfactory molding and extrusion cha~risdcs and obtain good molding and extrusion de composidons.
No reference is l~nown which is directod to the irnprovement of surface properties by blending two polymcrs havhg orientadon h the rnelt. A feature of the instant invendon that is totally unexpoc~d and highly remarkabb is the fact that compadble blends showing good mechanical and surface propcrdes are achieved by alloying t vo crystalline wholly aromatic copolyesters prepared frorn monomers having totally different structures, e.g., phenylene versus naphthalene or biphenylene or subsdtuted phenylene. In any event, as indicated earlier, alloys of materials having ordered structures would be expected to have reducod properdes.
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 properdes.

2~0Qg85 It is the general ob~ect of the present invention to provide novel, inexpensive,melt-ptocessibb alloys comprising hydroquinone poly(iso-terephthalates) containing residues of p-hydroxybenzoic acid polyrners which form highly tractable oriented melt phase, and which ate capable of melt extrusion to form quality, high performancefibers, filrns, three-dimensional molded arlicles, etc.
It is a futtherobpct of the present invention to provide novel, rnelt-processible alloys comprising hydroquinone poly(iso- tetephthalates) containing residues of p-hydrDxybenzoic acid, polymers which form a melt phase below 400C in the substantial absence of polymer degradation, unlike many other polymers which include relatively high concentrations of the 4Oxybenzoyl moiety.
These and oth objects, as well as the scope, natute and utilization of the invention will be apparent to those slcilled in the art from the following detailed description.
It was unexpectedly discovered that advantageous alloys can be forrned comprising a first LCP polyester, consisting essentially of units (I), (II), (m), and (IV) ~0~0~ ~OC~CO~

( I ) (II) t ~r ~ ~col 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 fsom about .05 to 9.0, and a second LCP polyestet polymer comprising at least one moiety selected ftom the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydroxynaphthalene, naphthalene dicarboxylic acid oxybisbenzoic acid and substituted hydroquinones wherein the said iety or ieties comprise at leas~ about S mole percent of the units in said second LCP polyester.
The first W 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 tractabb 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 2~20Q485 aeid, isophthalie acid, hydroquinone and hydroxybenzoie aeid while the second LCP
polyester comprises expensive monomers such as naphthalene diol, hydroxynaphthalene carboxylic aeid, naphthalene dicarboxylic acid, oxybisbenzoicacid, biphenol and subsdtuted hydroquinones such as phenyl, methyl, ethyl, t-butyl, styryl, or alpha-methyl styryl. With the excepdon of biphenol, eaeh of the expensive norner moiedes in the second LCP polyester ean impart orientadon in the melt at a level of at least abou~ 5% of the units in the polymer while biphenol is generally used with hydroxybenzoic acid or hydroxynaphthoie aeid moieties. Hydroxybenzoic acid moiedes also can impart orientadon in the melt at a level of at least about 5% of the units of the polymer. Aecordingly, the seeond LCP polyester must eomprise at least onemoiety seleeted from the group eonsisdng of hydroxybenzoic aeid, hydroxynaphthalene carboxylie acid, oxybisbenzoie aeid and substituted hydroquinone in a concentradon suffieient to provide at least about S mole percent of the units in said second LCP
polyester to provide onentadon in the melt. Of eourse, the first polyester has a higher coneentration of hydroquinone units than the seeond polyester.
The eoneentration of second LCP polyester can range from about 0.01 to 99 parts by weight per eaeh part by weight of first LCP polyester, preferably .3 to 99 parts by wdght and most preferably 0.3 to 3. In general, the higher the eoncentration of first LCP, the lower the eost of the alloy.

In somewhat greater detail while the first polyester of this invention having a meldng point under 420-C and a moleeular wdght of about 2,000 to 200,000 consists essendally of units (I), (II), (m), and (IV) ~ 0~0~ ~ O~ ~ CO~

( I ) (II) o~3C~

(m) r (IV) s 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 invendon 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, 2~0Q485 g 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 incolporated by reference.
One class of preferred LCP polyesters useful in this invention form a stable oriented melt phase at 340 to 400C, preferably from 340 to 380C; the melt phase is tractable and can be melt-extruded below its decomposition temperature to form quality, high performance fibers, films, molded articles, and the li1ce. Fabricated products of these polymers alone show high strength as well as goodretention of properties at high ternperatures. Materials filled with 30 percent by weight of glass fibers have heat distortion temperatures of over 240 to about 280C and higher, under a load of 264 psi. It is believed that the higher the amount of crystaL~inity of the polymer the higher the heat distortion temperature (EIDT) will be. The crystallization teqtures of these copolymers are in the range of from 300 to 340C, preferably from 310 to 340C; and their crystallizadon 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 ta 0.5, and p~ 1Ø
A second class of preferred LCP polyesters useful in this invendon form a stablc oriented melt phasc at about 250 to 360 C, thc 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 retendon of praperties at high temperatures. Advantageously, materials filled with 30 percent by weight of glass have heat distortion temperatures of ovcr 200 to about 24~C and higher, under a load of 264 psi. It is believed that the higher thc amount of crystallinity of the polymer the higher the heat distortiontemperaturc (HDl~ will be, also the higher the melting point.
This scoondclass of preferred LCP polyesters have the following approximate monomer ranges based on moles: s ~ 0.075 to 1.5, q z 0.05 to 0.58, r ~ 0.42 to 0.95, and p ~ 1Ø
The synthesis of the first LCP polyesters of the instant invention is described generally in Cotds et al., U.S. Patent No. 3,637,595 endtled "P-Oxybenzoyl Copolyesters," and in Finestone, U.S. Patent No. 4,742,149 entitled "Producdon of Melt Consistent Aromatic Polyesters"; the disclosure of the aforemendoned two patents is inc~poqated herein by reference.

The bulk condensadon of aromadc polyesters is described in the patent literatureand broadly considered involves an alkanoyladon step in which a suitable dicarboxylic acid, hydroxybenzoic acid and diol are reacted with an acid anhydride; a prepoly-merizadon 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 C2 to C4 monocarboxylic acid, is added in at least stoichiometric amounts. It is most preferred to use acedc anhydride; its amount is preferably from about S to about 20 mole percent over that required for the acetylation of all of the hydroxyl groups. The acetyladon reacdon takes place at about 140C for a period of dme of from about 2 to about 6 hours. The ~ion mixture is then hcated to about 240 to 320C at a rate of about 10 to 40DC per hour, and is kept at about 240 to 320C f approximately a few minutes to about 4 addidonal hours. The low molecular wdght polymer obtained is then solid state advanced to the required high molecular wcight by heating to a temperature of from about 265 to about 340C, 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, par~icularly an alkaline earth metal salt or an alkali metal salt, preferably potassium sulfate, during the preparation of the resin and parlicularly to the prepolymer melt pri to advancement of the final product to the desired degree of polymerizadon. The inco~poradon of stabilizing amounts of phosphites, as described in Cotds, U.S. Patent No. 4,639,504 is also advantageous.
These po1yesters commonly cxhibit O O
ll or ¦¦

