CA1121081A

CA1121081A - Reinforced polyarylene esters

Info

Publication number: CA1121081A
Application number: CA000305292A
Authority: CA
Inventors: Oliver D. Deex; Virgil W. Weiss
Original assignee: Monsanto Co
Current assignee: Solutia Inc
Priority date: 1977-06-13
Filing date: 1978-06-12
Publication date: 1982-03-30
Also published as: IT7824474A0; EP0000097A1; AU518000B2; BR7803761A; AU3703178A; IT1096718B; AR217302A1; DE2860458D1; JPS5413552A; EP0000097B1

Abstract

REINFORCED POLYARYLENE ESTERS
ABSTRACT

Molding resins comprising an intimate blend of polyarylene ester of 1,2-bis(4-hydroxyphenyl)ethane and a reinforcing filler. The molding resins provide molded poly-ester articles possessing improved fire safety performance, higher heat distortion temperature and resistance to flow at elevated temperatures.

Description

08-12~0361A

REINFORCED POLYARYLENE ESTERS
This invention relates to a molding resin, ~o a method of producing the molding resin and to shapea arti-cles formed from the molding resin. More particularlyt S it pertains to molding resins comprising a polyarylene ester containing recurring units derived from 1,2-bis(4-hydroxyphenyl~ethane and a reinforcing filler, to a method of producing such molding resins and to shaped articles formed from such molding resins.

Many polyesters have been suggested for use as molding resins and engineering thermoplastics since the earliest practical development of such polymers by Whin-field and DicksonO Although several of such polyesters and copolyesters have found commercial success as film and lS fiber products, few have been successful as molding resins and engine~ring thermoplastics. Two of the more success~
ful, polyethylene terephthalate and polytetramethylene terephthalate prepared from aliphatic diols and tere-phthalic acid, suffer from certain deficiencies as Pngin-eering thermoplastics. They are both quite flammable andhave rather low glass transition temperatures which can limit their use~ulness to relatively low temperatures.

Recently polyarylene esters from bis(hydroxyphenyl) ethane have been developed and have been found to give su perior fir~ safety performance and to be capable o~ yield-ing crystalline compositions which have superior solvent resistance and stress cracking resistance.

. The present invention discloses impxoved molding resins provided by the intimate blending of reinforcing ~illers with such polyarylene esters. The improved molding resins have been found to yield molded articles possessing a)improved fire safety per:Eormance, particularly reduced a~terglow, b)improved resistance to heat distortion and s)improved resistance to flow at elevated temperatures in comparison with reinforced polyalkylene~erephthalates. The molding resins ofthe presentinvention comprisean intimate blend ofa polyarylenees~er anda reinforcing filler, ranging from 2to 60weight percentof the total composition. Such poly-arylene esters consistessentially ofunits derivedfrom atleast oneC8 to C25 aromatic dicarboxylic acid and a diphenol comprising from~0 to 100 molpercent 1,2-bis-(4-hydroxyphenyl) ethane andfrom 40to Omol percentof atleast oneC6 toC25 di phenol.
Also disclQsed in the present invention is a pro-cess of manufacture of molding resin by intimately blending these polyarylene esters with a reinforcing filler and the shaped articles molded from these molding resins.
The polyarylene ester component of the molding resin of the present .invention is the condensation product of at leastone C8 to C25 aromatic dicarboxylic acid and a di-p~.enol comprising from 60 to 100 molpercent 1,2-bis(4-hy-droxyphenyl)ethane and from 40 to 0 molpercent of at least one C6 to C25 diphen~l. The polyesters are described in Bel-gîan Patent 850,978 andhave been found topossess superior fire safety performance.
~ile essentially any suitable C8 to C25 aromatic dicarboxylic acid and admixture thereof can be used in the preparation of the polyarylene esters, the preferred aro-matic dicarboxylic ac~ds comprise at least one acid of iso-phthalic acid, terephthalic acid, 3,3'-, 3,4'- and 4,4'-bibenzoic acids and bis(carboxyphenyl)ethers, bis(carboxy-phenyl~sulfides, bis(carboxyphenyl~sulfones, bis(carboxy-phenyl)methanes, 1,2-bis(carboxyphenyl)ethanes and 2,2-bis (carboxyphenyl3propanes in which the carboxy groups are in th~ 3 or 4 positions. Mixtures of one or more of the aro-matic dicarboxylic diacids with minor quantities, generally less than 25 mol percent, of C2 to C20 aliphatic diacids can also be used. The quantities of aliphatic diacids in general are selected so that they do not cause a sig-nificant 105s in Tg of the resulting polyestersO Prefer-08~ 0~61 ably the quantity is limited to a loss in Tg of not m~r~than 10C. The acid or admixture o~ acids is combinc~ with 1,2-bis(4-hydroxyphenyl)ethane or with 1,2-bis(4-hyd~oxy-phenyl)ethane in admixture with essentially any oth~r suit-able diphenol or mixture of diphenols to provide the ~ro-matic polyesters of the present invention. Represen~aeiye diphenols comprise at least one diphenol of resorcinol, hydroquinone t 3,3'-, 3,4'- and 4,4'- diphenols, or di-phenols represented by the formula:
R m R m (I) ~ ~ ~

