JPH0532772A - Copolyester carbonate derived from diaryldicarboxylic acid and derivative thereof and blend thereof - Google Patents

Abstract

PURPOSE: To provide copolyester carbonate constituted by reacting a dihydroxy compd. with a dicarboxylic acid compd. and a carbonate precursor in a specific ratio and improved in impact strength and glass transition temp. and low in ultraviolet sensitivity.

CONSTITUTION: A copolyester carbonate polymer is obtained by bringing a dihydroxy compd. into contact with a dicarboxylic compd. and a carbonate precursor and 50 mol% or more of the dicarboxylic acid compd. to be used is composed of a diaryldicarboxylic compd. containing two or more aromatic rings mutually connected by a positionally and angularly rigid internal bonding group and a molar ratio of the dicarboxylic acid compd. and the carbonate precursor is set so that the molar ratio of diester: carbonate groups of the above mentioned polymer becomes (0.02:1)-(20:1).

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to copolyestercarbonate polymers, resins and blends thereof, and more particularly to copolyestercarbonate polymers prepared from diaryldicarboxylic acid compounds.

[0002]

BACKGROUND OF THE INVENTION A wide variety of polycarbonate and copolyestercarbonate resins are known and are used as thermoplastics for various molded articles and components. Known resins also have a wide variety of physical properties, but more diverse physical properties are still required.

[0003]

In some recent applications, physical properties including improvement / improvement of tensile strength, impact resistance, hydrolysis resistance, solvent resistance and reduction of sensitivity to UV rays have been investigated. There is a desire to provide improved copolyestercarbonates.

Copolyestercarbonate resins are typically prepared by reacting a dihydroxy compound with a dicarboxylic acid compound and a carbonate precursor. The most widely used dicarboxylic acid compounds are terephthalic acid and isophthalic acid compounds.

By the way, it has been found that the use of another type of dicarboxylic acid compound brings about a desirable improvement in the physical properties of the copolyestercarbonate polymer resin.

[0006]

One feature of the present invention is a copolyestercarbonate polymer prepared by contacting a dihydroxy compound with a dicarboxylic acid compound and a polycarbonate precursor, wherein (a) the dicarboxylic acid compound used. 50 mole percent or more consists of a diaryldicarboxylic acid compound containing two or more aromatic rings that are linked to each other by a positional and angular well-defined rigid internal linking group, and (b) The molar ratio of dicarboxylic acid compound to carbonate precursor is such that the molar ratio of diester: carbonate groups of the polymer is 0.01: 1 to 2
It is a copolyestercarbonate polymer having a molar ratio of 0: 1.

Another feature of the present invention is a thermoplastic polymer blend comprising a thermoplastic polymer and a copolyestercarbonate polymer, wherein a dihydroxy compound is contacted with a dicarboxylic acid compound and a carbonate precursor to prepare the copolyestercarbonate polymer. However, (a) 50% by mole or more of the dicarboxylic acid used is diaryldicarboxylic acid containing two or more aromatic rings which are bonded to each other by a rigid internal bonding group which is defined positionally and angularly. (B) the molar ratio of the dicarboxylic acid compound to the carbonate precursor is such that the molar ratio of the diester: carbonate groups of the polymer is 0.02: 1 to 20: 1.
And (c) the polymer blend contains 0.5 weight percent or more of the copolyestercarbonate based on the total weight of thermoplastic polymer and copolyester polymer present. Is a thermoplastic polymer blend.

It has been surprisingly found that the polymers of the present invention exhibit improved properties including impact strength, gas transfer temperature and reduced UV sensitivity. Even more surprising is the finding that the polymers of the present invention can be used, for example, in the preparation of films to provide greater film thickness than other prior art polymers without the problem of increased crystallinity. Was obtained.

As mentioned above, the present invention relates to copolyestercarbonate polymers prepared by contacting a dihydroxy compound with a dicarboxylic acid and a carbonate precursor. This polymer has a molar ratio of the dicarboxylic acid compound and the carbonate precursor to the dihydroxy compound,
The resulting polymer has a diester: carbonate group molar ratio of 0.02: 1 to 20: 1, preferably 0.05: 1 to 15:
1, more preferably 0.06: 1 to 10: 1. The optimum ratio of diester groups to carbonate groups in the copolyestercarbonate polymer is related to the intended use of the polymer and must be determined by trial and error. The diester group is derived from the reaction between the dihydroxy compound and the dicarboxylic acid compound, and the carbonate group is derived from the reaction between the dihydroxy compound and the carbonate precursor.