end groups depending upon the synthesis route selected. As will be apparent to those sldlled in the art, the end groups optionally may be capped, e.g., acidic end groups may be capped with a varicty of alcohols, and hydroxyl end groups may be capped with a variety of organic acids. For instance, end capping units such as phenyl ester c- o~3 or methyl ester 2~Q485 --C ~CH3 optionally can be included at the end of the polymer chains.
The polymers can be annealed below their melting points for a period of dme 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 meldng podnts for a limited period of time (e.g., fo~ a few minutes).
The polyesters of the present invention tend to be substantially insoluble in all common polyester solvents such as hexafluoroisopropanol and o-chlorophenol, and accordingly are not susceptible to soludon processing. They can surprisingly be readily processed by known melt processing techniques as discussed hereafter.
The polyesters of the present invention commonly exhibit wdght average molecular weights of about 2,0no to about 200,00û.
These polyesters alone can be melt processed in the substandal absence of polycner degradation to form a variety of reladvely stiff shaped ar~icles, e.g., molded three-dimensional articles, fibers, films, tapes, etc. The polyesters are suitable for molding applicadons and may be Ided via standard injecdon molding techniques commonly udlized when forming molded ardcles. Unlike the polyesters commonly encountered in the prior art, it is not essendal that more severe injection molding condidons (e.g., higher temperatures), compression molding, impact molding, or plasma spraying techniques be udlized. Fibers or films may be melt extruded. In some instanccs, 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 a~matic comonomers other than (I)-(IV), such as biphenol, provided that the use of said carbonate linkages and/or comonomers does not unfava~ably affect the very attractive properties of ~he instant copolyesters.

SECOND LCP POLYESTER~i As indicated above the first LCP polyesters are blended with a second different LCP polyester comprising at least one moiety selected from the group consisting of hydroxybenzoic acid, hydroxynaphthalene carboxylic acid, dihydT~xy naphthalene, naphthalene dicarboxylic acid, oxybisbenzoic acid and substituted hydroquinones wherein the said moiety or moieties comprises at least about 5 mole percent of ~e units in said second LCP polyester.

2~0Q485 The preferred second LC~ polyesters consist essentially of one or more units H, J,K,L,andM

~0--R--0~ ~0--R,--C~ ~C--R2--~C--R3--~ ~--R4--0~
. L 1 M m havmg a molecular weightof 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, Rl is at least one member selccted 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 selec~d from thc group consisting of p-phenylene and m-phenylene, R4 is at least one ~ember selected from the group consisting of phenylene, biphenylenc and oxybiphenyl, h + j + k + 1 + m is approximately equal to 1, 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 the group consisting of naphthalene, phenyl, alkyl (t-butyl), araLIcyl (styryl or alpha-methyl styryl) or chlaro substituted phenylene, oxybiphenyl and biphenylene.
Unless stated to the contrary, each of the phenyl and phenylene groups are preferably - para and the naphthalcne groups arc drawn infra Suitable second LCP polycster useful in this invention include: a second polyester comprising units (lX), (X), and (XI):

~3 C~e (~C) f ~ g (X) (XI) wherein e is approximately equal to f; e is one; and g is in the range of from about 1.5 to about 5, preferably in dle range of from about 2 to about 4, based on the number of moles of monomer corresponding to units (IX); where the molecular weight of said polyester is in the range of from about 2,000 to about 200,000, said second polyesters when admixed with the first LCP yield blends that are easy to melt fabricate, display vastly improved moldability and physical properties, yield parts pleasing to the eye; and, surprisingly, show a reduced tendency to blisteron molding. A totally unexpected and surprising feature of the instant blends is that both their moldability and the surface characteristics of the molded objects obtained from them, are often bett than the corresponding properties of many of the individual polyesters. In addition, the materials display improved mechanical propetties over those of the constituent polymers. Heat distortion temperatures, both 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 Ioad 264 psi, particularly when alloyed with preferred class 1 polyesters.
Another second polyester comprises unit (V), (VI), (VII), and (VIII):

0~ 0~ ~ OC~ (~O~

(V) (VI) ., .

a~ d c (vm (VII) 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 the range of from about 0.5 to about 0.2; and d is in the range of from about I to about 7, preferably from about 2 to about 4, based on the total number of moles of nomercorrespon~ng 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 adrnixed with the first LCP yield blends that arc easy to melt fabricate and yield injection molded parts that surprisingly show a significantly de~eased tendency to bliste~. In addidon, the materials display improved mechanical propcrties over those of thc constituent polymers, as well as ~mproved proocssibility, compositcs with preferred class 1 polycster containing about 30 weight percent of glass fibers, have hcat distordon temperatures (HD'rs) of at least 240C, when measured under a load of 264 psi.
An additional second polyester polymer comprises at least 1 unit:
. xl-Ar-x2 (xm) wherein Ar comprises at least one member selected from the group consisting of:

2~QQ48S

and~/
( XlV) ( XV ) ( XVI ) ( XVII ) Xl and X2 are independendy oxy or carbonyl optionally in conjunction with units:
Xl -Ar-X2 (~vm) , wherein Xl and X2 are as previously defined, and the 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 dhe preferred class 1 polyester are generally easier to melt fabricate, display improved moldability and yield parts pleasing to the eye widh good surface characteristics. Unexpectedly, dle mate~ials usually have improved mechanical properties that are quite often superior to the pr~perties of the two constituent polymers. Heat disto~tion temperatures, 'ooth on neat and on 30 percent by weight glass filled blend compositions, are at least 175C and may be as high as 300C and even higher, when measu~ed 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 fonning an anisotropic melt phase at a temperature below approximately 350C apart from the blend. The polyester consists essentially of the recurring moieties (XIX) and (XX) which rnay include subsdtution of at least some of the hydrogen atoms present upon an aromatic ring:

~} ~o~3C~
(X~) (~) with said optional substitution if present being selected from the group consisting of an alkyl group of 1 to 4 carbon atoms, an aL~coxy group of 1 to 4 carbon atoms, halogen, and n~ixtures of the foregoing. The wholly arornatic polyester there disclosed comprises approximately 10 to 90 mole percent of moiety (~X) and approximately 90 to 10 le percent of moiety (XX).