H OH
wherein the hydroxyl groups are in the 3- or 4- position~, Y is 0, S, SO2, C=0, CX2, CH(CH3), C(CH3)2, (CH2)2 or (CH2)3 and R is H or a Cl to C4 alkyl radical. Example~
of diphenols according to formula I include resorcinol, hydroquinone, bis(4-hydroxyphenyl)methane, 1,2-bis(3-hy-droxyphenyl)ethane, l-(3-hydroxyphenyl)-2-(4-hydroxyphenyl) ethane 2,2-bis(4~hydroxyphenyl)propane, bis(4-hydroxy-phenyl)ether, bis(4-hydroxyphenyl)sulfide and bis(4-hy-droxyphenyl)sul~one.

While the diphenol may contain at least 60 mol per-cent 1,2-bis~4-hydroxyphenyl)ethahe, it is preferred to use a diphenol which comprises at least 90 mol percent, 1,2-bis(~-hydroxyphenyl~ethane because these polyesters are generally crystalline and exhibit a rather rapi~ rate of crystallization and polyarylene esters in which 1~2-bis(4-hydroxyphenyl)ethane is substantially the only di-phenolic component which can be used to advantage to ob-tain more rapid rates of crystallization.

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The inherent viscosi~y of the polyesters de~
mined at 30C. and in a solvent combination o 60 p~
by weight phenol and 40 parts by weight sym-tetrachlor ethane at a concentration of 0.5 g per dl, is at le~
0.5 and is preferably at least 0.7. The selection o acid and diphenol components is made so that the poly-ester preferably has a glass transition temperature of at least 100C. and a melt viscosity at 350C. determined in a capillary rheometer at a shear rate of 100 sec o less than 105 poise. For crystalline polyesters prepared by condensation of aromatic diacid and diphenol comprising at least 90 mol percent 1,2-bis(4-hydroxyphenyl)ethane, the aromatic dicarboxylic acid is preferably selected so that the melting point of the polyaryle~e ester is less than 350C. A preferred group of the polyarylene e~ters comprises those polyesters obtained by condensation of a diphenol comprising at least 90 mol percent 1,2 bis(4-hydroxyphenyl)ethane and a dicarboxy:Lic acid comprising at least 67 mol percent isophthalic ~Icid. O this group, 29 one of the preferred combination is obtained from 1,2~
bis(4-hydroxyphenyl)ethane and isophtha7ic acid without addi~ional components. Such preferences are based on the availability and cost of the acid as well as on the de-sirable glass transition and melting points of the re-sulting polyesters.

