CA2044416A1 - Copolyestercarbonate polymers derived from diaryl dicarboxylic acids and their derivatives and blends thereof - Google Patents

Abstract

ABSTRACT

This invention relates to copolyestercarbonate polymers which are prepared with diaryl dicarboxylic acid compounds, particularly biphenyldicarboxylic acid compounds. Such copolyestercarbonate polymers show good physical properties including high glass transition tem-peratures and low ultraviolet radiation sensitivity.
The thermoplastic copolyestercarbonates can be used to prepare films or molded articles or blended with other thermoplastic resins to give thermoplastic polymer blends for molding purposes.

36,665-F

Description

2 0 ~

COPOLYESTERCARBONATE POLYMERS
DERIVED FROM DIARYL DICARBOXYLIC ACIDS
AND THEIR DERIVATIVES AND BLENDS THEREOF

This invention relates to copolyestercarbon-ate polymers, resins, and blends thereof and more ~ 5 particularly to such polymers prepared from a diaryl dicarboxylic acid compound.

A wide variety of polycarbonate and copolyes-tercarbonate resins are known and usefully employed asthermoplastics for a variety o~ molded articles and com-ponents. In spite of the wide diversity of physical properties associated with the known resins, there re-mains a need for even more diverse physical properties.
For some of today's current applications it is desirable to provide copolyestercarbonate resins with improved physical properties including increased tensile and impact properties, improved hydrolytic and solvent resistance and reduced sensitivity to ~V radiation.

Typically, copolyestercarbonate resins are prepared by reacting a dihydroxy compound with a dicar-boxylic acid compound and a carbonate precursor. The 367665~F -1-2 0 ~

dicarboxylic acid compounds most commonly employed are those of terephthalic acid and isophthalic acid.

It has now been discovered that the desirable improvements in such physical properties of copolyester-carbonate polymer resins can be obtained by using alter-native dicarboxylic acid compounds.

In one aspect, this invention is a copolyester-carbonate polymer prepared by contacting a dihydroxycompound with a dicarboxylic acid compound and a car-bonate precursor characterized in that (a) at least 50 mols percent of the dicarboxylic acid compound employed comprises a diaryl dicarboxylic acid compound containing two or more aromatic rings which are connected together ~ by a positionally and angularly well defined rigid in ternal linking group, and (b) the mole ratio of dicar-boxylic acid compound to carbonate precursor is such that the pol~mer has a molar ratio of diester:carbonate groups from 0~02:1 to 20:1.

In another aspect, this invention is a ther-moplastic polymer blend comprising a thermoplastic poly-mer and a copolyestercarbonate polymer characterized inthat the copolyestercarbonate polymer is prepared by contacting a dihydroxy compound with a dicarboxylic acid compound and a carbonate precursor wherein (a) at least 50 mole percent of the dicarboxylic acid compound employed comprises a diaryl dicarboxylic acid compound containing two or more aromatic rings which are con-nected together by a positionally and angularly well defined rigid internal linking group, (b) the mole ratio of dicarboxylic acid compound to carbonate precursor is such that the polymer has a molar ratio of diester:car-36,665-F -2 - ;, 20~l16 bonate groups from 0.02:1 to 20:1 and ~c) in that the polymer blend contains at least 0.5 weight percent of th~ said cupolye3Lercarbona~e by to~al weight of thermoplastic polymer and copolyestercarbonate polymer present.

Surprisingly, it has been found that the poly-mers of the present invention exhibit improved proper-ties including impact strengths, glass transition tem-peratures, and reduced ultraviolet radiation sensitiv-ity. Even more surprisingly, it has been found that the polymers of the present invention may be used~ for exam-ple, in preparing films where the thickness of the film prepared can be greater than that for other polymers in the prior art without the problem of a crystallinity - buildup.

As described hereinabove, this invention is a copolyestercarbonate polymer prepared by contacting a 2~ dihydroxy compound with a dicarboxylic acid compound and a carbonate precursor. The polymer is characterized in that the mole ratio of dicarboxylic acid compound and carbonate precursor with respect to the dihydroxy com-pound is such that the resulting polymer has a molarratio of diester:carbonate groups from 0.02:1 to 20:1, preferably from 0.05:1 to 15:1 and more preferably from 0.06:1 to 10:1. The optimum ratio of diester groups to carbonate groups in the copolyestercarbonate polymer depends on the intended application of the polymer and should be determined by trial and error. Diester groups originate from the reaction of the dihydroxy compounds with the dicarboxylic acid compound, and carbonate - groups from the reaction of the dihydroxy compound and carbonate precursor.

