CA1152691A - Copolyester carbonate compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Copolyester-carbonates are obtained employing different chain stoppers and the polyester portions thereof can be comprised of diacid chloride copolymers.
This combination yields copolyester-carbonates having physical properties which permits them to be used in a broad range of applications.

Description

~ 6g 1 8CL-2860 This invention relates to copolyester-carbonate compositions containing different types of chain stoppers.
Copolyester-carbonates and the methods for preparing them are known such as disclosed in U.S. Patent No.
3,030,331 - Goldberg - April 17, 1962, U.S. Patent No.
3,169,121 - Goldberg - February 9, 1965 and U.S. Patent No.
3,207,814 - Goldberg - September 21, 1965. In addition, U.S. Patent No. 4,097,457 - Sakai et al - June 27, 1978 discloses the use of various molecular weight regulators (also referred to as "chain stoppers" and "end cappers") to obtain high molecular weight aromatic polycarbonates by means of an improved process. Further, U.S. Patent No. 3,697,481 -Bialous - October 10, 1972 discloses the use of chroman as a chain stopper for high molecular weight aromatic polycarbonates.
The use of copolyester-carbonates is desirable as such resins are generally easier to process and result in an economic savings in both manufacturing and materials cost.
However, the use of such resins is limited as they do not generally exhibit the highly desirable physical properties of high molecular weight aromatic polycarbonates.
It has now been found that copolyester-carbonates can be obtained whose physical properties permit them to be used in a broader scope of applications. This is accomplished by employing different chain stoppers in their production as well as employing such chain stoppers at varying concentrations.
In general, the copolyester-carbonate compositions of the inyention can be represented by the general formula C ~ ~ - B ) ( A ) C

wherein the - ~ A - B-t-- block represents the polyester moeity where B is bonded only to A and the ( A ) block ~`

represents the polycarbonate moeity. Thus, in the foregoing general formula A can be a dih~dric phenol, a phenolic copolymer and mixtures thereof, B is a member selected from the group consisting of diacid chlorides and mixtures thereof; C is a member selected from the group consisting of chroman-I, p-cumylphenol, 7-hydroxy-4-methyl-coumarin, p-phenylphenol, p-tritylphenol, and mixtures thereof; m and n are integers of about 1 to 2,000.
These copolyester-carbonates can be prepared by well known processes such as by interfacial polymerization or phase boundry separation, interesterification, and the like. These processes typically include dissolving the reactants in a suitable solvent medium under controlled pH
conditions and in the presence of a suitable catalyst and acid acceptor and then contacting these reactants with a carbonate precursor. A molecular weight regulator; i.e., chain stopper, is generally added to the reactants prior to contacting them with a carbonate precursor.
The dihydric phenols that can be employed in the practice of this invention are bisphenols such as bis (4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxy-3, 5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3, 5-dibromophenyl)propane, etc.; dihydric phenol ethers such as bis(4-hydroxyphenyl)ether, bis(3,5-dichloro-4-hydroxyphenyl)ether, etc.;dihydroxydiphenyls such as p, p'-dihydroxydiphenyl, 3,3'-dichloro-4, 4-dihydroxydiphenyl, etc.; dihydroxyaryl sulfones such as bis(4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, etc.;
dihydroxy benzenes, resorcinol, hydroquinone, halo- and alkyl-substituted dihydroxy benzenes such as 1,4-dihydroxy-2, ~ ~ ~2 ~91 5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, etc.;
and dihydroxy diphenyl sulfoxides such as bis(4-hydroxyphenyl) sulfoxide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, etc.
A variety of additional dihydric phenols are also a~ailable such as are disclosed in U.S. Patent No. 2,999,835 -Goldberg - September 12, 1961, U.S. Patent No. 3,028,365 -Schnell et al - April 3, 1962, and U.S. Patent No.
3,153,008 - Fox - October 13, 1964. Also suitable are copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis (3,5-dibromo-4-hydroxy-phenyl)propane, etc. It is also possible to employ two or more different dihydric phenols or a copolymer of a dihydric phenol with a glycol or with hydroxy or acid terminated polyester, or with a dibasic acid as well as blends of any of the above materials.
The acid dichlorides that can be employed are both the aromatic and the saturated aliphatic dibasic acids. The saturated, aliphatic dibasic acids which are derived from straight chain paraffin hydrocarbons, such as oxalic, malonic, dimethyl malonic, succinic, glutaric, adipic, pimelic, suberic, azelic and sebacic acid and the halogen-substituted aliphatic dibasic acids. Aliphatic carboxylic acids containing hereto atoms in their aliphatic chain, such as thio-diglycollic or diglycollic acid can also be used as well as unsaturated acids such as maleic or fumaric.
Suitable examples of aromatic and aliphatic aromatic dicarboxylic acids which can be used are phthalic, isophthalic, terephthalic, homophthalic, o-, m-, and p-phenyl-enerdiacetic acid; the polynuclea~ aromatic acids such as diphenic acid, and 1~4~naphthalic acid. Preferred acid dichlorides are isophthaloyl dichloride (IPC12), and `~ 8CL 2860