Since molding cycles are preferably rapid, it i~desirable that a crystalline polyester crystallize in the short period during which the polymer is coolin~ in the mold. Thus a molding material for uses where high temper-ature dimensional stability is important, needs to have arapid rate of crystallization. The glass transition ~em-perature, the melting point and the rate of crystalliza-tion can be determined by means of differential scanning calorimetry as described in Belgian Patent 850,978.

08~

The crystallization rate is exprcssed ~ ~he in-verse of ~he time required for one half of th~ cry~tal-lization exotherm observed when a sample is coolcd at a rate of 20C. per minute. A rate of crystalliz~tion of ~bout 0.2 minutes 1 or greater as determined by ~his method is satisfactory in injection molding of polymers because the cooling rate in the molding operation is generally much faster than the cooling rate used in the determination of rate of crystallization. However, a crystallization rate of about 0.5 minutes or greater is more preferable and fox rapid molding cycles a cry-stallization rate of a~out one minute 1 or greater is even more preferred.

The polyarylene ester component of the present in-vention can be produced by a convenient method such as by melt condensation or solvent condensation of mixtures of aromatic dicarboxylic acids and diphenol diesters selected to provide polyarylene esters of the desired fire safety performance and procAessability. They can be produced by melt or solution pol~merization of selected mixtures of phenol esters of aromatic dicarboxylic acids and diphenols and by interfacial polymerization of salts of diphenols and aromatic dicarboxylic acid dihalides. Thus, while the com-bination is formally a condensate of diacid and diphenol, in practice the reactants are diacids and diphenol esters, or phenyl esters of diacids and diphenols, or salts of diphen-ols and diacid halides. One method of preparation is the melt condensation of mixtures of aromatic dicarboxylic acids and diphenol diesters. Another method is the melt condensation o mixtures of aromatic dicarboxylic acid~
and diph~nol diesters to a prepolymer sta~e of inherent viscosity in the range of 0.1 to 0.4 followed by solid state pol~merization to advance the polymer to an inherent viscosity above 0O5~

08-12 03~1A

The molding resins of the present inventlon ~r~
prepared by intimately blending the polyarylene e~tcr with sufficient reinforcing filler which is generally from 2 to 60 weight percent of the total composition.
Preferably, the amount of reinforcing filler is in the range of from 5 to 40 weight percent of the total com-position to achieve a sufficient degree of reinforcement without an excessive increase in melt viscosity. It i~
to be understood that the indicia of reinforcement are increases in the tensile strength, stiffness or impact strength of the filled composition in comparison with the unfilled composition.

In general, any reinforcement can be used such as granular, plate-like, acicular or fibrous fillers of suitable size for reinforcement. The fillers may be metallic such as aluminum, iron, ni.ckel, copper or ~inc or may be non-metallic such as carbon filaments, sili-cates, clays, calcined clays, asbestos, silica, titanium dioxide, titanate whiskers, glass flakes and fibers and the like.

The preferred reinforcing fillers include any kind of glass fibers usually used for reinforcing thermo-plastic resins and are relatively soda free glasses com-prising lime-alumin~m borosilicate glass such as types "C" and "E" glass. The fibers may be in the ~orm sf filaments, or bundled into strands, ropes or rovings a~d the like. They are -conveniently used in the form of chopped strands of up to 5 cm. in length and prefera~ly in the range o~ 0.3 c~ to 2.5 cm. in length. Other addi-tives such as colorants, plasticizers, stabilizers,hardeners and the like can be incorporated into the molding resins.

08-12~0361~
,, Blending of the polyarylene ester and ~he rein-forcing filler is carried out in any convenient way, such as by dry mixing pellets or powder of polyarylene ester with the filler and melt blending and extrusion, or by adding Xiller to molten polyarylene ester, blending and extrusîon The polyarylene ester, the reinforcing filler and any other additives are preferably as ~ree as possible of water. Mixing is preferably carried out in as short a time as possible to provide a sufficiently intimate and uniform blend and at a temperature selected for adequate melt viscosity but .insufficient to cause thermal degrada-tion of the resin. The blend can be extruded and cut up into molding compounds such as granules, pellets, etc. by conventional techniques.