36,665-F _3_ -.

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2 0 ~

The polymer is further characterized in that of the tutal dicar~oxylic acid culllylJuild employed to pre-pare the polymer, at least about 50 mole percent, pre~-erably at least about 70 mole percent and more prefer-ably at least about 85 mole percent is a diaryl dicar-boxylic acid compound containing two aromatic rings which are connected together by a positionally and angularly well defined rigid internal linking group.
1~
The rigid internal linking group confers a rod-like geometry to the diaryl dicarboxylic acid com-pound. Exemplary of such rigid internal linking groups are a covalent bond, a cycloaliphatic or heterocyclic ring (wherein preferably the aryl groups o~ the dicar-~ boxylic acid are associated with the same atom center of the. ring), -C=C-, -C 3 C- , -COO- ~ ~NHCO-, -NHCOO-, -C_N-, --C=C-C--, ll Fl il -ISI- , -S- , -C-o 36,665-F _4_ .
:

: ' " ' ~ , .. ~ ... . .

20~4~16 and -N=C-N-. The preferred rigid internal linking group for the copolyestercarbonate polymers of the present ln~-erl~io~ is a co-~alent bond.

The diaryl dicarboxylic acid compound is a dicarboxylic acid, a dicarboxylic chloride or mixtures thereof. Each aryl ring is substituted by at least one carboxylic acid or carboxylic acid chloride group. In addition, the aryl aromatic rings are optionally and independently substituted with from 1 to 4 substituents exemplary of which when not hydrogen are halogen, C1_ alkyl groups~ oxy-C1-6 alkyl groups, oxyaryl, phenyl, benzyl, or mi~tures thereof. Preferred substituents for the present invention when not hydrogen are chlorine, bromine, C1_6 alkyl groups, especially methyl, though it - is most preferred when none of these substituents are present on the aryl ring.

Exemplary of suitable diaryl dicarboxylic acid compounds for use in the present invention include 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarbox-ylic acid, 4,4'-biphenyldicarboxylic acid chloride, 3,4'-biphenyldicarboxylic acid chloride and mixtures thereof. Especially preferred are the 4,4'-dicarboxylic acid and acid chloride isomers. The remaining mole fraction of dicarboxylic acid compound required, if any, for preparing the polymer can be composed of one or more suitable dicarboxylic acids or dicarboxylic acid chlorides, different than the diaryl dicarboxylic acid compound described hereinabove, and familiar to one skilled in the art of preparing polyester polymers.

Suitable dicarboxylic acid compounds can be aliphatic, alicyclic, heterocyclic, aromatic, cr 36,665-F _5_ ` 20~4~1~

mixtures thereof. Hydroxy acids may also be used in small quantities in the preparation of the polymers of thi3 il-lv~r~ti~r-l.

Suitable aliphatic dibasic acids are those derived from straight-chain paraffin hydrocarbons such as oxalic, malonic, dimethyl malonic, succinic, glu-taric, adipic, pimelic, subaric, azelaic, and sebacic acid. Also included are the halogen-substituted ali-phatic dibasic acids. Aliphatic carboxylic acids con-taining heteroatoms and their aliphatic chain, such as thiodiglycollic or dlglycollic acid may also be ~sed.
Also useful are such unsaturated acids as maleic or fumaric.
~ Suitable alicyclic dicarboxylic acids include trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclo-hexanedicarboxylic acid, and 1,3 cyclohexanedicarboxylic acids; and alkyl-, alkoxy-, or halogen-substituted derivatives o~ the above said alicyclic dicarboxylic acids.
,:
Aromatic dicarboxylic acids suitable ~or use in the making o~ polymers of the present inventlon include terephthalic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenylether-4,4'-` -dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4j4'-dicarboxylic acid, biphenyl-ethane-4,4'-dicarboxylic acid, isophthalic acid, biphe-nylether-3,3'-dicarboxylic acid, diphenoxyethane-3.3'--dicarboxylic acid, biphenylethane-3,3'-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid and 1,5--anthraquinonedicarboxylic acid; and alkyl-, alkoxy-, or halogen-substituted derivatives of the above said aro-36,665-F -6-:

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2~444~

matic dicarboxylic acids such as chloro terephthalic acid, dichloro terephthalic acid, bromo terephthalic acid~ mathyl terepfltnalic acid, dimethyl t~-rapllt~-lalie acid, ethyl terephthalic acid, methoxy terephthalic acid and ethoxy terephthalic acid.