2 ~ j 9 1 terephthaloyl dichloride (TPC12) as well as mixtures thereof.
These diacid chlorides can also be reacted with bisphenol-A, hereinafter referred to as "BPA", such as is disclosed in U.S. Patent No. 4,238,597 issued December 9, 1980 assigned to the same assignee as this case. The diacid chloride/BPA
copolymers can then be employed for the polycarbonate portion of the copolyester-carbonate of the invention.
It is preferred that the molar ratio of the diacid chloride to the dihydric phenol range from 10:90 to 45:55.
The acid acceptor employed can be either an organic or an inorganic acid acceptor. A suitable organic acid acceptor is a tertiary amine and includes such materials as pyridine, triethylamine, dimethylaniline, tributylamine, etc. The inorganic acid acceptor can be one which can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
The carbonate precursor employed can be either a carbonyl halide, a carbonate ester or a haloformate. The carbonyl halides which can be employed are carbonyl bromide, carbonyl chloride and mixtures thereof. Typical of the carbonate esters that can be employed are diphenyl carbonate, di-(halophenyl) carbonates such as di-(chlorophenyl) carbonate, di-(bromophenyl) carbonate, di-(tri-chlorophenyl) carbonate, di-(tribromophenyl) carbonate, etc., di-(alkylphenyl) carbonate such as di(tolyl) carbonate, etc., di-(naphthyl) carbonate, di-(chloronaphthyl) carbonate, phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, etc., or mixtures thereof. The halo-formates suitable for use herein include bishaloformates of dihydric phenols (bischloroformates of hydroquinone, etc.) or glycols (bishaloformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). While other carbonate ~;''~~

11~i;2~i91 precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred.
Also included are the polymeric derivatives of a dihydric phenol, a dicarboxylic acid and carbonic acid.
These are disclosed in U.S. Patent No. 3,169,121 - Goldberg -February 9, 1965.
The catalysts which can be employed can be any of the suitable catalysts that aid the polymerization of the bisphenol-A and the acid dichloride with phosgene. Suitable catalysts include tertiary amines such as triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammonium compounds such as tetraethylammonium bromide, cetyl triethylammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propylammonium bromide, tetramethylammonium chloride, tetramethylammonium chloride and quaternary phosphonium compounds such as n-butyl-triphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.
The solvent system employed is one in which the reactants can be accepted but which is inert with respect to the reactants. For example, an aqueous organic solvent system can be employed wherein the organic member can readily accept the reactants, but be inert to them.
Exemplary of such organic members are methylene chloride, chlorobenzene, cyclohexanone, carbon tetrachloride, and the like. Preferably, the organic portion of the solvent system is methylene chloride.
Also included herein are branched copolyester-carbonates wherein a polyfunctional aromatic compound is reacted with the dihydric phenol, the carbonate precursor and the acid dichloride to provide a thermoplastic randomly branched copolyester-carbonate. These polyfunctional aromatic compounds contain at least three functional groups ~ 69~ 8CL-2860 which are carboxyl, carboxylic anhydride, halo-formyl or mixtures thereof. Examples of these polyfunctional aromatic compounds include trimellitic anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic anhydride, and the like. Preferred polyfunctional aromatic compounds are trimellitic anhydride or trimellitic acid, or their haloformyl derivatives.
Also included herein are blends of a linear and a branched copolyester-carbonate.
According to the invention, modified copolyester-carbonates can be produced to exhibit one or more desired properties by varying the type and amount of chain stopper employed. For example, copolyester-carbonates having improved heat distortion temperatures, improved tensile strength, and the like, can be readily obtained and yet the overall physical properties of these copolymers are about equivalent to those of a typical high molecular weight aromatic polycarbonate.
The chain stoppers that can be employed in the practice of this invention can be represented by the following formulae:
(I) R7~ R