The polymer has a positionally and angularly about not less than about 50 mol%, preferably not less than about 70 mol%, more preferably not less than about 85 mol% of the total amount of the dicarboxylic acid compound used for preparing the polymer. A further feature is a diaryldicarboxylic acid compound containing two aromatic rings that are linked together by a well-defined rigid internal linking group.

This rigid internal linking group makes the diaryldicarboxylic acid compound in rod form. Examples of such rigid internal linking groups are covalent bonds, alicyclic rings or heterocycles (provided that the aryl group of the dicarboxylic acid is related to the same atomic center of the ring), -C = C-, -C. ≡ C-, -COO
-, -NHCO-, -NHCOO-, -C = N-,

[0012] The preferred rigid internal linking groups for the copolyestercarbonate polymers of the present invention are covalent bonds.

The diarylcarboxylic acid compound is a dicarboxylic acid, a dicarboxylic acid chloride or a mixture thereof.
Each aryl ring is substituted with one or more carboxylic acid groups or carboxylic acid chloride groups. In addition to this, optionally and independently, the arylaromatic ring may be substituted with 1-4 substituents. Examples of the substituent when it is not hydrogen are halogen,
It is a C _1-6 alkyl group, an oxy-C _1-6 alkyl group, an oxy-aryl group, a phenyl group, a benzyl group or a mixture thereof. Substituents when not hydrogen suitable for the present invention are chlorine,
Bromine, a C _1-6 alkyl group, especially methyl. However, it is most preferred when these substituents are not present on the aryl ring.

Examples of diaryldicarboxylic acid compounds suitable for use in the present invention include 4,4'-biphenyldicarboxylic acid, 3,
There are 4'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid chloride, 3,4'-biphenyldicarboxylic acid chloride and mixtures thereof. 4,4'-carboxylic acid and its acid chloride are particularly preferred. The remaining molar fraction of the dicarboxylic acid compound required to prepare the polymer, if any, is determined by one or more suitable dicarboxylic acid or dicarboxylic acid salts well known to those skilled in the art of polyester polymer preparation other than the diaryldicarboxylic acid compounds described above. It can be composed of objects.

Preferred dicarboxylic acid compounds are aliphatic, cycloaliphatic, heterocyclic, aromatic dicarboxylic acid compounds or mixtures thereof. A small amount of hydroxy acid may be used in the preparation of the polymer of the present invention.

Suitable aliphatic dibasic acids are those derived from straight chain paraffin hydrocarbons such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, subaric acid, azelaic acid. And sebacic acid. Also included are halogen-substituted aliphatic dibasic acids. Aliphatic carboxylic acids containing heteroatoms and aliphatic chains can also be used, for example thiodiglycolic acid or diglycolic acid. Unsaturated acids such as maleic acid and fumaric acid are also useful.

Suitable cycloaliphatic dicarboxylic acids include trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid; and alkyls of said cycloaliphatic dicarboxylic acids. There are-, alkoxy- or halogen-substituted derivatives.

Aromatic dicarboxylic acids suitable for use in producing the polymer of the present invention include terephthalic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl ether-4,4'-dicarboxylic acid. Acid, diphenoxyethane-4,
4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, biphenylethane-4,4'-dicarboxylic acid, isophthalic acid, biphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3,3 '-Dicarboxylic acid, biphenylethane-3,3'-
Dicarboxylic acid, naphthalene-1,6-digalvonic acid and 1,5-anthraquinone dicarboxylic acid; and alkyl-, alkoxy- or halogen-substituted derivatives of the aromatic dicarboxylic acid,
Examples are chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid, and ethoxyterephthalic acid.

Examples of hydroxy acids are hydroxyglutaric acid, mandelic acid, various isomers of hydroxybenzoic acid and hydroxybiphenylcarboxylic acid.

The monocarboxylic acid and diacid chloride derivatives of the dicarboxylic acids mentioned above are also suitable for the preparation of the polymers according to the invention. Additional examples of suitable dicarboxylic acid compounds or hydroxycarboxylic acid compounds are described in US Pat. Nos. 3,637,595, 3,975,487 and 4,118,372. When using diaryldicarboxylic acids in combination with other suitable dicarboxylic acids, the aromatic carboxylic acids mentioned above are preferred.