Examples of hydroxy acids are hydroxy glutaric acid, mandelic acid, the various isomers of hydroxy ben-zoic acid and hydroxy biphenyl carboxylic acid.

The mono- and diacid chloride derivatives of the above-mentioned dicarboxylic acids are also suitable for preparing the polymers of the present invention.
Further examples of suitable dicarboxylic acid compo~lnd~
or hydroxy carboxylic acid compounds are given in U.S.
~ Patents 3,637,595; 3,975,487; and 4?118,372. When the diaryl dicarboxylic acids are used in combination with other suitable dicarboxylic acids, preferred are the above-mentioned aromatic carboxylic acids.

The dihydroxy compound used in preparing the copolyestercarbonate polymer of the invention can be an aliphatic, alicyclic, heterocyclic or aromatic dihydroxy compound which has two hydroxyl groups capable of react~
ing with the carboxylic acid or acid chloride and car-bonate precursor to give the polymer of the present invention. Combinations of one or more of these dihy-droxyl compounds can be used to make the copolyester-carbonate polymers.

It is preferred for this present inventionthat the dihydroxy compound employed comprises at least about 50 mole percent, preferably at least about 70 mole percent and most preferably from 90 to 10Q mole percent 36,665-F -7-, ` ` 2 ~ 1 6 of a dihydroxy diaryl compound. The dihydroxy diaryl compound is represented by the formula H~ (A~m ~ - B-H

(X)y (X)y wherein A is selected from the group consisting of a divalent hydroc~rbon containing from one to about 15 car~on a~oms, a halogen-substituted divalent hydrocarbon . radical containing from one to about 15 carbon atoms and ; 15 divalent groups such as -S-, -S-s-? --? -C=C-~ -C=N-, O O

~ c , s , s .. o :` 20 .
a covalent bond or any other rigid linking group as defined hereinabove; B independently is oxygen, sulfur or a divalent radical such as -ORO-, wherein R is a C1_6 hydrocarbon; X, when not hydrogen, is independently . selected from the group consisting of halogen, a mono-valent hydrocarbon radical such as an alkyl group or from 1 to 6 carbon atoms, an aryl group of from 6 to 18 carbon atoms, an aralkyl group of from 7 to 14 carbon 3 atoms, an oxyalkyl group of from 1 to 6 carbon atoms, and an oxyaryl group of from 6 to 18 carbon atoms; m is O or l and y is a whole number integer of from O to 4.

Typical of some of the dihydroxy diaryl com-:~ pounds that are advantageously employed are bisphenols 36,665-F -8-~`
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g such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxy-phenyl)-l-phenylethane, 2,2 bis(4-hydroxyphenyl)propane (dlso ~o~ onl~ k~low~l as bisphenol A), 2,2-uis(4-llydruxy--3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)hep-tane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2--bis(4-hydroxy-3,5-dibromophenyl)propane;
dihydroxyphenyl ethers such as bis(4-hydroxy-phenyl)ether, bis(3,5-dichloro-4-hydroxyphenyl)ether;
dihydroxy biphenyls such as 4,4'-dihydroxybiphenyl, 3,3'-dichloro-4,4'-dihydroxy biphenyl, 2,2',6,6'--tetrabromo-3,3',5,5'-tetramethyl-4,4'-dihydroxybiphe-nyl; dihydroxy aryl sulfones such as bis(4--hydroxyphenyl)sulfone, bis(3,5-dimethyl-4--hydroxyphenyl)sulfone; and dihydroxy biphenyl sulfides and sulfoxides such as bis(4-hydroxyphenyl)sulfide and ~ bis~4-hydroxyphenyl)sulfoxide; or mixtures thereof.