The molding resins can be molded in any equipment conveniently used for reinforced thermoplastic composi tions e.g., a 14 gm. Arburg machine with temperature in the range of 250 to 350C. and mold temperature of lOb to 150C. can be used. Depending on the molding properties o the polyarylene ester, tne amount of reinforcing filler and the crystalli~ation behavior of the polyarylene ester, those skilled in the art will be able to make the conven-tional adjustments in molding cycles to accommodate the composition.

The invention is further illustrated but is not in-tended to be limited by the following examples in which ratios of monomers are mol ratios and all other part~ and percentages are by weight unless specified otherwiseO

EX~MPLE A
_ _ POLY(1,2-BISt4-HYDROXYPllENYL)ETHANE)ISOPHTHAL~TE

A charge consisting of 8.2 parts of isophthal~
acid and 14.8 parts of 1,2-bis(4-acetoxyphenyl)ethane i~
placed in a reaction vessel equipped with a stirrer, con~
denser and receiver. The vessel is evacuated and purg~d with nitrogen -three times~ A nitrogen blanket is mai~
tained in the reactor while it is heated to 250 C, for about three hours during which period approximately 3.5 4.0 parts of acetic acid distills. Thereupon the veS
is evacuated to a pressure of 125 mm. and heating at 2~5~
is continued for one half hour duriny which period an add~-tional 1 to 1.5 parts of acetic acid distills. The va~u~
is then increased to reduce the pressure to about 0.1 to 0.2 mm. and the temperature is raised to 290 C~ for an additional hour. Ak this point the reaction mixture ba~
comes so viscous that further stirring is diffioult.
Heating is stopped, the reaction mixture is again blanX~t~
; with nitrogen and allowed to cool. The resultant polym~
is light yellow in color, crystalline and demonstrates a~
inherent viscosity of 0.57 in the phenol~tetrachloroeth~na solvent.

EXAMPLE B
POLY ~ 2-BIS(4-~YDROXYPHENYL)ETHANE~ISOPHTHAL~TE
A similar reaction is carried out under the sam~
conditions and with th~ reactants and equipment describQd in Example A except that a~ter the initial three hour period the temperature is raised to 275C. and the pre~
sure is reduced to 125 mm. for 30 minutes. Thereafter, the.temperature is raised to 290 C. during the final per~od a~ high vacuum of 0.1 to 0.2 mm. The resultant polymer demonstrates an inherent viscosiky of 0.83 and is crystal~
line and a clear light yellow in color.

_g_ EXAMPLES C ~ U
Examples C to U are carried out by reacting mix-tures of diphenol diacetates and isophthalic acid by the melt method of Example A, with adjustment in the tempera-ture and heating cycle appropriate for the rheology andmorphology of the particular polyest~r or by melt poly-merization to a prepolymer followed by solid state poly-merization of the crystalline polyester. Compositions and physical property data are set forth in Table 1. Melt ~iscosities are determined at 316 C. with a SieglaCf-McKelvey Rheometer at a shear rate of 100 sec 1, using a capillary with a length to diameter ratio of 25 to 1.

The data show that polyester combinations contain-ing high levels of 1,2-bis(hydroxyphenyl)ethane and acids such as isophthalic acid are opaque and exhibit crystal-line melting points below 300 C~ and crystallize rapidly while in contrast, polyester combinations containing sub-stantial amounts of other diphenols and polyester combin-ations containing substantial amounts of substituted acids such as 5-t-butyl-isophth,alic acid are amorphous.

Fire safety performance is conveniently determined by the Underwriter's Laboxatory "Test for Flammability of Plastic Materials - UL-94, September 17, 1973" using the ratings which became effective February 1, 1974. The polyesters of 1,2-bis-(4-hydroxyphenyl)ethane are found to be superior in their UL-94 rating to polyesters con-taining a substantial amount of bisphenol A(2,2-bis~4 hydroxyphenyl)propane.