2~[)Q485 The polyester disclosed in U.S. Patent No. 4,184,996 is a melt processible wholly aromatic polyester which is capable of fo~ning an anisotropic melt phase at a temperature below approximately 325C apart from the blend. The polyester consists essentially of the recurring moieties (XX), (XXI), and (XXII):
~o~c~o~T~
(XX) (XXI) (XXII) 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 (XX~; and approximately 20 to 30 le percent of iety (~XII). Each of the moieties of the polyester is free of ring substitution.
Thc polyester disclosed in U.S. Patent No. 4,256,624 is a melt processible wholly aromatic polyester capabb of fcrming an anisotropic mclt phase at a temperature below approximately 400C apart from the blend. The polyester consists essentially of the recurr~ng moieties (XIX), (XXIII) and (X~V) which may include substitution of at least some of the hydrogen atoms present upon an aromatic ring:
~ llt ~o ~ o~c (X~) (X~) (XXIV) wherein Ar is as previously deflned; with said opdonal subsdtudon, 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 le percent of iety (XIX), approx~mately S to 45 mole percent of moiety (XXm), and approximately S to 45 mole pe~cent of moiety (X~V).
Any of the LCP polyesters based on substituted hydroquinones discussed above can be used as the second LCP polyester such as poly phenyl substituted phenylene terephthalates of U.S. Patent No. 4,159,365.

2~0Q485 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, that small internal blisters or voids may also be detnrnental to rnaterial performance.
Moldings based on polymers that show ientation in the melt, display skin-core effects. Hence, phenomena observed in these systems are often analogous to thoseencountered in coatings and composites. In composites, for example, blistering and delamination occur especially between two layers of different composidon. In coatings, blistering is known to be a loealized delamination at an interfaee; it depends on the diffusion of chemieals sueh as water and degradation by-produets. The differenee in the d~ermal expansion eoefficient bet veen acoating and the substrate ean ereate stresses and may weaken the interfaee. A blister rnay then form with less pressure difference, due to voladles, than in cases where these slresses are absent.
In surnmary thus, blistering is due to a surface layer delaminadon and can be eaused either by trapped voladles or by built-in stresses. Most probably botll factors are at work.
Two types of blistering are eneountered with polymeric materials: (1) molding blisters and (2) oven blisters. Blisters which occur during molding generally indicate the presence of degraded material. Quite often parts having aeceptable surfaee charaeteristics are obtained upon molding. However, when these parts are treated at high ternperatures for a certain period of time, blisters ("oven blisters") often appear. These do not neeessarily indicate the presence of degraded material as a result of molding.
It is of paramount im~e that molding of the polymer does not yield parts having a blistered surfaee. It should be noted that the configuradon 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 partieular molding compound is most probably of inadequate quality. If, on the other hand, a good looking molding part is obtained, there is no assuranee as to what the results of "oven testing" will be. For high temperature applicadons, it is imperadve that oven blistering be also either abscnt or sigr~ficantly minimi~ The oven test and the method of blister rating are described in ~e E~lal The blends of the instant invention show a considerably decreased tendency to blister--both dunng molding and in the oven test.
Molding compounds may be formed from the subject copolyesters and blends by incorporating therein f~ers such as ta1c, wollastonite or dtanium dioxide; and/or reinforcing agents, e.g., glass fibe~s. One attractive application of the novd copolyesters of the instant invention is, for example, in ovenware. Both the 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. Patentapplication entitled "Novel Plastic Ovenware Compositions," Serial No. 255,753. Ar~cles 2C~0Q485 may also be molded from a molding compound which includes, as one component, theblend of the present invendon. Such a molding compound incorporates into the blend of the present invention approximately 1 to 80 percent, preferably approximately 10 to 70 percent, by weight, based upon the 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, graphidc carbon fibers, amorphous carbon fibers, synthetic polymeric fibers, aluminum fibers, aluminum silicate fibers, oxide of aluminum fibers, tdtanium fibers, magnesium fibers, rock wool fibers, stoe1 fibers, tungsten fibers, etc.
Representadve filler materials include calcium silicate, silica, clays, talc, ~ca, carbon black, dtanium dioxide, wollastonite, polytetrafluoroethy1ene, graphite, alumina trihydrate, sodium aluminum carbonate, barium ferrite, etc. The molding compounds are useful in a variety of applicadons including high temperature applications, for example, in coo~ware and electrical artic1es, and the like.
It has been found in accordance with this invention that a uniform and pleasing appearancc can be imparted to ovenware arlicles and any undesirable bubbling can be suppressed or minimized by the 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 800C, 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 the present invendon are characterized by a low wdght loss on ignitdon, a low iron content analyzed æ iron oxide, and a closely controlled particle size.
The weight loss on ignition of the suitable talcs is not more than 6 percent or less at 950C and is 2 pcrcent or less at 800C. The iron content analyzed as iron oxide (Fe203) will not be more than about 1 percent and that of the pardcularly preferred talcs will not be me than about 0.6 percent and may be less. In addidon, the pardcle size distribudon of the talc must preferably be such that about 90 to 95 percent of the particks are kss tban about 40 microns.
Experiments and tests carried out have demonstrated quite conclusively that it is essendal to use such talc in order to ~ealize the objectives of the present invention. The use of other fo1ms of talc does not provide satisfactory properdes in the flnished molding product. However, such other forms of talc can be employed in conjuncdonwith the specified talcs in amounts of from about 0.05 percent to about 20 percent of the requircd forms of talc.
The talcs containing the minimum amounts of decornposable material will be presented in amounts of from about 1 percent to about 60 percent based on the total 2~t0Q485 composition wdght 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 other talc. The rutile titanium dioxide will be present in a proportion of from about 2 percent to about 20 percent based on the wdght of the total composition. The preferred range is from about 2percent to about 15 percent.
In the mold ng compositions of the present invention, the resins will generally comprise from about 35 percent to about 8S percent and the total inerts from about 65 percent to about 15 percent. Foropdmum results, the inerts will comprise from about 40 percent to about 55 percent of the mokling composidons. The inerts will comprise up to about 55 percent of highly refined talc and from about 0 to about 10 percent of dtanium dioxide.
The composidons of the present invendon can be prepared by extrusion in ~rdD~e with genera11y known pracdce. For example, a twin screw extruder can be employed with addidon of the polymer, selected talc, and dtanium dioxide at the feed throat and with addidon of the glass roving at both the vent and feed thr~at.
The composidons so prepared can then be injection molded according to general pracdce using techmques familiar to the injeclion molding field.

