JPS59166528A - Polycarbonate showing improved heat resistance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Polycarbonates are well-known thermoplastic materials that have found use as thermoplastic engineering materials in many industries and industries due to their many advantageous properties. Polycarbonates exhibit excellent properties such as toughness, flexibility, impact resistance and heat resistance.

Generally, polycarbonate is made of 2 such as bisphenol-A.
It is produced by the reaction of a hydric phenol with a carbonate precursor such as phosgene.

Although currently available conventional polycarbonates are truly useful in a wide range of applications, they nevertheless exhibit substantially most of the advantageous properties of conventional polycarbonates to a substantial degree, and There is a need for polycarbonates that also exhibit heat resistance greater than (19) in applications involving high-temperature environments.

It is therefore an object of the present invention to provide a polycarbonate which exhibits to a substantial extent substantially all of the advantageous properties of conventional polycarbonates, while at the same time exhibiting improved heat resistance.

The present invention provides polycarbonate resins that exhibit substantially most of the advantageous properties of conventional polycarbonate resins to a substantial extent, while exhibiting improved heat resistance.

These polycarbonates have a general formula (wherein R is each independently selected from a halogen group, a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, R1 is each independently selected from a monovalent hydrocarbon group, and X is 8 ~represents a cycloalkylidene group containing about 16 ring carbon atoms, where n is independently selected from integers having a value of 0 to 4, and m is the number of substitutable hydrogen atoms present on O to X. (selected from an integer having a value up to) generally consists of at least one repeating structural unit.

It has now been discovered that carbonate polymers can be obtained which exhibit improved heat resistance while at the same time retaining to a substantial extent substantially most of the other advantageous properties of conventional polycarbonates.

These novel polycarbonates are composed of (1) a carbonate precursor; X represents a cycloalkylidene group containing from 8 to about 16 ring carbon atoms, n is each independently selected from an integer having a value from 0 to 4, and m is (21) is an integer having a value from 0 to the number of hydrogen atoms present on X available for substitution.

Preferably, the halogen group represented by H is selected from chlorine and bromine.

The monovalent hydrocarbon group represented by H is selected from alkyl, aryl, aralkyl, alkaryl, and cycloalkyl groups.

Preferred alkyl groups represented by H are those containing 1 to about 8 carbon atoms. Some non-limiting examples of these alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-
Including butyl group, pentyl group, neopentyl group, etc. Preferred aryl groups represented by H are those containing 6 to 12 carbon atoms, namely phenyl, naphthyl and biphenyl. Preferred aralkyl and alkaryl groups represented by H are those containing from 7 to about 14 carbon atoms. Some non-limiting examples of these alkaryl and (22) and aralkyl groups include benzyl,
Contains tolyl group, ethylphenyl group, etc.

Preferred cycloalkyl groups represented by H are 4-
Contains 6 ring carbon atoms and includes cyclobutyl, cyclopentyl and cyclohexyl groups.

The monovalent hydrocarbon oxy group represented by H is preferably selected from alkoxy and aryloxy groups. Preferred alkoxy groups are those containing from 1 to about 8 carbon atoms and include, for example, methoxy, butoxy, propoxy, impropoxy, and the like. A preferred aryloxy group is a phenoxy group.

Preferred R's are each independently selected from monovalent hydrocarbon groups, with alkyl being the preferred hydrocarbon group.

The monovalent hydrocarbon group represented by R' is an alkyl group,
Selected from aryl, alkaryl, aralkyl, and cycloalkyl groups.

Preferred alkyl groups are those containing 1 to about 8 carbon atoms (23). Some non-limiting examples of these alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, and the like. Preferred aryl groups include those containing 6 to 12 carbon atoms, namely phenyl, naphthyl and biphenyl.

Preferred aralkyl and alkaryl groups represented by R1 are those containing 7 to about 14 carbon atoms. Some non-limiting examples of these preferred aralkyl and alkaryl groups include benzyl, tolyl, ethylphenyl, and the like. Preferred cycloalkyl groups represented by R1 include those containing 4 to 6 ring carbon atoms, namely cyclobutyl, cyclopentyl and cyclohexyl.

A preferred monovalent hydrocarbon group represented by R1 is an alkyl group.

In the dihydric phenol compound of formula (11), when more than one R substituent is present on the aromatic residue, they can be the same or different.

Similarly, when more than one R1 substituent is present on the cycloalkylidene group represented by X, they may be the same or different.

In formula (11), m represents an integer having a value of O to about 6.

A preferred dihydric phenol of formula (II) is phenol/L[4,4'-hisphenol.

Some non-limiting examples of dihydric phenols represented by the formula ill =23! (27) etc.

The novel dihydric phenol of formula (11) is formed by
Preferably, they are made by reacting certain ketones with phenols in the presence of an acid catalyst and a cocatalyst such as butyl mercaptan.

The particular ketone reactive component is selected from ketones represented by the general formula where R1, m and X are as described above. In particular, the ketone of the formula (Ill) is a ketone of the general formula 1 (wherein R1 is as described above, and Y is 7 to about 15 carbon atoms forming a ring structure containing 8 to about 16 carbon atoms together with 10-1 groups). m' is an integer having a value from 0 to the number of substituted hydrogen atoms present on Y).