R8 R ~-- R6 (Chromanyl) ~ ~2691 8CL 2860 wherein Rl, R2 and R4 are CH3; and, R3 and R5-R8 are H.
(II) CH3 ¦ ~ OH

(p-Cumylphenol) (III) C ~ C ~ _ OH

(p-Tritylphenol) 10 ~IV~ HO ~ O

(7-Hydroxy-4-methyl-coumarin) (V) ~ OH

(p-Phenylphenol) Of the foregoing chain stoppers, chroman-I of the chromanyl group is preferred and it has the following structure:

20 (VI) ~ ~ CH3 OH
(Chroman-I) Fillers may be employed in compositions of the present invention, preferably in amounts ranging from about 2-30% by weight of the composition.
Details of the invention will become more apparent from a consideration of the following examples which are set forth to illustrate the best mode currently known to practice the invention. In the examples parts and percentages are by weight unless otherwise stated.

~2691 Obtaining Chroman-I Concentrate Approximately 500 gm unpurified BPA by-products were collected from a BPA manufacturing facility. The BPA
by-products were kept in a molten state at about 130 C
using electrical heating tape.
To a 4-necked round bottom flask equipped with a mechanical stirrer, water cooled condenser, dropping funnel and heated with electrical tape there was added 500 gm of methylene chloride. 500 gm of the molten by-products were poured into the dropping funnel and the temperature maintained at 130C. To the well stirred methylene chloride solution there was added the molten by-products and the rate of addition controlled the methylene chloride reflux rate. The temperature of the solvent was 40 C and had a dark color. After addition of about half of the molten by-products, yellow colored crystals formed in the solution. (With higher ratios of methylene chloride to crude by-products, the solids can be dissolved in methylene chloride solution at 40 C, and upon cooling, the BPA-Chroman-IPP dimmer crystallizes from the methylene chloride mixture.) After complete addition of the by-products, the thick yellow mixture was cooled and filtered. The filter cake was washed with fresh methylene chloride to afford a white solid.
The whit~ chroman-I concentrate filter cake was dried at 100C for 24 hours. The yields averaged about 96 to 150 gm ~20 to 30~ based on crude by-productl.
The chroman-I concentrate obtained was analyzed using liquid chromatography and compared with the BPA
by-products which were analyzed in the same way. The results are shown in Table I below:

TABLE I

Liquid Chromatograph Analyses of BPA By-Pxoducts and Chroman-I Concentrate BPA By-Products Chroman-I
tWt~ %)Concentrate (Wt.
Com~onent -BPA 41.7 75.5 ,p-BpA 13.0 1.1 Cyclic IPP Dimer11.7 8.8 Chroman-I 7.1 13.5 BPX-I 1.6 0.1 IPP 1.0 ---Spiro Bi-indane 0.5 ---Phenol 1.6 ---Uncalibrated Components 21.8 1.0 From Table I above, it can be seen that the chroman-I component was increased almost 100%, the BPA
was increased over 50% and the cyclic IPP dimer was decreased about 25% while the remaining components were almost completely eliminated.

Polymerization of Polyester-Carbonate Using Chroman-I Concentrate as Chain Stopper To a ten gallon reactor vessel there was added 2112 g of BPA, 916 g of chroman-I concentrate (from Example 1) in 4 liters of methylene chloride, 8 liters of water, 5.5 liters of methylene chloride, 21 ml of triethylamine, 5.1 g of sodium gluconate. At pH 9-10, 457 g of isophthaloyl dichloride in 1 liter of methylene chloride was added over a 5 min. interval while controlling the pH with 35% aqueous caUstic. The pH was lowered to 5-6 with phosgene and phosgene was deli~ered at 36 g/min. for an additional 5 min.
The pH was then adjusted to 11 and phosgenation continued at 36 g/min. for 40 min. while controlling the pH with 35%