The preferred dihydroxy diaryl compounds are the bisphenol compounds, especially the 4,4'-bisphenols optionally substituted by a halogen or a C1_6 hydrocar-bon radical and biphenyl compounds. Exemplary of such diaryl dihydroxy compounds are 2,2-bis(4-hydroxyphe-- nyl)propane, l,l-bis(4-hydroxyphenyl)-1-phenylethane, 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-4,4'-dlhy-droxybiphenyl, 2,2-bis~4-hydroxy-3,5-dichlorophenyl)-propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 4,4'-dihydroxybiphenyl and bis(4-hydroxyphenyl)sulfide also referred to as 4,4'-thiodiphenol.
The remaining portion of dihydroxy compound required in the reaction of preparing the copolyester-carbonate polymer of the present invention may be com-posed of a dihydroxy diaryl compound different from the preferred compounds described hereinabove or it may 36,665-F -9-, 20~4416 consi~t of one or more aliphatic, alicyclic or aromatic diols commonly used in the preparation of polyester or polycarbonate poLyoi3.

Suitable diols are aliphatic diols including straight-chain and branched aliphatic diols sueh as eth-ylene glycol, propylene glycol, butylene glycol, and neopentyl glycol; alicyclic diols such as trans-1,4-cy clohexanediol, cis-1,4-cyclohexanediol, trans~1,4-cyclo-hexanedimethanol, cis-1,4-cyclohexanedimethanol, trans--1~3-cyclohexanedimethanol; and alkyl-, alkoxy-, or halogen-substituted derivatives of the above said ali-cyclic diols such as trans-1,4-(1-methyl)cyclohexanediol and trans-1,4-(1-chloro)cyclohexanediûl.
- Suitable aromatic diols include hydroquinone, resorcinol, 2,6-naphthalenediol, 1,6-naphthalenediol~ A
variety of additional aromatic diols are also available and are disclosed in U.S. Patents 2,999,835; 3,028,365 and 3,153,008.

It is also possible to use, in addition to the aromatio diols, aromatic mercaptophenols, aromatic hydroxy amines and aromatic diamines. Exemplary of ~uch compounds are benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalenedithiol 9 2,7-naphthalenedithiol, 4-mer-captophenol, 3-mercaptophenol, 6-mercaptonaphthol, 7-mercaptonaphthol, 4-aminophenol, n-methyl-4--aminophenol, 1,4-phenyldiamine, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino--1-naphthol, 4-amino-4'-hydroxybiphenyl and mixtures thereof. Additional aromatic hydroxy amines and aromatic diamines are disclosed in U.S. Patent 4,726,998.

36,665-F -10-- , , .
' ~ ' ~ ' ' '. , , ;'` ' ' ' 204~

1 1 .

The carbonate precursor may be either a car-vonyi naiide, a diaryl car-bonate or a bishaloforma1e.
The carbonyl halides include carbonyl bromide, carbonyl chloride and mixtures thereof. The bishaloformates suitable for use include the bishaloformates of dihydric phenols such as bischloroformates of 2,2-bis(4-hydroxy-; phenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)-propane, hydroquinone or bishaloformates of glycols such as ethylene glycol. While all of the above described carbonate precursors are useful, carbonyl chloride, also known as phosgene, is preferred.

The copolyestercarbonate polymers of the pres-ent invention may be obtained by various known processes ~ using solution or interfacial polymerization techniques such as described, for example, in the EncyclopediaofPoly-merScienceandTechnology, 1969, Vol. lO, p. 726 and the publication "Polyester", Pergamon Press (1965) p. 448 etseq.. Exemplary of methods by which copolyestercarbon-ates may be produced are those methods described in U.S.
Patents 3,169,121; 4,105,633; 4,156,069; 4,194,038;
4,238,596; 4,238,597; 4,252,93g; 4,255,556; 4,260,731;
4,287,787; 4,330,662; 4,355,150: ~,360,656; 4,369,303;
4,374,973; and 4,388~455.
~' The polymers of the invention may9 in addition to being used for molding purposes, be employed as the base for preparing thermoplastic molding compositions by being compounded with conventional molding aids such as, for example, antioxidants, antistatic agents, inert fillers such as glass, talc, mica, clay, hydrolytic stabilizers such as the epoxides as disclosed in U.S.
Patents 3,489,716; 3,839,247; and 4,138,379; color 36,665-F

' `

2~4~41~

stabilizers such as organophosphites, thermal stabilizers such as phosphites; flame retardants and mold release ageht3~ The polyulers Ol the invention show reduced sensitivity to UV radiation over those of the prior art but if required UV radiation absorbers such as benzophenone~ and benzotriazoles can be incorporated into the thermoplastic molding composition.