.Examples The following exampbs serve to give specific illustradons of the pracdce of thisinvendon but they are not intended in any way to limit the scope of this invention. The examples and comparadve exampbs are plotted on the triangular phase diagranL
~limd~L PrQcedure~
The following p~clures were used to obtain the data given in the examples.
A. &~ Measurements 1. Apearatus X-Tay diffracdon data were obtained using a Philips XRG-3000 X-ray generator equipped with a vertical difractometer, a long, fine focus copper X-ray tube, a Paar HTK-10 high temperature diffractometer attachment and a Paar HTK-heat controller. Diffractometer posidon is controlled by computer, which a1so measures and records radiadon count Tate produced by sampb crystallinity and sampb temperature.
(a) Determinadon of the Polvmer Meldn~ Point A sampb of the polymer is submitted to a preliminary X-ray diffracdon scan between 15 and 25 degrees two-theta angle by increasing the 2QoQ4as temperature by increments of 60C within a temperature range from about 200 to about 480C. This aUows dete~mination of the approximate temperature at which the peaklocated at approximately 19.7 degrees two-theta (4.50 A d-spacing) reaches its minimum valuc, i.e., an approximate melting point. A second-degree polynomial equation is derived f~m the above data; this polynomial equation now allows to follow the peak angle as the sample temperature is vaTied. The temperature at which the peak height reaches a mi~m (i.e., touches the baseline), is considered to be the meldng point. The polymer sample is now heated and cooled at a rate of 100C per minutebetween the previously mendoned temperature limits, and its melting point is deter-mined Since the melting point of a crystaUine matelial often changes on heating and cooling (due to recrystaUizadon, further polymerization, etc.), the sample is cooled and reheated. This aUows determinadon of the meldng point on the second heating cycle.
Generally, the second cycb yields a meldng point which remains approximately constant if additional headng or cooling cycles are perfom~ Therefore, the va1ueobtained in the second headng cycle is taken æ the polymer meldng point.
(b) Crvstallizadon Temperature (onset of crvstaUizadon) The crystaUine meldng point is measured by foUowing the intensity of the X-ray diff~acdon of the most intensivc peak as a functdon of temperature. The most intensive diffracdon peak is located at a spacing of about 4.5 ~.
Based on litcrature data [J. Polymer Sci., Polym. Chem. Ed., 14, 2207 (1976); J.Polymer Sci., Polym. Chem. Ed., ~, 2249 (1983)], the subject peak has been tentadvely æsigned to the distance between the polymer chains. The point at which the intensity rcaches a minimum is considered for the polymer mdt temperature. The rate of temperature change is 100 C per minute. The onset of crystallization is measured while the sample is oooled at 100C per minute. The temperature at which the peak emerges f~m the baseline during the second cooling cycle is considered as the onset of crystallization.
(c) ~stalL~zadon Rate At every temperature below the sample meldng point, the intensiq of X-ray diffracdon of a crystalline material can be expressed æ counts per second (or any unit of dme). The increase in the number of counts per unit of dme while the sample is being cooled at a certain rate (100C per minute) is therefore propordonal to the rate of crystallizadon. A temperature interval stardng at the onset of crystallizadon and 40C below that temperature was arbitrarily ~hosen. Rates of cTystaUizadon are expressed as the increase in counts per minute for a sarnple cooled within these temperature limits during the second cooling cycle.

2~0Q48S

B . DMA Flexmal Modulus The n~ent is perfolmed using a Dupont l)ynamic Mechanical Analyzer (I)MA), Model 982 in conjunction with a thermal analyzer, Model 1090.
The DMA measures changes in the viscoelasdc properdes of materials as a function of time and temperature. Tests are conducted at a heating rate of 5C per minute. When the run is complete, the stored data is analyzed; the storage modulus (very similar to the flexural modulus) and the loss modulus are calculated and plotted as a function of temperature. The modulus is expressed in GPa's and the temperature in degrees Cendgradc. 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" (CE;) as used in this applicadon is a measure of the flow of a weighed sample when pressed on a Carver press at S,000 pounds. It is also an indirect measurc of the polymer molecular wdght; the higher the CF value at a given temperature, the lower is the molecular weight of the wholly aromadc polyester.
CF is measured from the area of a disc obtained from a sample of powdered material of given weight, usually O.S to 1.0 grams which has been pressed between two parallel plates. In carrying out the detem~ination of this characteristic, a sample is pressed between two sheets of aluminum foil which in tum are backed bychromium-plated steel plates 6" ~ 6" x 1/4". A Carver 2112-X Model No. lS0-C
hydraulic press modified for 800F is used to press the sample. The particular tempc~ature of the press is that indicated in each sample run. The sample material is allowed to stand for S minutes between the plates at holding pressure in order that the temperature of the material can equilibrate with the press temperature. A load of S,000 pounds is then applied for 2 minutes. The CF is then calculated on the followingbasis. The area of the plessed molding compound is measured by cutting an aluminum sandwich out of the sample pressed between the two aluminum foil sheets. The aluminum foil has a hlown araJwdght relationship called the foil factor. The area is namaliDd for the pressure of the applied load and that number is multiplied by 100 to give a number g~ater than 1. The compressive flow is then calculated by means of the following equation:

2C~0Q485 ~F ¦ (Wt. of ctt~le (sandwich) - wt. of sam~lo X 50) ¦ X 100 Applied Load (Kg) X wt. of sample D. Blister Rating Samples to be tested are preconditioned at 20 to 25C, 50 + 5 percent relative humidity for 48 hours. Test sample lot n~nally includes five tensile bars (1/8" thic~), five HDT bars (5" x 1/2" x 1/4" thick) and five flex bars (S" x 1/2" x 1/8" thick). The samples are carefully inspected and any existing cracks and/or blisters are circled. The samples a~e then annealed in an o~ren which has been equilibrated at 232C (450F) for a period of 4 hours. They are then removed, cooled and inspected. Rating codes follow:
0 - no new blisters;
1 - very slight blist~ing (one or t vo 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 t'nan half of of the specimen surface).
The numerical blister radng is calculated using the equation:
n R = 1/n i ~; 1 Xi2 where R = n~ical blister rating (0-16); n = number of samples tested, Xi = blister rating sample i (~4).
~ the a'oove calculation, the 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 within the range of 0 (no blistering) to 16 (severe blistenng, woqst case).

E. eterrnina~Qf thç Fiber l~in,~
Fiber ratings were obtained using a hot bar apparatus with a temperature range from 270 to 415C. A 2 to 5 gram sample of polymer is thinly and evenly sprinkled on the upper portion of the hot bar using a spatula and is allowed to melt.
Using a large pair of tweezers, grab a small portion of rnaterial from the melted pool and slowly draw a fiber at a steady speed. The following rating system is used:

2~0Q4as 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 length fiber with intermediate level of tenacity or material draws a long fiber with poor strength 3 - Material draws a long fiber with 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 wdght A - An additional rating of A is added if the melted material is clear which indicates the rnaterial is amorphous in the melt state P. VPS
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 that 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 recdved and preconditioned for7-day intervals at 75%
Relative Humidiy/Roarn Temperature.
2. The vapor phase unit used was Model No. 912 II manufactured by HTC.
3. The primary vapar was FC-70 Fluorinert, an inert fluorochemical manufactured by 3M Company. The vapor was at a temperature of 428F (220C).
4. The socondary vapo,r was Genesolv D, a trichlortrifluoroethane manufactured by Alliod Chernical Company. The vapor was n~untained at a tempera~e of app~ imately117F(47C).
5. The sampks w~e lowered through the secondary vapor into the plimary vapor and allowed to dwcll 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. Sarnples were examined for blistering. If no blistering is evident, then the samples are considered passed. If blisters are evident, the sample has failed.