_ g _ ~ 691 8CL-2860 aqueous caustic. The solution was diluted with 7 liters of methylene chloride, and the phases separated. The methylene chloride-polymer phase was washed with O.OlN
HCl, and 3 times with water (standard work-up procedure).
The resin was precipitated with high pressure steam to yield a white powder which was dried in a nitrogen purged fluid bed dryer. The blended copolyester-carbonate resin obtained had an IV in methylene chloride at 25C of 0.48 dl/g.
The resin was stabilized with standard stabilizing amounts of a phosphite and an epoxide as disclosed in German Patent 1,694,285. This resin product was then fed to an extruder operating at a temperature of about 550F to extrude the resin into strands and the extruded strands were chopped into pellets. The pellets were then injection molded at about 600F into test samples measuring about 3" x 2" x 1/8".

The same procedure was followed as in Examp'e 2 except that phenol was employed as chain stopper in place of the chroman-I concentrate.

Various physical properties of the test samples obtained in Examples 2 and 3 were determined according to the following test procedures:
Heat distortion temperature under load ~DTUL) of the molded samples, with and without a commercial glass filler, was determined according to ASTM D-648. The molded samples containing the glass filler were obtained in the same manner as described abo~e except that the glass filler in an amount of 9% by weight of the copolymer resin was mixed with the copolymer resin powder by tumbling the ingredients together in a laboratory tumbler prior to ~SZ691 extruding the mixture.
Yellowness Index (YI) was determined according to ASTM D-1925 on samples molded at 600 F;
Notched Izod (NIl and Unnotched Izod ~UNI1 impact on the 1/8 n thick molded samples were determined according to ASTM D-256;
Flexural Yield (FY) and Flexural Modulus (FM) were determined according to AST~ D-790;
Tensile Yield (TY), Tensile Break (TB) and Tensile Elongation (TE) were determined according to ASTM D-638; and, Melt Index (MI) was determined according to modified ASTM D-1238.
The results obtained are set forth in TABLE II
below wherein "CR-I" identifies the chroman concentrate and "PHL" identifies phenol.

~2691 d~
~ o ~ o r 3 "~ u~ o o O ~ O 1~ ~ ~ ~ ~ cn o :~ ~ ~ ~ o ~ ~
~ d~ ~ u~

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o u~ ~

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U _ E~ h 1~ i D :~

~2691 8CL-2860 The results in Table II above indicate that the physical properties of a copolyester-carbonate chain stopped with chroman-I concentrate are about comparable to that of a copolyester-carbonate chain stopped with phenol but usin~ half the diacid chloride concentration in the chroman-I chain stopped copolyester-carbonates.

Polymerization of Copolyester-Carbonate Employing Diacid Chloride-BPA Copolymer and Chain Stopped with Chroman-I Concentrate To a ten gallon reactor vessel was added 1938 g (8.5 moles) of BPA, 7 liters of methylene chloride, 5.5 1 of water, 14 ml (1 mole %) of triethylamine, 3.4 g of sodium gluconate and 80 g (3.0 mole %) of a commercially obtained chroman-I (92% chroman). At pH 9-10, 304 g (1.5 moles) of isophthaloyl dichloride (IPC12) in one liter of methylene chloride was added over a 3 minute period while controlling the pH with 35% aqueous caustic. The pH was lowered to 5-6, and then phosgene was delivered at 36 g/min. for 5 minutes.
The pH was adjusted to 11 and phosgenation continued at 36 g/min. for 22 minutes while controlling the pH at 11 with 35% aqueous caustic. The solution was diluted with 5 liters of methylene chloride followed by the standard work-up procedure to afford a white powder. The resin was stabilized as in Example 2 above. Test samples of this resin were obtained as described in Example 2 and their physical properties were compared with those of the copolyester-carbonate of Example 3 wherein phenol (PHL) was employed as the chain stopper. The results are shown in Table III below wherein the commercially obtained chroman stopper is identified as "C~CR-I".