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PREPARATION OF MOLDING RESINS

Polyisophthalate of 1,2-bis(4-hydroxyphenyl) ethane prepared as in Example C, is extruded and chopped to yield pellets of approximately 3 to 5 mm in length and

2 mm in diametex. 85 parts by weight of the pellets are blended in a tum~le blender with 15 parts by weight of chopped glass strand, 4.8 mm length, containing B00 fila-ments of .13 micron,diameter per strand supplied by Owens 10 Corning Fiberglas Corporation under the trade name Owens- !
Corning Fiberglas 4~9. The blend of polyester and glass fiber is force fed to the chopper o~ a single stage ex-truder heated to 320C. and is slowly extruded through the strand die. The strand is cooled and c'hopped to provide lS pellets of molding resin.

The molding resin is injection molded in a 14 gm.
Arburg machine at a temperature of 315C. and a mold temper-ature of 122C. to provide test bars, The test bars are tested or tensile strength and elon~ation, AST~ D-638;
flexural strength and modulus~ ASTM D-790; impact strength AST~ D-256; heat distortion ASTM D-648. The data are pre-sented in T~ble 2.

EXAMPLES ? and 3 Molding,resins are prepared as in Example l with the polyisophthalate of l,2-bis(4-hydroxyphenyl)ethane and respectively 22.5 and 30 parts by weight'of glass fiber per 100 parts by weight of total composition. The molding resins are injection molded into test bars and subjected t~ physical testing. The data are pxesen~ed in Table 2.

PHYSICAL PROPERTIES OF ARTICLES MOLDED FROM THE
POLYISOPHTHALATE OF 1, 2 -BIS ~ 4 -HYDROXYPIIENYL) ETHANE
. Examples Wt. % Glass Fiber ' 15 22.5 30 'None Tensile Strength, Kg cm 10.5 12 12.7 6.3 X 10-2`
Elongation % ' 4.4 3.1 1.8 18 Modulus Kg. cm 2 X 10 5.3 7.0 8.4 2.3 Izod(64 cm X 1.3 cm X 0.18 0.24 0.26 0.25 0.64 cm~ Kg m HDTUL, C. (16.4 cm X 158 183 204 137 ' 1.3 cm X 0.~4 cm;
18.6 kg cm~~
Example 2 is subjected to the Underwriter's UL-94 test~ The rating for samples,1.58 mm in thickness is V-0 (average flame out time within 5 seconds, no afterglow~.
In comparison, the polyester of Example 2 without glass fiber rein~orcement is rated V-o (average flame out time within 3 seconds with a$terglow). A test bar of Example 2 with a heat distortion temperature of 183C. was subject-ed to a load in the range of 0.14 to 0,28 kg cm 2 for 20 minutes at 210 C. No flow or deformation occurs. In contrast, a test bar of a reinforced polytetramethylene terephthalate, containing 30 weight percent glass fiber, having a heat distortion temperature of 212C, show~ con-siderable flow and deformation under similar conditions and fails the UL-94 test.

Molding resins are prepared as in Example l.by blending polyarylene ester Examples Kl L, M, ~, P and R
with 30 weight percent of the total composition of Owens-Corning Fiberglas 419. The molding resins ar~ molded in-to test bars. Considera~le enhancement of the tensile 08-12-0361~

strength~ modulu~ and heat distortion temperature is ob-tained i~ co~parison with the unfilled polyester~.

These exampIes are prepared for comparative pur-poses~ A polyarylene ester similar to Example U comprising the condensation product o~ bisphenol A and isophthalic acid, of inherent viscosity 0.8 is blended with glass fiber in the manner described in Example 1. The molding resins thus obtained are molded into test bars and tested for physical properties. Examples 10, 11 and 12 contain 15, 22.5 and 30 weight percent of glass fiber; Example 13 is the unreinforcedpolyester. The data are presented in Table

3 and show that the heat distortion temperature of this polyester is relatively unaffected by the reinforcing fil-ler in contrast to the pronounced effect obtained in Exa~-ples 1-3 comprising the polyisophthalate of 1,2-bis(4-hydroxyphenyl)ethane.