G. Miscellaneous 2~Q485 The flexural strength of the experimental samples was rneasured according to the procedure of ASTM D-79~84A; and HDT (DTllL) data were obtained using the method as described in ASTM D648. Tensile strength were measured in accord with ASTM D-638.

pol~rmerization~
ExamDle P-l This is an example of the synthesis of a novel polyester based on terephthalic acid, isophthalic 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.

Item In~redient Amount A Terephthalicacid 5.311 kg B Isophthalic acid 3.541 kg C p-Hydroxybenzoic acid 3.680 kg D Hydroquinone 5.868 kg E Acedcanhydride 15.645 g F Magnesiurn acetate tetrahydrate 0.46 g G Triphenyl phosphite 7.36 g 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 dis~llate receiver. Aft purging with nitrogen, the contents were heated with stirring to 141C
and held under reflux at that temperaturc for 3 hours. Distillation was then started whilc incrcasing thc tcmperature over a 4.8 hour period to 285C. Item G was then injected into thc vessel. Aher an additional 15 minutes the contents of the vessel were transfcrred to a sigma blade mixcr that had been preheated to 320C. After mixing for 4 hours at this tcmperature under an atmosphere of nitrogen, the mixer was cooled to near room tcmperature whcre the contents were removed as a granular solid.
The mclting point of the polymer (X-ray) was 359C; its crystallization temperature was 336C with a crystallization rate of 2,400.
A sample of the polymer was melted, extruded and pelletized with a twin screw extruder. The pellets werc molded into test specimens. The resulting testing showed superior high tcmperature perfo~mance with a heat distortion temperature of 250C and a flexural modulus of 570,000 psi as measured at 250C 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 2~0Q485 extruder and molded into test specimens. The heat distortion .~emperature of theobtained composite was 264C and its flexural modulus (by DMA) was 520,000 psi as measured at 250~C. (ASTM-D4065) Example P-2 The ingredients were the same as in Example P-l with the excepdon that the amount of item F was 14.16 grams, and that item G was not used in the preparatdon.
The equipment was the same as in example 1 and the operating procedure is described below.
After purging with nitrogen, the contents were heated with stir ing to 141C andheld under reflux at that temperature for 3 hours. Distillation was then star~ed with increasing the temperature over a 3.6 hour period to 250C. The reaction mixture was then stir~ed for 1 hour at 250-260C.
The contents of the vessel were transferred to a sigma blade mixer which had been preheatcd to about 250C. The material was mixed while the temperature was increased to 300C and mixing was continued for a total of S hours at that temperature.
A molding composition cont~ining 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 spccimens. The hcat distorlion temperature of the obtained composite was 250C and its flexural modulus (by DMA) was 420,000 psi as measurcd at 250C. (ASTM-D4065) ~xample P-3 The ingredients were the same as in Example P-2 with the excepdon of item F
the amount of which was 7.08 grams; also, 16.00 grams of triphenyl phosphite were added pri~ to transfer of the reacdon mixture to the sigma b1ade mixer. Otherwise, the procedure was the same as in Examplc P-2.
The melting point of the polymer (X-ray) was 359C; its crystallization temperature was 329C with a crystallizatdon ratc of 2,500.
A molding oompositdon containing 70 wdght pcrcent of the above polymer and 30 wdght pcrcent of miL~ed glass fibc;r was prepared by compounding on a twin screw extruder and molded into test specimens. The hcat distordon temperature of the obtained composite was 268C and its flex~al modulus (by DMA) was 480,000 psi asmeasured at 250DC. (ASTM-D 4065) Example P4 This is an example of the synthesis of a novel polyester based on terephthalic acid, isophthalic acid, ~hydroxybenzoic acid and hydroquinone in the nominal mole rado of 0.6:0.4:0.75: 1. The following ingredients were combined in the manner described:

Item In~dient Amount A Terephthalic acid 4.829 kg B Isophthalic acid 3.219 kg C p-Hydroxybenzoic acid 5.018 kg D Hydroquinone 5.334 kg E Acedc anhydride 15.645 kg F Magnesium acetate te~hydrate 0.46 g G Triphenyl phosphite 7.36 g These ingredients were processed as described in Example P-l.
The melting point of the polymer (X-ray) was 353C; its crystallizadon temperature was 331C with a crystallizadon rate of 2,100.
A molding composition containing 70 weight percent of the a~ove polymer and 30 weight percent of rnilled glass fiber was prepared by compounding on a twin screw extruder and molded into test specimens. The heat distorlion temperature of the obtained composite was 240C.
Addidonal polymers were examined in Tables lV and Vl. The polymers of Tables lV and Vl were prepared using the mole percentage of nomers delineated in the table and reacting there in the same manner as P-l to P4.

Example P-5 This is an example of the syndlesis of a novd polyester based on terephthalic acid, isophthalic acid, p-hydroxybenwic acid, and hydroqlunone in the nominal mole ratio of .414V.58581.4285/1.()15. The following ingredients were combined in themanner desc~ibed.

~m In~redient Arnount A T~eph~alic acid 3.761 kg B Isophthalic acid 5.319 kg C p-Hyd~xybenzoic acid 3.235 kg D Hydroquinone 6.108 kg E Ace~canhydride 15.776 g F Ma~esium acet~e tetrahy~ate7.06 g G Tnphenyl phosphite 16.00 g 2~0~48~;

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, the contents were heated with stirring to 141-C
and held under reflux at that temperahue for 3 hours. Distillation was then started while increasing the temperature 20 C~r to 259-C. Item G was then injected into the vessel.
After the reactorreached 263'C the oontents of the vessel were transferred to a sigma blade mixer that had been preheated to 300 C. After mixing for S hours at this temperature under an atmosphere of nitrogen, the mixer was cooled to near room temperature where the oontents were removed as a granular solid.
Thc meldng point of the polymer (X-ray) was 268-C; its crystallizadon temperature was 248-C with a crystallizatdon ratc 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 performanoe with a heat distordon temperature of 238-C.

ExamDle P-6 This example describes the preparation of a polyester in the laboratofy. It is to be noted that the preferred method is desc~ibed in Example P-7 and the followingwherein the polymers were produced in scaled-up size in the pilot plant. There acontinuous mcthod of in sfn~ polymenzation was udlized whicb is more demonstrative of scale-up production and economies. Unfortunately in scale-up production, physical and rnechanical operating paramcters can be varied as oompared to laboratory producdon. Thc polyest had thc molar composidon: terephthalic acid~lsophthalic acid/p-hydro~tybcnzoic acid/hydroquinone 0.5/0.5/1.0/1.0 (see Coffls et a1., U.S.
Patent No. 3,637,595; examplc no. 10, noted as dcsignadon"x" on Figure 1).
A 5 1iter resin flaslc equipped with a stirrer, condenscr system designed both for reflux and disdlladon, and a headng mantlc 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 acedc anhydridc.