The dihydro compound used to prepare the copolyestercarbonate polymer of the present invention is an aliphatic or alicyclic compound having two hydroxyl groups capable of reacting with a carboxylic acid or acid chloride and a carbonate precursor to form the polymer of the present invention. It is a cyclic, heterocyclic or aromatic dihydroxy compound. It is also possible to produce a copolyestercarbonate polymer by combining one or more of these dihydroxy compounds.

In the present invention, the dihydroxy compound used is greater than about 50 mole percent of the hydroxydiaryl compound, preferably greater than about 70 mole percent, and most preferably
It is preferable to contain 90 to 100 mole percent. This dihydroxydiaryl compound is represented by the following formula.

[0023]

[Chemical 1]

However, in the above formula, A is a divalent hydrocarbon group containing 1 to about 15 carbon atoms, a halogen-substituted divalent hydrocarbon group containing 1 to 15 carbon atoms, and -S-, -O-, -C. = C-, -C
= N =, Selected from the group consisting of divalent groups such as covalent bonds or other rigid linking groups as defined above; each B independently being oxygen, sulfur or -ORO-, where R is a C _1-6 hydrocarbon. Is a divalent group; when X is not hydrogen, halogen, a monovalent hydrocarbon group such as an alkyl group having 1 to 6 carbon atoms, 6 to 18
Independently selected from the group consisting of aryl groups of carbon atoms, oxyalkyl groups of 1 to 6 carbon atoms and oxyaryl groups of 6 to 18 carbon atoms; m is 0 or 1 and y is
It is an integer from 0 to 4.

Some representative examples of dihydroxydiaryl compounds which are advantageous for use are bisphenols such as (4-hydroxyphenyl) methane, 1,1-bis (4-vidroxyphenyl) -1-phenylethane, 2 , 2-Bis (4-hydroxyphenyl) propane (widely known as 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;
Dihydroxyphenyl ethers such as bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether; dihydroxybiphenyls such as 4,4'-hydroxybiphenyl, 3,3'-dichloro- 4,4 '
-Dihydroxybiphenyl, 2,2 ', 6,6'-tetrabromo-3,
3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl;
Dihydroxyaryl sulfones such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; and dihydroxybiphenyl sulfides and sulfoxides such as bis (4-hydroxyphenyl) sulfide and bis ( 4-hydroxyphenyl) sulfoxide; or mixtures thereof.

Suitable dihydroxydiaryl compounds are:
Bisphenol compounds, especially 4,4′-bisphenols (optionally substituted with halogen or C _1-6 hydrocarbon groups) and biphenyl compounds. Examples of such diaryldihydroxy compounds include 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -1-
Phenylethane, 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 (also called 4,4'-thiodiphenol).

The remaining portion of the hydroxy compound required for the reaction for preparing the copolyestercarbonate polymer of the present invention is a dihydroxydiaryl compound different from the above preferred compounds, or one or more aliphatic compounds widely used in the preparation of polyester or polycarbonate polyols. It can be composed of a diol, an alicyclic diol or an aromatic diol.

Suitable diols include linear and branched chain aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol and neopetyl glycol; cycloaliphatic diols such as trans-1,4-cyclohexanediol, cis-. 1,4-cyclohexanediol, trans-1,4-cyclohexanedimethanol, cis-1,4-cyclohexanedimethanol, trans-1,3-cyclohexanedimethanol; and alkyl-, alkoxy- or alicyclic diols thereof. Halogen-substituted derivatives such as trans-1,4-
(1-Methyl) cyclohexanediol and trans-1,4-
It is (1-chloro) cyclohexanediol.

Suitable aromatic diols include hydroquinone,
There are resorcinol, 2,6-naphthalenediol, and 1,6-naphthalenediol. A variety of other aromatic diols are also available, U.S. Pat. Nos. 2,999,835; 3,023.
No. 8,365 and No. 3,153,008.

In addition to aromatic diols, aromatic mercaptophenyls, aromatic hydroxyamines and aromatic diamines can also be used. An example of such a compound is benzene
-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 4-mercaptophenol, 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. Other aromatic hydroxyamines and aromatic diamines are disclosed in US Pat. No. 4,726,998.

The carbonate precursor is either a carbonyl halide, a diaryl carbonate or a bishaloformate. Carbonyl halides include carbonyl bromide, carbonyl chloride and mixtures thereof. Suitable bishaloformates used include bishaloformates of dihydric phenols such as 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl). -Propane, hydroquinone bischloroformate or ethylene glycol such as bishaloformate. While all of the above carbonate precursors are useful, carbonyl chloride (also known as phosgene) is preferred.