The copolyestercarbonate polymers of the present invention can also be employed with other ther-moplastic polymers to prepare thermoplastic polymer blends. Suitable thermoplastic polymers for this pur-pose include thermoplastic polyurethanes, polyesters, polycarbonates, polyalkylenes such as polypropylene and polyethylene, copolymers thereof and mixtures thereof.
-When the copolyestercarbonate polymers of thepresent invention are used to prepare thermoplastic polymer blends, advantageously the blend comprises at least 0.5 weight percent, preferably at least 5 weight percent, and more preferably frum 10 to 99 weight percent of said copolyestercarbonate polymer by total weight thermoplastic polymer and copolyestercarbonate polymer present.

The following examples are given to further illustrate the invention as construed by the inventors.
However, these examples are not to be interpreted as limiting the scope of the invention in any way. Unless stated otherwise, all parts and percentages are given by weight.

36,665 F -12-. .~
.

20~441~

Where reported, the following tests are carried out to characterize the polymers of the invention using the ~est pruee~ures ~s in~ic~ted. -Inherent visc03ity (IV) is determined in methylene chloride at 25C and using a concentration of 0.5 gtdL. The glass transition temperature (Tg) is determined by differential scanning calorimetry at a heating rate of 20C/minute. The extrapolated onset value is reported.

The following tests are performed using compression molded specimens (0.125 inch (3.2 mm) thickness) prepared at 80C to 120C above Tg. Notched Izod impact resistance is determined according to ASTM
D-256, wherein a 0.01-inch (0.254 mm) notch radius is employed. Tensile properties including tensile modulus - (TM), tensile strength at yield ~TY), elongation at yield (EY), and post-yield stress drop (PYSD) are measured according to ASTM D-638. The determination of PYSD is described by Bubeck et al. in PolymerEngineering andScience, 24, 1142 (1984). Specific gravity (SG) is measured by ASTM D-792. Resistance to hydrolysis is determined by measuring the weight loss resulting from immersion in 10N NaOH solution. The critical strain for crazing is determined after a 30-minute exposure period according to the procedure of Wyzgoski, GeneralMotors Research Publication (~MR-3779 ( 1981 ) .
The sensitivity of the polymer to ultraviolet (UV) radiation is determined by measuring the change in yellowness index (YI) of compression moldings after exposure to a Hanovia 450W medium pressure mercury arc lamp or a Q~V testing chamber. YI is determined according to ASTM D-1925.

36,665-F -13-: .
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204~41~

~xampie 1 This example describes the synthesis of a bis-phenol A/4,4'-biphenyldicarboxylate copolyestercarbonate having a diester~carbonate molar ratio of 1.0:1.

A two-liter (L) flask equipped with a thermom-eter, nitrogen and phosgene inlets,-and a paddle stirrer 0 connected to a Cole Parmer Servodyne is charged with 99.44 g (0.436 mole) of bisphenol A, 89.7 g (1.134 mole) of pyridine, and 1.18 L of methylene chloride. The resulting clear solution is stirred at 300 rpm, cooled to about 16C, and then 60.79 g (0.218 mole) of 4,4'--bi-_ phenyldicarboxylic acid chloride is added to the flask over a period of about 4 minutes, resulting in an exo-therm to about 20C. The clear solution is ~tirred for 10 minutes, 1.64 g (0.011 mole) of p-tertiary-butylphe~
nol is added, and then 22.5 g (0.23 mole) of phosgene is added to the flask over 15 minutes, while maintaining the contents of the flask at 14C to 29C. ~ethanol (3 mL) and HCl (3N, 160 mL) are added, the contents of the flask are stirred an additional 30 minutes, and then poured into a 2-L separatory-funnel. The methylene chloride phase containing the copolyestercarbonate is separated, washed again using 215 mL of 0.5N HC1, and then passed through a column (300~mL bed volume) of macroporous cation-exchange resin. The polymer is then isolated by adding one volume of the methylene chloride solution to a mixture of 2.4 volumes of hexane and 1.2 volumes of acetone in an explosion-resistant blender, and then collecting the resulting precipitated product by filtration.