The above mixturc was heated at rcflux for a period of 3 hours; vigorous sdrring was maintained throughout the re~cdon. At the end of the reflux period collec-tion of distillate was star~ed The reaction mass was then heated at a rate of about 30C

2C~0Q~85 per hour to 311C at which point 98.2 percent of the theoretdcal disdllate 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 placcd in a drum and was heated in a nitrogen stream, while rotadng, to a temperature of 330C; and hcld at that temperature for two hours. The product was removed from the drum aftcr cooling.
The melting point of the polymer (X-ray) was 325C; its crystallization temperature (onset of crystallization) and crystallization rate (both measured via X-ray techniques) were 299C and 2,242, respective1y.
A po~ion of the product was pelletized and injection molded into test spedmens. Thc neat polymer had a HDT of 226C, a flex strength of 16,000 psi, a flex rnodulus of 1.85 X 106 psi and a blister ratdng of 16.
Anotherpo~ion of the product was compounded with milled glass fiber to prepare a pelletized material cont~ining 30 percent glass. Injection molding yielded test specimens which were very brittlc. Therefore, to lun HDT analyses, 1/8" Flex Bars were used. The HDT was 233C.

Exam~le P-7 This example describes the preparadon 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:
lEm In~n2gi~ Amount A Terephthalicacid 3.678 kg B Isophthalicacid 3.678 kg C ~Hydroxybenzoic acid 6.115 kg D Hydroquinone 4.948 kg E Accticanhydride 15.782 kg F Magnesium acetate tetrahydrate 7.06 g G Tripheny1phosphite 16.00 g Iterns A through F werc charged to a 15-gallon, oil heated vessel equipped with an anchor typc stirrer, rcSux condenser, after condenser, injecdon port, and distillate recdver. Aftcr purging with nitrogen, the contents were heated with stirring to 141C
and held undcr rcflux at that temperature for 3 hours. Distillation was then started while increasing the temperature 30C/hour to 273C. Item G was then injected into thevessd. After the reactor reached 277C the contents of the vessel were transfelred to a sigma blade mixer that had been preheated to 285C. After rnLxing for S hours at this temperature under an atmosphere of nitrogen, the mixer was cooled to near room temperature where the contents were reved as a granular soli~

;~C?~3Q4~5 The me1ting point of the polymer (X-ray) was 349C; its crystallization temperature was 331C 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 with a 264 psi heat distortion temperature of only 214C.

Blends Aeyaradve Examples Example B-l Preparation of polyester having the following molar composition: 0.25 moles isophthalic acid/0.75 moles terephthalic acid/3.0 moles p-hydroxybenzoic acid/1.0 mole 4,4'-biphenol. A mixture of:
184 Ibs of terephthalic acid;
61 Ibs of isophthalic acid;
612 lbs of low ash p-hydroxybenzoic acid;
275 Ibs of 4,4'-biphenol;
868 Ibs of acetic anhydride; and 40.1 grams (88.5 ppm) of magnesium acetate tetrahydrate was placed in a 325 gallon Iecto~ and heated with sti~Ting until distillation star~ The rector was held at this temperature for 3 hours. Distillation was started and the temperature increased until 400 pounds of dis~llate had been co11ected. The contents were pressured into a 200 gallon reactor and the temperature was increased at a rate of 30C per hour until the contents reached 313C. Then the contents were poured into a mechanical mixer and mixed at 290 to 300C for 5 hours. Six batches of polymers were made with compressive flows at 330C from 55 to 74, and polymer had very good color.

ExamDle B-2 Preparation of polyeste~ 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:

2C)0Q485 llçm In~redient Amount A Terephthalic acid 1.638 kg B p-Hydroxybenzoicacid 5.039 kg C 4,4'-Biphenol 1.837 kg D Acetic anhydride 6.600 kg E Potassium sulfate 0.5 g F Pentaerythritol diphosphite 6.6 g Items A through E were charged into the rector and heated to 307C over a period of 10 hours with distillation of acetic acid. Item F was then added and heating was continued for 6 minutes to a melt temperature of 310C. The contents of the vessel were transfe~ed to a sigma blade mixer tha~ had been preheated to 335C. The temperature was raised to 350C and mixing was continued at 350C 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.

~le B-3 The naphthalene-based polyester used in the instant blends was Vectra~9 A950, produced by dle Hoechst-Celanese Corporation and composed of about 73 mole percent 4-oxybenzoyl moiedes (XX) and 27 mole percent of 6-oxy-2-naphthoyl moiedes (XIX):

~ ~C}
Preoaration of Po!~este~ Blendc General Polyesters prepared as described in preparadve examples 1 and 2 were formulated into a 30 percent glæs filled composidon, compounded and pelledzed. The blends contained as a percentage of the resins phase, either 0, 10, 21 or 40 weight percent of polymer (b). The formuladons were compounded and pelletized on a 25 mm diameter Berstorff twin sc~ew extruder. The batrel profile temperature forcompounding was:
Barrel zone 1 = 320 to 325C
Barrel zone 2 = 355 to 362C
Barrel zone 3 = 355 to 376C

2C~0Q485 Barrel zone 4 = 365 to 395C
Barrel zone 5 = 380 to 400C
Barrel zone 6 = 370 to 380C
Barrel zone 7 = 360 to 370C
Die = 355 to 380C
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 377C
F~ont zone about 382C
Nozzle about 388C
The mold tem~erature was set at 121C and the injection pressure was in the range of 1,000 to 1,360 psi. The molding machine screw rpm was about 330.
The folmulations of Table VII were compounded and pelletized on a 25 mm diameter Berstorff twin screw extruder. The barrel p~ofile temperature for compounding was:
Barrel zone 1 = 293 to 320C
Barrel zone 2 = 360 to 376C
Barrel zone 3 ~ 375 to 400C
Barrel zone 4 = 395 to 405C
Bar,rel zone 5 = 390 to 400C
Barrel zone 6 = 370 to 385C
Barrel zone 7 = 375 to 387C
Die = 370 to 387C
The screw rpm was 175 with an output of about 10 to 13 pounds per hour.
The above materials we~e molded on a 75 ton, 3 ounce Newbury injection molding machi~e having the following barrel temperature profile:
Rear zone about 377C
Flont zone about 382C
Noz~e about 388C
The mold tempcrature was set at 120C for composition no.7 and at 66C for all other compositions. The injection pressure was 1,000 psi and the lding machine screw rpm was about 330.
Blends of Table XI (test nos. 21-32):
Barrel zone 1 = lS0 to 176C
Banel zone 2 = 270 to 345C
Barrel zone 3 = 285 tO 365C
Barrel zone 4 = 275 to 370C