PHYSICAL PROPERTIES OF ARTICLES MOLDED FROM THE
20 POLYISO ~ ~ ~ ~ ~OPANE
Examples -- . .
Wt. ~ Glass Fiber 15 22.5 30None Tensile Strength kg cm 2 9.333.2 12.5 7.7 Elongation ~ 5.63.9 3.8 4.0 _~ -4 Modulus kg cm X 10 4.05.8 6.7 2.24 HDTUL, C, 18.6 kg cm 175 173 177 160 Molding resins containing 30 weight percent glass fiber are prepared in the manner of Example 1 from poly~
ester Example~ S and T, The molding resins are molded S into test bars. T~e tensile strength and modulus of the polyesters are enhanced by the addition of glass fiber.
However, little improvement in heat distortion temperature is obtained.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

l. A molding resin comprising an intimate blend of a polyarylene ester and a reinforcing amount of a reinforcing filler, wherein the polyarylene ester consists essentially of units derived from at least one C8 to C25 aromatic dicar-boxylic acid and a diphenol comprising from about 60 to 100 mol percent 1,2-bis(4-hydroxyphenyl)ethane and from about 40 to 0 mol percent of at least one other C6 to C25 diphenol and wherein the inherent viscosity of the polyarylene ester at 30°C. determined at a concentration of 0.5 grams polyester per 100 ml solution in a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of sym-tetrachloroethane is at least about 0.5, and the melt viscosity of the poly-arylene ester at 350°C. determined at a shear rate of 100 sec -1 with a capillary rheometer is less than about 105 poises.
2. The molding resin of claim l wherein the reinforcing filler is a granular, plate-like, acicular or fibrous filler and comprises from about 2 to about 60 weight percent of the molding resin.
3. The molding resin of claim 2 wherein the reinforcing filler is a fibrous non-metallic filler.
4. The molding resin of claim 2 wherein the reinforcing filler is glass fiber.
5. The molding resin of claim 2 wherein the aromatic dicarboxylic acid comprises at least one acid selected from the group consisting of isophthalic acid, terephthalic acid, t-butyl-isophthalic acid, 3,3'-, 3,4'- and 4,4'-bibenzoic acids and bis(carboxyphenyl)ethers, bis(carboxyphenyl)-sulfides, bis(carboxyphenyl)sulfones, bis(carboxyphenyl)-methanes, 1,2-bis(carboxyphenyl)ethanes, and 2,2 bis(4-carboxyphenyl)propanes, wherein the carboxy groups are in the 3- or 4-positions.
6. The molding resin of claim 2 wherein the C6 to C25 diphenol comprises at least one diphenol selected from the group consisting of resorcinol, hydroquinone, 3,3'-, 3,4'-and 4,4'-diphenols, 1,2-bis(3-hydroxyphenyl)ethane, 1-(3-hydroxyphenyl)-2-(4-hydroxyphenyl)ethane, and diphenols represented by the formula wherein the hydroxyl groups are in the 3- or 4-positions, Y is 0, S, SO2, C=O, CH2, CH(CH3), C(CH3)2, or (CH2)3, and R is H or a C1 to C4 alkyl radical and n = 0 to 4.
7. The molding resin of claim 2 wherein the C6 to C25 diphenol comprises at least one diphenol selected from the group consisting of hydroquinone, resorcinol, bis(4-hydroxy phenyl)methane, 1,2-bis(3-hydroxyphenyl)ethane, 1-(3-hydroxy-phenyl)-2-(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)-propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) sulfide and bis(4-hydroxyphenyl)sulfone.
8. The molding resin of claim 2 wherein the diphenol comprises from about 90 to 100 mol percent 1,2-bis(4-hydroxy-phenyl)ethane and from about 10 to 0 mol percent of at least one C6 to C25 diphenol.
9. The molding resin of claim 2 wherein the inherent viscosity of the polyester is at least about 0.7.