36,665-F _14_ ~' ' 2~416 The precipitated product is then dried in a vacuum oven at about 120C for 48 hours. The resulting product weighs 136.5 g, has an IV of 0.72 dL/g, and exhibits a diester:carbonate ratio of t.0:1 as deter-mined by nuclear magnetic resonance and infrared spec-troscopy. This material is designated Sample No. 1.

For purposes of comparison, the general proce-dure of` this example is employed to prepare a bisphenolA/terephthalate copolyestercarbonate polymer having a diester~carbonate ratio of 1.0:1. For this comparison material, designated Sample No. G1, terephthaloyl chlo-ride is employed instead of 4,4'-biphenyldicarboxylic acid chloride.
-The properties determined for Samples No. 1and C1 are set forth in Table I. As can be seen ~rom these results, the compositions according to the present invention exhibit improvements in Tg, Notched Izod, ten-sile properties, hydrolytic stability and solvent resistance when compared to comparative compositions.
;:

, ' 36,665-F -15-- . ': ~ . .
.' ' ' - 2 ~ 1 6 TABLE I

Sample No. 1 C1*
IV, dL/g 0.72 0.68 Tg, C ~ 204 186 N. I~od, ft-lb/in (J/m) 6~7 5.0 (357.8) (267.0) TY, psi (MPa~ 9,219 9,042 (63.56) (62.34) EY, % 10.0 8.6 PYSD, (%) 4.8 8.1 TM, 105 psl MPa 3.3 3.3 (2,275.27) (2,275.27) Weight Loss in 10N NaOH, %, 500 hr 3.4 13.7 Critical Strain, Isopropanol, % 3.0 Z.O
SG 1.20 1.20 *Not an example of the invention Example 2 To further describe the scope of this inven-tion, additional bisphenol A/4,4'-biphenyldicarboxylate copolyestercarbonate polymers having diester:carbonate molar ratios from 0.06:1 to 10:1 are prepared according to the general procedure of Example 1. These results are.recorded in Table II.

The molecular weight of the resulting polymer is observed through the inherent viscosities (IV).
Higher inherent viscosity values indicate polymer with greater molecular weight. Examples 2 to 11 are prepared so as to have the inherent viscosities as reported in Table II.

36,665-F -16-, : , .: . . .

204~416 In Samples 4 and 5, and Examples 6 and 7, the difl~r~ t inherar,t vL3co~i~ies are obtained by using different quantities of p-tertiary-butylphenol. Smaller quantities provide for higher molecular weights as evidenced by greater inherent viscosities.

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_1 9 Example 3 To furtner describe ths utility of this inven-tion, bisphenol A/4,4'-biphenyldicarboxylate (BP) co-polyestercarbonate polymers are exposed to UV radiation, as shown in Table III (Sample Nos. 1, 4, 12). For comparison, bisphenol A/terephthalate (T) copoly-estercarbonate polymers are also exposed (Sample Nos.
C1-C3). Sample Nos. 12, C2 and C3 are prepared accord-ing to the general procedure of Example 1. As evidenced by the resulting change in YI ~YI), the compositions of the present invention exhibit a significant reduction in yellowing following UV exposure.

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Example 4 To fur~her describe the scope of this invan-tion, additional copolyestercarbonate polymers are pre~
pared according to the general procedure of Example 1.
Diols utilized for the compositions of this example include bisphenol A (BA); 2,2-bis(4-hydroxy-3,5-dichlo-rophenyl)propane (TCBA); 2,2-bis~4-hydroxy-3,5-dibromo-phenyl)propane (TBBA); 4~4'-dihydroxybiphenyl (DHB);
4,4'-thiodiphenol (TDP); 1,1-bis(4-hydroxyphenyl)-1-tO -phenylethane (also known as bisphenol AP, BAP); and 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-4,4'-dihy-droxybiphenyl (TTDHB). Esters utilized include 4,4'--biphenyldicarboxylate (BP), terephthalate (T), and isophthalate (I). The results for these compositions are set forth in Table IV (Sample Nos. 13 22).

.

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204~6 Example 5 To further describe the scope o~ this inven-tion, this example describe~ the preparation of a ther-moplastic polymer blend of bisphenol A polycarbonate resin and a copolyestercarbonate polymer resin of the present invention.