2C~ Q~8 Barrel zone 5 = 270 to 370C
Barrel zone 6 = 280 to 365C
Barrel zone 7 = 275 to 360C
Die = 270 to 355C
Blends of Table XI (test nos. 33-40):
Barrel zone 1 = 185 to 301C
Barrel zone 2 = 370 to 385C
Barrel zone 3 = 385 to 400C
Barrel zone 4 = 390 to 400C
Barrel zone 5 = 385 to 390C
Barrel zone 6 = 375 to 380C
Barrel wne 7 = 370 to 376C
Die = 370 to 374C
Blends o~ Table XI (test nos. 41-44):
Barrel zone 1 = 320C
Barrel zone 2 = 355 to 360C
Barrel zone 3 = 370 to 375C
Barrel zone 4 = 390 to 395C
Barrel zone 5 = 390C
Barrel zone 6 = 370C
Barrel zone 7 = 370 to 376C
Die = 350 to 375C
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 abovc mati~s were mol~ed on a 75 ton 3 ounce Newbury injection lding machine having the following balTel temperature p~ofile:
Blends of Table XI (test nos. 21-32):
Rear zone = 376 to 337C
F~nt zone = 271 to 337C
Nozzlc = 282 to 348C
Blends of Table XI (test nos. 33-40):
Rear zone = 337 to 388C
~ont zone = 332 to 382C
Nozzle = 343 to 393C
Blends of Table XI (test nos. 41-44):

ZC~ 85 Rear zone = 299 to 371C
Front zone = 288 to 377C
Nozzle = 299 to 382C
The mold temperature was set at 66C for composidons 21 to 32 and 36; it was 99C for no. 44 and 120C in all other examples. The injection pressure was:
17000 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 thc table shows that the blends can generally be fabricated at lower temperatures than the corresponding controls; thereore there is less chance of decomposidon and concurrently bss blistering.

~mmary of Tables Tables I - V: P~openies of Neat and Glass-Filled Polvmers Tables I - m Additional matelials that were prepared are listed in Tables I, II, and m.
Table I lists the polyesters useful in this invention which by themselves have desirable propenies.
Table lI lists borderline resins.
Tablc m lists polymers whose propenies are relatively poor.
Table IV: Polvmas Runs 1 to 26 in Table IV do not cespond to same run numbers in Tables I, II, and m.
Tablc V: Polvm Fibcr Rating Runs 1 to 79 in Table V do not correspond to the same number runs in Tables I, lI, m, and IV.
Tables ~ xm: Blends of Polvesters (a) and (b) and their properdes The blends have lower injecdon molding temperatures than the base polymer showing they can be fabricated at lower temperatures. The data clearly show that the blends display improved mechanical properdes -- see, for example, Table VII flexural strengths, test nos. 3 ~ugh 6. Ov~all, a significant and unexpected improvement in su~face propenies (blister rating) is also observed. The high HDT's of the novel blends are notewarthy; they are inte mediate between those of the constituent polymers of the blends. This in tum could be interpreted as a result of compatibility for the instant highly crystalline polyesters. DMA modulus data show that stiffness is maintained up ;~OOQ485 to quite high temperatures, making the present materials useful at elevated tempera~ures.
In conclusion, therefore, the blends of this invention possess a combination of toughness, surface, and high temperature properties ~at could not be anticipatedbeforehand.

TABLE I

PrQ~erties Melting Cryst.
Example C o mDo s i tiQ n Point Temp. Cryst.
. (a) ~ C) ~ Rate (b) 0~20 0~80 S~00 340 316 2000 6 0~50 O~S0 2~00 367 334 2473 7 O~S0 0~50 1~25 351 315 2500 8 0~60 0~40 0~60 366 329 2420 9 0~538 0~462 0~538 341 308 1350 0~571 0~429 0~429 384 325 1636 11 0~60 0~40 0~333 357 330 3115 12 0~53 0~47 0~333 343 300 2210 13 0~60 0~40 0~2S0 393 331 1920 _ (a) Thc polymas wcrc p~epared via methods similar to that used in Example 7. In all of thc cxamplcs, p is onc.
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- 6~ -2C~Q4 8 5 T~U~LE V
FIBER Fl~T9NG OF P~LY~ERS

Monomers ~ ~ ~ Fiber No. mQl~ % mQ~ 9'o mQl~ % E~

.
1 1.0 21 0.0 0 3.7 79 ~A
2 0 0 0 1.0 33 2.0 67 3-A
3 0 7 23 0.3 10 2.0 67 0 4 0.3 10 0.7 ~3 2.0 67 0 0.7S 30 0.25 10 l.S 60 0 6 0.5 20 0.5 20 l.S 60 0 7 0.2 8 0.8 32 l.S 60 8 0.1 4 0.9 36 1.5 60 3 9 0.0 0 1.0 40 1.5 60 3 0.0 0 1.0 40 l.S 60 3 11 0.3 13 0.7 31 1.2S 56 3 12 0.7 31 0.3 13 1.25 56 0 13 0.0 0 1.0 44 1.25 56 14 0.4 18 0.6 27 1.2S 56 lS 0.S 2S 0.5 2S 1.0 50 0 16 0.6 30 0.4 20 1.0 50 0 17 0.5 2S 0.5 2S 1.0 50 0 18 0.2 10 0.8 40 1.0 50 3 19 0.1 S 0.9 4~ 1.0 50 0.0 0 1.0 50 1.0 50 21 0.0 0 1.0 S7 0.75 43 0 22 0.2 11 0.8 46 0.75 43 3 23 0.4 23 0.6 34 0.75 43 3 24 0.S 28.S 0.S 28.5 0.75 43 0.8 46 0.2 11 0.75 43 0 26 0.666 3~ 0.333 19 0.7S 43 0 27 0.S 30 0.S 30 0.667 40 0 28 0.383 23 0.617 37 0.667 40 0 29 0.6 37 0.4 2S 0.6 38 0 0.4616 30 0.S384 3S 0.S38 3S 0 31 0.S4 3S 0.46 30 0.54 35 32 0.446 29 0.5S4 36 0.S38 3S 0 33 0.0 0 1.0 67 0.S 33 0 34 0.6 40 0.4 27 0.S 33 0 3S 0.6 40 0.4 27 0.S 33 0 36 0.6 40 0.4 27 0.S 33 0 37 0.4S 30 0.5S 37 0.S 33 2 38 0.4S 30 0.55 37 0.5 33 39 0.45 30 0.5S 37 0.S 33 2 T~UB~ V (Con~nued~