10. A molding resin comprising an intimate blend of a crystalline polyarylene ester and from about 2 to about 60 weight percent of the total composition of a reinforcing filler, wherein the polyarylene ester consists essentially of units derived from at least one aromatic dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid, t-butylisophthalic acid, bis(4-carboxy-phenyl)ether, bis(4-carboxyphenyl)sulfide, bis(4-carboxy-phenyl)sulfone, bis(4-carboxyphenyl)methane, 1,2-bis(4-carboxyphenyl)ethane, 2,2-bis(4-carboxyphenyl)propane, 3,3'-, 3,4'- and 4,4'-bibenzoic acids, and units derived from a diphenol comprising from about 90 to 100 mol percent 1,2-bis(4-hydroxyphenyl)ethane and from about 10 to 0 mol percent of at least one C6 to C25 diphenol and wherein the inherent viscosity of the polyarylene ester at 30°C. deter-mined at a concentration of 0.5 grams polyester per 100 ml solution in a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of sym-tetrachloroethane is at least about 0.5, and the melting point of the polyarylene ester is less than about 350°C.
11. The molding resin of claim 10 wherein the reinforcing filler is a granular, plate-like acicular or fibrous filler.
12. The molding resin of claim 10 wherein the reinforcing filler is a fibrous non-metallic filler.
13. The molding resin of claim 10 wherein -the reinforcing filler is glass fiber.
14. The molding resin of claim 10 wherein the C6 to C25 diphenol comprises at least one diphenol selected from the group consisting of hydroquinone, resorcinol, bis(4-hydroxy-phenyl)methane, 1,2-bis(3-hydroxyphenyl)ethane, 1-(3-hydroxyphenyl)-2-(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide and bis(4-hydroxyphenyl)sulfone, and wherein the inherent viscosity of the polyarylene ester is at least about 0.7.
15. The molding resin of claim 10 wherein the polyarylene ester has a crystallization rate of at least about 0.2 min -l.
16. The molding resin of claim 10 wherein the polyarylene ester has a crystallization rate of at least about 0.5 min -l.
17. A molding resin comprising an intimate blend of a crystalline polyarylene ester and from about 2 to about 60 weight percent of the total composition of a reinforcing filler wherein the polyarylene ester consists essentially of units derived from an aromatic dicarboxylic acid com-prising at least about 67 mol percent of isophthalic acid and a diphenol comprising at least about 90 mol percent of 1,2-bis(4-hydroxyphenyl)ethane and wherein the inherent viscosity of the polyarylene ester at 30°C. determined at a concentration of 0.5 grams polyester per 100 ml solution in a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of sym-tetrachloroethane is at least about 0.7, and the melting point of the polyarylene ester is less than about 350°C.
18. The molding resin of claim 17 wherein the reinforcing filler is a granular, plate like, acicular or fibrous filler.
19. The molding resin of claim 17 wherein the reinforcing filler is a fibrous non-metallic filler.
20. The molding resin of claim 17 wherein the reinforcing filler is glass fiber.
21. The molding resin of claim 17 wherein the polyarylene ester has a crystallization rate of at least about 0.2 min -1.
22. The molding resin of claim 17 wherein the polyarylene ester has a crystallization rate of at least about 0.5 min -1.
23. A molding resin comprising an intimate blend of a polyarylene ester and from about 2 to about 60 weight percent of the total composition of a reinforcing filler, wherein the polyarylene ester consists essentially of recurring units represented by the formula and has an inherent viscosity at 30°C. determined at a con-centration of 0.5 grams polyester per 100 ml solution in a solvent mixture of 60 parts by weight of phenol and 40 parts by weight of sym-tetrachloroethane of at least about 0.7.
24. The molding resin of claim 23 wherein the reinforcing filler is a granular, plate-like, acicular or fibrous filler.
25. The molding resin of claim 23 wherein the reinforcing filler is a fibrous non-metallic filler.
26. The molding resin of claim 23 wherein the reinforcing filler is glass fiber.