Bisphenol A/4~4'-biphenyldicarboxylate copoly-estercarbonate polymer (87.6 g~ prepared according to the general procedure of Example 1 and having I~ - 0.56 dL/g and a diester:carbonate ratio of 1.0:1) is mixed with a bisphenol A polycarbonate polymer (32.4 g, IV =
0.53 dL/g) in one liter of methylene chloride. The blend is then isolated by precipitation using hex-_ ane/acetone and an explosion-resistant blender. The precipitated product is dried in a vacuum oven and then compression molded. The following results are obtained for the molded blend composition: notched izod = 7.7 ft-lb/in (411.2 J/m); TY - 9,261 psi (63.85 MPa); EY -8.8 psrcent; PYSD - 9.0 percent; and TM = 300,000 psi (2,068.43 MPa).

Example 6 An additional advantage of the composition of this invention is resistance to crystallization during the solvent-casting of films. The preparation of films of bisphenol A polycarbonates in a thickness of at least 3 0.005 ~0.127 mm) inch by solvent-casting from a methylene chloride solution results in crystalline films, as evidenced by opacity and a melting transition (differential scanning calorimetry analysis). Non--crystalline films of comparative bisphenol A/terephthalate copolyestercarbonate polymers can be 3h,665-F -23-2 ~ 1 6 -~4-prepared when the diester:carbonate ratio is in the range of 0.05 to 1.5. In contrast, the corre~ponding die3tee~:c~rbonate r~nge for non-cey~taiiirle fil[n prepa-ration is from 0.05 to 10.0 for the bisphenol A/biphenyldicarboxylate copolyestercarbonate polymers of this invention.

;~

36,665-F -24-:
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~ .

Claims (10)

1. A copolyestercarbonate polymer prepared by contacting a dihydroxy compound with a dicarboxylic acid compound and a carbonate precursor characterized in that (a) at least 50 mole percent of the dicarboxylic acid compound employed consists of a diaryl dicarboxylic acid compound containing two or more aromatic rings which are connected together by a positionally and angularly well defined rigid internal linking group, and (b) the mole ratio of dicarboxylic acid compounds to carbonate precursor is such that the polymer has molar ratio of diester:carbonate groups from 0.02:1 to 20:1.

2. The polymer of Claim 1 wherein the dicarboxylic acid compound is one or more selected from the group consisting of 4,4'-biphenyldicarboxylic acid,

3,4'-biphenyidicarboxylic acid, 4,4'-biphenyldicarbox-ylic acid chloride and 3,4'-biphenyldicarboxylic acid chloride.
3. The polymer of Claim 1 wherein the internal rigid linking group is selected from the group consisting of a covalent bond, a cycloaliphatic or 36,665-F -25-heterocyclic ring, -C=C-, -C?C-, -COO-, -NHCO-, -NHCOO-, -C=N-, -C=C=C-, , , , and -N=C=N-.

4. The polymer of Claim 1 wherein the diaryl dihydroxy compound is one or more diaryl dihydroxy compounds selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 4,4'-dihydroxybiphenyl and bis(4-hydroxyphenyl)sulfide.

5. The polymer of Claim 1 wherein the molar ratio of diester groups:carbonate groups is from 0.05:1 to 15:1.

6. The polymer of Claim 5 wherein the molar ratio of diester groups:carbonate groups is from 0.06:1 to 10:1.

7. The polymer of Claim 1 wherein the carbon-ate precursor is phosgene.

8. The polymer of Claim 1 wherein the dihy-droxy compound is a bisphenol, the diaryl dicarboxylic acid compound is a biphenyldicarboxylic acid and/or biphenyldicarboxylic acid chloride and the carbonate precursor is phosgene.

9. A thermoplastic polymer blend comprising a thermoplastic polymer and a copolyestercarbonate polymer 36,665-F -26-of any of Claims 1 to 8 characterized in that the polymer blend contains at least 0.5 weight percent of the said copolyestercarbonate by total weight of thermoplastic polymer and copolyestercarbonate polymer present.

10. The thermoplastic polymer blend of Claim 9 wherein the copolyestercarbonate polymer is prepared from a dihydroxy compound which is a bisphenol A, a diaryl dicarboxylic acid compound which is a biphenyl-dicarboxylic acid and/or biphenyldicarboxylic acid chloride and a carbonate precursor which is phosgene.

36,665-F -27-