The copolyestercarbonate polymer of the present invention can be prepared by various known methods using a solution polymerization method or an interfacial polymerization method, for example, Encyclopedia of Polymer Science an
dTechnology, 1969, Vol. 10, p. 726 and book "Polyeste"
r "(Pergamon Press 1965), page 448, etc. can be obtained by the method described in U.S. Pat. No. 3,1.
69,121; 4,105,633; 4,156,069; 4,19.
No. 4,038; No. 4,238,596; No. 4,238,597; No. 4,252,
No. 939; No. 4,255,556; No. 4,260,731; No. 4,287,78
No. 7; No. 4,330,662; No. 4,355,150; No. 4,360,656
No. 4,369,303; 4,374,973 and 4,388,45
This is the method described in No. 5.

In addition to molding, the polymers of the present invention include conventional molding aids such as antioxidants; antistatic agents; inert fillers such as glass, talc, mica and clay; hydrolysis stabilizers such as US Pat. No. 3,489,716, No. 3,839,247 and No.
Epoxides as disclosed in 4,138,379; color stabilizers such as organic phosphites; heat stabilizers such as phosphites; for preparing thermoplastic molding compositions by incorporating flame retardants and mold release agents. Also used as a substrate. The polymers of the present invention exhibit lower UV sensitivity than that of the prior art, but UV absorbers such as benzophenone and benzotriazole can also be incorporated into this thermoplastic molding composition if desired.

The copolyestercarbonate polymers of the present invention can also be used with other thermoplastic polymers to prepare thermoplastic polymer blends. Suitable thermoplastic polymers for this purpose include thermoplastic polyurethanes, polyesters, polycarbonates, polyalkylenes such as polypropylene and polyethylene, their copolymers and mixtures thereof.

When the copolyestercarbonate polymer of the present invention is used in the preparation of a thermoplastic polymer blend, the blend comprises 0.5% based on the total weight of thermoplastic polymer and copolyester polymer in which the copolyestercarbonate polymer is present. More than weight percent,
Preferably 5 weight percent or more, more preferably 10 to
It is advantageous to include 99 weight percent.

The following examples are presented to further illustrate the present invention as understood by the inventors. However, these examples should not be construed as limiting the scope of the invention in any way. All parts and percentages are by weight unless otherwise stated.

The following tests were conducted to characterize the polymers of the present invention using the test methods indicated. Intrinsic viscosity
(IV) was measured using a concentration of 0.5 g / dL in methylene chloride at 25 ° C. The glass transition temperature (Tg) was measured by a differential scanning calorimeter at a heating rate of 20 ° C / min. Report extrapolated values.

The following tests were performed on compression molded test specimens (thickness 3.2 mm (0.125 inch)) prepared at a temperature 80 to 120 ° C. higher than Tg.
Was performed using. Notched Izod impact resistance is ASTM
The notch radius is 0.254 mm (0.01
Inches). Tensile properties, including tensile modulus (TM), tensile strength at yield (TY), elongation at yield (EY) and stress reduction after yield (SYSD) were measured according to ASTM D-638. PYSD is measured by Polymer, such as Babeck.
Engineering and Science, 24, 1142 (1984). Specific gravity (SG) was measured by ASTM D-792. The hydrolysis resistance was quantified by measuring the weight loss when immersed in a 10N NaOH solution. The critical stress of crazing is Wyzgoski (Wyz
goski), General Motors Research Publication GMR-377
According to the method of 9 (1981), it measured after 30 minutes exposure.

The sensitivity of the polymer to ultraviolet (UV) radiation was quantified by measuring the change in compression molding index (YI) after exposure to a Hanovia 450W medium pressure mercury arc lamp or QUV laboratory. YI was measured according to ASTM D-1925.

[0040]

Example 1 This example illustrates the synthesis of bisphenol A / 4,4'-biphenyl dicarboxylate copolyestercarbonate with a diester: carbonate molar ratio of 1.0: 1.