~ ~;2691 Ut _ ~ o ,, dP ~ ,, o~3 I .
~:1 1~ ~1 1 o ~: o ~a ~ ~ I I
O N O
N
O I I
I~ i l O ~ CO
_ _ N ~r ~Q

h O $ 1~
U Q H
h ~ u-) 3 l a) ~ ~ 0~ ~
. ci~ t~ ~ N
l h IS~ ~ O
~ I $ ~1 ~ ~ ~ I I
0 æ ~
~1 Ei >1 H O O O ~
~t g O 1~ ~ O
o Q ~ ~ a~
o U~ ~ o~
H ~.) __ N
.~ ~o n ~ rC d~
O ~ u~ ~ O CO
~ 1 ~q 3 ~o~ i~l In ~
S ~ ~ N
4~ ~L
0~ O O O
OU~ o O Ul ~ ~ ~ ~
u 1~

h O

U .. s~ '~
~ 5~ 0~ ~ ~
dP ~ ~ _ ~

S S E~ H H ~H

i2691 The results in Table II above reveal that about the sa~e physical properties can be obtained when chroman-I
is used as a chain stopper in pIace of phenol, but that less polyester is needed when chroman-I is employed than when phenol is employed.
EXAMPLES 6-lQ
Following the procedure of Example 5, additional copolyester-carbonates were prepared using other diacid chlorides at ~arying molar ratios for the diacid chloride-BPA
copolymer portion and employing other chain stoppers at mole % concentrations based upon BPA. Test samples of these copolyester-carbonates and that of Example 5 were molded as described in Example 2 and their physical properties - determined as described in Example 4. The results are shown in Table IV wherein "IPC12" identifies isophthaloyl dichloride, "TPC12" identifies terephthaloyl dichloride, "PCP"
identifies p-cumylphenol, and "IV" denotes the intrinsic ~iscosity of the resin in methylene chloride at 25C.
_ _ ~Z691 a~
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a c~-- H H HE~ E~ l H H H E~E-l E-l ~1 o 3 ~n a~ u~

X ~ O -~ In ~D1` 00 ~ O
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Z~91 The results in Table IV reveal that there is little difference in the physical properties of the copolyester-carbonates without glass. When glass is added, however, heat distortion temperatures (~TUL) generally increase and Notched Izod (NI) values generally decrease.
In additional tests employing a molar ratio of terephthaloyl dichloride (TPC12): BPA of 10:90 to obtain the TPC12/BPA copolymer portion of the copolyester-carbonate and using the commerciallly obtained chroman-I as the chain stopper, a DTUL of 302F at 264 psi was obtained. In the same copolyester-carbonate, replacing phenol with p-cumylphenol as the chain stopper raised the DTUL 1-2F, but when phenol was replaced with the commercially obtained chroman-I as the chain stopper, the DTUL was increased 5-7F.

-The same procedures were followed as in Examples 5-10 to obtain additional sa~.ples of copolyester-carbonates which were filled with different types of commercially obtained glass fillers at varying concentrations as well as with a particulate,solid spherical filler commercially available under the trademark SPEREFIL 10, am anhydrous calcium sulfate fiber (ACSF), and a mica commercially available under the trademark "Suzerite ~lica 200 MP" (Suzerite). The copolyester-carbonate resins were prepared from an isophthaloyl dichloride (IPC12) /BPA copolymer wherein the mole percent of IPC12/BPA was 30:70. The commercial glass fillers employed were a non-bonding glass (NBG), a bonding glass fiber (BGF), and glass beads (GB). The physical properties of the tes;t samples obta~n~d from these resins are listed in Table V below.

- ~7 -~ 691 8CL-2860 TABLE V

Physical Properties of Copol~ester-Carbonates _ Containing Commercial Fillers Type of Filler DTUL @ 264 psi UNI
Filler ~t % ~ F) (ft-lb~sl MI
NBG 290 40 3.80 Spherefil 10 10 281 40 4.08 Suzerite 15 309 9 ---~
The results of Table V above indicate that commercial type fillers can be included in the copolyester-carbonate compositions of the invention at typical concentrations to generally enhance their DTUL property without deleteriously affecting their impact property.

To 95 parts of a commercially obtained aromatic polycarbonate having an intrinsic viscosity of about 0.51 dl/g there was added 5 parts glass fibers (BGF, Example 11) and standard amounts of the stabilizers of Example 2. This well blended mixture was then fed to an extruder operating at a temperature of about 550F to extrude the resin into strands which were then chopped into pellets as in Example 2. To 95 parts of the pellets there was added 5 parts of a chemical blowing agent as disclosed in U.S. Patent No. 4,097,425 -Niznik - filed June 27, 1978 and this pellet-blowing agent mixture was then foam molded at molding temperatures of about 550-600 F to obtain foamed test samples measuring about

3" x 2" x 1/8".