-MonQmers ~ r ~ Fiber No. n~ nh~ % n~ % Ra~n~

.
0.45 30 O.SS 37 O.S 33 2-L
41 0.45 30 O.SS 37 O.S 33 42 0.45 30 O.SS 37 O.S 33 43 0.45 30 O.SS 37 O.S 33 2-L
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49 0.53340 0.467 35 0.33 25 2 S0 0.47 3~ 0.53 41 0.3 23 1-2 Sl 0.44 34 0.56 43 0.29 23 3-L
52 0.44 34 0.56 43 0.29 23 2 53 0.44 34 O.S6 43 0.29 23 3-L
54 0.44 34 0.56 43 0.29 23 3 0.44 34 0.56 43 0.2g 23 2 56 0.4 31 0.6 47 0.29 22 2 57 0.6 48 0.4 32 0.25 20 58 O.S 40 O.S 40 0.25 20 2 S9 0.0 0 1.0 80 0.25 20 2-A
0.45 36 0.5S 44 0.25 20 3 61 0.3 24 0.7 56 0.25 20 62 0.4 33 0.6 49 0.22 18 2 63 O.S 42 O.S 42 0.2 16 2 64 O.S6 48 0.44 37 0.176 lS
0.4S 38 O.SS 47 0.176 lS 2 66 0.61 52 0.39 33 0.18 lS
67 0.4118 35 O.S882 50 0.176 lS 3 68 0.4118 35 0.5882 50 0.176 lS
69 0.4118 3S 0.5882 S0 0.176 15 0.42 38 0.58 52 0.11 10 2 71 0.55 S0 0.45 40 0.11 10 72 0.48 43 0.52 47 0.11 10 73 0.0 0 1.0 90 0.1 10 74 0.7 64 0.3 27 0.1 9 0 O.S 4S.5 ~.5 45.5 0.1 9 3 76 0.3 27 0.7 64 0.1 9 77 0.45 36 O.S5 44 0.25 20 2 78 0.5 42 0.5 42 0.2 16 2 79 0.42 34 0.58 46 0.25 20 2 0.47036 0.530 41 0.30 23 2 TA~l~E VII
BLENDS OF POLYESTERS (a) and (b) Polyester (weight %) Test ~ Ll~ ~ % wt. of No. P-l P,-l B-2 Glass Fibertl) 100.0 -- -- --2 70.0 -- -- 30 3 63.0 7.0 -- 30 4 55 .0 1 5.0 -- 30 S 42.0 28.0 -- 30 6 0.0 70.0 - 300 7 100.0 -- 0.0 --8 90.0 -- 10.0 --9 78.6 -- 21.4 --10 50.0 -- 50.0 --1 121 .4 -- 78.6 --12 10.0 -- ~0.0 --13 0.0 -- 100.0 --14 70.0 -- 0.0 30 lS 63.0 -- 7.0 30 16 5S.0 -- lS.0 30 17 35.0 -- 35.0 30 18 lS.0 55.0 30 19 7.0 -- 63.0 30 0.0 70.0 30 (1) Hemy and Friclc, untreated 3016 (1/16") glass fiber.
t2) Based on OC497 glass ro~/ing (Owens-Corning).

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OF BLENDS OF POLYESTERS OF TABLE V~

Test , Notchcd Unnotched (ft-lbl~n.) 14 0.70 2.00 0.90 2.70 16 1.22 5.61 17 2.30 12.80 18 2.50 15.30 19 2.40 17.50 2~ 2.30 8.70 .
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Z~Q485 TABLE ~
BLENDS OF POLYESTERS

-Polvester (Weight %~ _ Test (a) (b) (b) (b) GlassMelt Temp.
F~ )( C ) 21100.0 (con~ol) -- -- -- -- 383 22 78.6 -- -- 21.4 -- 373 23 20.0 -- -- 80.0 -- 32 1 24 (con~l) -- -- 100.0 -- 286 , (I) Hcn~y and Frick, 1/16" milled glass fiber.

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Tensile Flex % % % %Tensile % Mod Flex Mod Blister x 106 ~n~h ~ lQ6 ~1: ~ine 30 -- 17950 1.02.98 23550 2.27 223 0.13 30 -- -- -- -- 21850 2.22 231 3.4 63 7 30 -- 13250 0.6 2.5 21130 2.20 248 4.3 63 7 30 -- -- -- -- 21890 2.24 247 4.1 54 14 2g 3 -- -- -- 24114 1.96 201 3.2 68~ 0 29 3 -- -- -- 17560 1.97 253 9.0 A: 0.45 moles ~eph~alic acid 0.55 moles isophthalic acid 0.50 moles p-hydroxybenzoic acid 1.0 moles hydroquinone B: Q75 moles tephthalic acid 0.25 moles isophthalic acid 3.0 ~hydroxybenzoic acid 1.0 biphcnol

Claims (25)

1. A blend comprising a first LCP polyester polymer consisting essentially of units (I), (II), (m), and (IV).

( I ) (II) (m) (IV) 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 from 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 pans by weight per each part by weight of first LCP polyester.

3. The blend of Claim 1, wherein the first LCP polyester forms a stable oriented melt phase at about 340 to 400° C, s=0.25 to,0,55 q =0.5 to0.66,r=0.334 to 0.5, and p = 1Ø

4. The blend of Claim l, where the first LCP polyester filled with 30%o 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 = 1Ø

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), (II), (III), and (IV).

( I ) (II) ( III ) (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, 1, K, L, and M:

having a moiecular weight of about 2,000 to 200,000, wherein R is at least one member selected from the group consisting of naphthalene and phenyl substituted phenylene, allyl subsdtuted phenylene, aralkyl substituted phenylene and chloro substitutedphenylene, R1 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 ofnaphthalene 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 + I + m is approximately equal to 1, h + j + k = 0.05 to 1, h + m is approximately equal to k + I
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) (Vl) (VII) (VIII) 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 onc unit Xl -Ar-X2 (Xlll) wherein Ar comprises at least one member selected from the group consisting of ( XIV) ( XV ) ( XVI ) and ( XVII ) X1 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 (XIX) and (XX) which may be substituted by one or mare C1 to C4 alkyl groups, C1 to C4 alkoxy groups or halogen atoms; and whereinsaid second polyester comprises from about 10 to about 90 mole percent of units (XIX) and from about 90 to about 10 mole percent of units (XX).
(XIX) (XX)

14. The alloy of Claim 12, wherein the second LCP polyester consists essendally of the recurring units (XX), (XXI), (XXII):

(XX) (XXI) (XXII) and wherein said second polyester comprises from about 40 to about 60 mole percent of units (XX); from about 20 to about 30 mole percent of units (XXI); and from about 20 to about 30 mole percent of units (XXn).

15. The alloy of Claim 12, wherein the second LCP polyester consists essentially of the recurring units (XIX), (XXIII), and (XXIV) (XIX) (XXIII) (XXIV) which may be substituted by one or more C1 and C4 alkyl groups, C1 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 (XIX); from about 5 to about 45 mole percent of units (XXIII); 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) (VIII) (VII) 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 the 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 one unit XI - Ar - X2 (XIII) wherein Ar comprises at least one member selected from the group consisting of:

( XIV) ( XV ) ( XVI ) and ( XVII ) X1 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 R8 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) (VIII) (VII) wherein a is approximately equal to b + c, b is in the range from about 0.5 to 1.0, c is in the 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 l, 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.
X1 -Ar-X2 (XIII) wherein Ar comprises at least one member selected from the group consisting of:

(XIV) (XV) (XVI) and (XVII) X1 and X2 are independently selected from the group consisting of carbonyl and oxy.