In a 2 liter flask equipped with a thermometer, nitrogen and phosgene inlets, and a paddle stirrer connected to a Cole Parmer Servodyne, 99.44 g (0.436 mol) bisphenol A, 89.7 g pyridine (1.134 g) pyridine.
Mol) and 1.18 L of methylene chloride. The resulting clear solution was stirred at 300 rpm and cooled to about 16 ° C., then 60.79 g (0.218 mol) of 4,4′-biphenyldicarboxylic acid chloride was added to about 4 ° C.
When added to the flask over the course of a minute, it exotherms about 20 ° C
Became. The clear solution was stirred for 10 minutes, 1.6 g (0.011 mol) of p-tertiary butylphenol was added, and phosgene 22.5 was added.
g (0.23 mol) was added to the flask over 15 minutes. Meanwhile, the flask contents were maintained at 14-29 ° C. methanol
(3 mL) and HCl (3N, 160) and add 3 more flask contents.
After stirring for 0 minutes, the mixture was poured into a 2-L separating funnel. Separate the methylene chloride phase containing polyester carbonate and
After washing again with 1 215 ml, it was passed through a macroporous cation exchange resin column (bed volume 300 mL). Next, 1 volume of methylene chloride was added to a mixture of 2.4 volumes of hexane and 1.2 volumes of acetone in an explosion-proof blender to isolate the polymer, and the obtained precipitate was collected by filtration.

The precipitated product was then dried in a vacuum oven at about 120 ° C for 48 hours. The product obtained has a weight of 13
6.5 g, 0.72 dL / g, and the diester: carbonate ratio was 1.0: 1 as determined by nuclear magnetic resonance and infrared spectroscopy. This material is referred to as Sample 1.

For comparison purposes, using the general procedure of the examples,
Bisphenol A with a diester: carbonate ratio of 1.0: 1
/ A terephthalate copolyestercarbonate polymer was prepared. In this comparative material (referred to as sample C1), 4,4'-
Terephthaloyl chloride was used instead of biphenyldicarboxylic acid.

The measured properties of Sample 1 and Sample C1 are shown in Table 1. As can be seen from these results, the composition of the present invention shows an improvement in Tg, notched Izod, various tensile properties, hydrolysis stability and solvent resistance as compared with the comparative composition.

[0045]

[Table 1]

[0046]

Example 2 To further illustrate the scope of the present invention, a bisphenol A / 4,4'-biphenyldicarboxylate copolyestercarbonate polymer having a diester: carbonate molar ratio of 0.06: 1 to 10: 1 was prepared in Example 1. Further preparation was carried out according to the general procedure of. The results are shown in Table 2.

The molecular weight of the obtained polymer depends on the intrinsic viscosity (I
Observed via V). Higher intrinsic viscosity values indicate higher molecular weight polymers. Examples 2-12 were prepared with the intrinsic viscosities reported in Table 2.

In Samples 4 and 5 and Examples 6 and 7, various intrinsic viscosities were obtained by varying the amount of p-tertiary butylphenol. The lower the amount, the higher the molecular weight, which is indicated by the higher intrinsic viscosity.

[0049]

[Table 2]

[0050]

Example 3 To further illustrate the benefits of the present invention, bisphenol A / 4.4'-biphenylcarboxylate (BP) copolyestercarbonate polymers as shown in Table 3 were exposed to UV light. For comparison, the bisphenol A / terephthalate (T) copolyestercarbonate polymer (Samples C1-C3) was also exposed. Samples 12, C2 and C3 were prepared according to the general procedure of Example 1. The resulting YI change (TI) shows that the compositions of the present invention have significantly reduced yellowing after UV exposure.

[0051]

[Table 3]

[0052]

EXAMPLE 4 To further illustrate the scope of this invention, an additional copolyestercarbonate polymer was prepared according to the general procedure of Example 1. The diol used in the composition of this example was bisphenol A (BA); 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane (TCBA); 2,2-bis (4-hydroxy-3). , 5-Dibromophenyl) propane (TB
BA); 4,4'-dihydroxybiphenyl (DHB); 4,4'-thiodiphenol (TDP); 1,1-bis (4-hydroxyphenyl) -1-phenylethane (also known as bisphenol AP, BAP); and 2,2 ', 6,6'-tetrabromo-3,3', 5,
5'-Tatramethyl-4,4'-dihydroxybiphenyl (TTD
HB). The esters used were 4,4'-biphenylcarboxylate (BP), terephthalate (T) and isophthalate (I). The results of these compositions are shown in Table 4 (Samples 13-22).

[0053]

[Table 4]

[0054]

EXAMPLE 5 To further illustrate the scope of the present invention, this example illustrates the preparation of a thermoplastic polymer blend of a bisphenol A polycarbonate resin and a copolyestercarbonate polymer of the present invention.