~l5Z69~
EXAMPLE~ 13-15 The same procedures were followed as in Example 12 except that copolyester-carbonates were emplo~ed using different chain stoppers in place of the commercial polycarbonate. The ph~sical properties of the samples obtained from these examples were determined as in Example 4 above and the results obtained are shown in Table VI below.

269~

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a~~ .,~ x d~ X X , ~ --Hf~ ~ ~ `1 H
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~2691 8CL-2860 The results in Table VI reveal that the physical properties of copolyester-carbonates are generally better than those of polycarbonate and that the chroman-I chain stopped copolyester-carbonate of the invention at a lower diacid chloride concentration is comparable to phenol chain stopped copolyester-carbonates.

Claims (25)

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

1. A copolyester-carbonate composition represented by the general formula wherein A can be a dihydric phenol, a phenolic copolymer, and mixtures thereof; B is a member selected from the group consisting of diacid chlorides and mixtures thereof; C is a member selected from the group consisting of chroman-I, p-cumylphenol, 7-hydroxy-4-methyl-coumarin, p-phenylphenol, p-tritylphenol, and mixtures thereof; and, m and n are integers of about 1-2,000.

2. The composition of claim 1 wherein said dihydric phenol is bisphenol-A.

3. The composition of claim 1 wherein said phenolic copolymer is the reaction product of a diacid chloride and a dihydric phenol.

4. The composition of claim 3 wherein said diacid chloride is a member selected from the group consisting of aromatic dibasic acids and saturated aliphatic dibasic acids.

5. The composition of claim 4 wherein said diacid chloride is isophthaloyl dichloride.

6. The composition of claim 4 wherein said diacid chloride is terephthaloyl dichloride.

7. The composition of claim 3 wherein said dihydric phenol is bisphenol-A.

8. The composition of claim 3 wherein the molar ratio of said diacid chloride to said dihydric phenol is in the range of about 10:90 - 45:55.

9. The composition of claim 8 wherein said molar ratio is in the range of ahout 15:85 - 40:60.

10. The composition of claim 1 which includes an inert filler in an amount of about 2-30% by weight of said composition.

11. The composition of claim 10 wherein said inert filler is a member selected from the group consisting of non-bonding glass, bonding glass fibers, glass beads, particulate solid spherical fillers, anhydrous calcium sulfate fibers, mica, and mixtures thereof.

12. The composition of claim 10 wherein C is phenol.

13. A foamed article obtained from a thermoplastic copolyester-carbonate composition represented by the general formula wherein A can be a dihydric phenol, a phenolic copolymer, and mixtures thereof; B is a member selected from the group consisting of diacid chlorides and mixtures thereof; C is a member selected from the group consisting of chroman-I, p-cumylphenol, 7-hydroxy-4-methyl-coumarin, p-phenylphenol, p-tritylphenol, and mixtures thereof; and, m and n are integers of about 1-2,000.

14. The composition of claim 13 wherein said dihydric phenol is bisphenol-A.

15. The composition of claim 13 wherein said phenolic copolymer is the reaction product of a diacid chloride and a dihydric phenol.

16. The composition of claim 15 wherein said diacid chloride is a member selected from the group consisting of aromatic dibasic acids and saturated aliphatic dibasic acids.

17. The composition of claim 16 wherein said diacid chloride is isophthaloyl dichloride.

18. The composition of claim 16 wherein said diacid chloride is terephthaloyl dichloride.

19. The composition of claim 15 wherein said dihydric phenol is bisphenol-A.

20. The composition of claim 15 wherein the molar ratio of said diacid chloride to said dihydric phenol is in the range of about 10:90 - 45:55.

21. The composition of claim 20 wherein said molar ratio is in the range of about 15:85 - 40:60.

22. The composition of claim 13 wherein C is phenol.

23. The composition of claim 13 which includes an inert filler in an amount of about 2-30% by weight of said composition.

24. The composition of claim 23 wherein said inert filler is a member selected from the group consisting of non-bonding glass, bonding glass fibers, glass beads, particulate solid spherical fillers, anhydrous calcium sulfate fibers, mica, amd mixtures thereof.

25. The composition of claim 23 wherein C is phenol.