Prepared according to the general procedure of Example 1, IV
= 0.56 and the diester: carbonate ratio is 1.0: 1.
87.6 g of the bisphenyl A / 4,4′-biphenylcarboxylate copolyestercarbonate polymer of ## STR4 ## was mixed with bisphenol A polycarbonate polymer (32.4 g, = 0.53 / g) in 1 liter of methylene chloride. The blend was then isolated using hexane / acetone and an explosion proof blender. After drying the precipitated product in a vacuum oven,
It was compression molded. The following results were obtained with this molded blend composition: Notched Izod = 411.2
J / m (7.7 feed pounds / inch); TY = 63.85 MPa
(9.261 psi); EY = 8.8 percent; PYSD = 9.0 percent; and TM = 2,068.43 MPa (300,000 psi).

[0056]

Example 6 An additional advantage of the composition of the present invention is that it resists crystallization during solvent casting of films. 0.127 mm (0.005 inch) thickness by solvent casting from methylene chloride solution
When the above bisphenol A polycarbonate film was prepared, opacity and melting transition
A crystalline film was obtained as shown by (differential scanning calorimetry analysis). Diester: carbonate ratio of 0.05 to 1.
In the range of 5, an amorphous film of the bisphenol A / terephthalate copolyestercarbonate comparative polymer can be prepared. On the other hand, the bisphenol A of the present invention
/ Biphenyl dicarboxylate copolyestercarbonate polymer, the corresponding diester: carbonate range for amorphous film preparation is 0.05 to 10.0
Met.

Continued front page    (72) Inventor Kenneth A. Badett             48640, Midra, Michigan, United States             And Diana 2800 (72) Inventor Guo Xiu Jie Lee             48640, Midra, Michigan, United States             And barrel coat 10

Claims (10)

[Claims] 1. A copolyestercarbonate polymer prepared by contacting a dihydroxy compound with a dicarboxylic acid compound and a carbonate precursor, wherein (a) 50 mol% or more of the dicarboxylic acid compound used is:
Consisting of a diaryldicarboxylic acid compound containing two or more aromatic rings connected to each other by a positional and angularly defined rigid internal linking group, and (b) a mole of the dicarboxylic acid compound to the carbonate precursor. The ratio is such that the diester: carbonate group molar ratio of the polymer is 0.02: 1.
A copolyestercarbonate polymer, characterized in that the ratio is between 20 and 20: 1. 2. The dicarboxylic acid compound is 4,4′-biphenyldicarboxylic acid, 3,4′-biphenyldicarboxylic acid, 4,4′-
The polymer of claim 1, which is one or more selected from the group consisting of biphenyldicarboxylic acid chloride and 3,4'-biphenyldicarboxylic acid chloride. 3. The rigid linking group inside is a covalent bond, an alicyclic ring or a heterocyclic ring, —C═C—, —C≡C—, —COO.
-, -NHCO-, -NHCOO-, The polymer of claim 1 selected from the group consisting of: 4. The diaryldihydroxy compound is 2,2-
Bis (4-hydroxyphenyl) propane, 2,2 ', 6,6'-tetrabromo-3,3', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2-bis (4- Selected from the group consisting of hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4'-dihydroxybiphenyl and bis (4-hydroxyphenyl) sulfide. The polymer of claim 1 which is one or more diaryldihydroxy compounds that are: 5. The polymer of claim 1 wherein the molar ratio of diester groups: carbonate groups is 0.05: 1 to 15: 1. 6. The polymer of claim 5 wherein the molar ratio of diester groups: carbonate groups is 0.06: 1 to 10: 1. 7. The polymer of claim 1, wherein the carbonate precursor is phosgene. 8. A polymer according to claim 1, wherein the dihydroxy compound is bisphenol, the diaryldicarboxylic acid compound is biphenyldicarboxylic acid and / or biphenyldicarboxylic acid chloride, and the carbonate precursor is phosgene. 9. A thermoplastic polymer blend comprising a thermoplastic polymer and the copolyestercarbonate polymer of claims 1-8, wherein the polymer blend comprises a total weight of thermoplastic polymer and copolyestercarbonate polymer present. As a basis, a thermoplastic polymer blend characterized by containing 0.5% by weight or more of the copolyestercarbonate. 10. The heat of claim 9 wherein the copolyestercarbonate polymer is prepared from a bisphenol A dihydroxy compound, a biphenyldicarboxylic acid and / or a biphenyldicarboxylic acid chloride diaryldicarboxylic acid, and a phosgene carbonate precursor. Plastic polymer blend.