The phenol reactant is selected from phenols represented by the general formula where R and n are as previously described.

In order to obtain novel dihydric phenols of the formula (Il), one mole of the ketone of the formula (Ilrl(29)) is reacted in the presence of an acid catalyst, preferably in the presence of an acid catalyst and a co-catalyst such as butyl mercaptan. IVI with 2 moles of phenol.Generally the phenol reactant is present in excess.Rather than utilizing only one reactant, a mixture of two different phenols may be used.

Some non-limiting examples of suitable acid catalysts that may be used include hydrochloric acid, hydrobromic acid, poly(styrene sulfonic acid), sulfuric acid, benzene sulfonic acid, and the like.

The phenol of formula 1 is formed by the reaction between the ketone of formula (fill), the phenol, and the ketone of formula (2 of formula 11).
The reaction is carried out under conditions of temperature and pressure in the presence of an acid catalyst to form the hydric phenol.

Generally, the reaction proceeds satisfactorily at a temperature of from room temperature (25°C) to about 100°C and a pressure of about 1 atmosphere.

The amount of acid catalyst used is a catalytic amount. Catalytic amount means an amount effective to catalyze the reaction between the ketone and phenol to form a dihydric phenol. Generally this amount will range from about 0.1% to about 10%. In practice, however, the sailor products formed during the reaction dilute the acid catalyst, making it slightly less effective (slowing the reaction) than in its (30) undiluted state, so it is usually used in slightly larger amounts. used for

In preparing the carbonate polymers of the present invention, a single dihydric phenol of formula (It) may be used, or a mixture of two or more different dihydric phenols of formula (11) may be used.

The carbonate precursor reacted with the dihydric phenol of formula (11) can be a carbonyl halide, diaryl carbonate or bishaloformate. A preferred carbonate precursor is a carbonyl halide. The carbonyl halide is a carbonyl chloride,
Selected from carbonyl bromide and mixtures thereof. A preferred carbonyl halide is carbonyl chloride, also known as phosgene.

The novel carbonate polymers of the present invention have at least one compound represented by the general formula () (1) () % formula % (31) where R, R'', X, m, and n are as described above. Contains one repeating unit.

These high molecular weight aromatic carbonate polymers generally range from about 10,000 to about 200,000, preferably about 20
000 to about 100,000.

Also included here are randomly branched thermoplastic polycarbonates. These randomly branched polycarbonates contain (i1 carbonate precursor-1 (11) at least one dihydric phenol of formula (11), and (ii
il can be made by reacting small amounts of polyfunctional organic compounds. Polyfunctional organic compounds are generally aromatic and function as branching agents. This polyfunctional aromatic compound contains at least three functional groups selected from hydroxyl groups, carboxyl groups, haloformyl groups, carboxylic anhydride groups, and the like. Some representative polyfunctional aromatic compounds are described in U.S. Pat.
No. 184 (these US patents are incorporated herein by reference).

Some non-limiting examples of these polyfunctional aromatic compounds include trimellitic anhydride, trimellitic acid, trimethyl trichloride, mellitic acid, and the like.

One method for producing the high molecular weight aromatic carbonate polymers of the present invention includes using an aqueous caustic solution, an organic water-immiscible solvent such as methylene chloride, at least one dihydric phenol represented by the general formula +11, phosgene, etc. Includes a heterogeneous interfacial polymerization system using a carbonate precursor-1 catalyst and a molecular weight modifier.

Another useful method of producing the carbonate polymers of the present invention is to use an organic solvent system in which the organic solvent system also functions as an acid acceptor, at least one dihydric phenol of the formula (Il), a molecular weight modifier, , catalysts, carbonate precursors such as phosgene, and the use of molecular weight modifiers.

The catalyst used herein can be any catalyst suitable for assisting in the polymerization (33) reaction of dihydric phenol with a carbonate precursor such as phosgene to produce polycarbonate. Suitable catalysts include, but are not limited to, tertiary amines such as triethylamine, quaternary ammonium compounds, and quaternary phosphonium compounds.

The molecular weight regulator used can be any known compound that adjusts the molecular weight of carbonate polymers by a chain termination mechanism. These compounds include, but are not limited to, phenol, tertiary butylphenol, chromane, and the like.

The temperature at which the phosgenation reaction proceeds is from below 0°C to 100°C.
You can change the above. Reaction at room temperature (25℃)
The process proceeds satisfactorily at temperatures from to about 50°C. Since the reaction is exothermic, the rate of phosgene addition or the use of low boiling solvents such as methylene chloride can be used to control the reaction temperature.

The carbonate polymers of the present invention may optionally be supplemented with certain commonly known and used (34) additives such as antioxidants; antistatic agents; fillers such as glass fibers, mica, talc, clays, etc. ; Impact modifier; Ultraviolet absorber such as benzophenone, benzotriazole, cyanoacrylate, etc.; Plasticizer; Hydrolysis stabilizer such as U.S. Pat. Nos. 3,489,716 and 4,138,379
and No. 3,839,247 (incorporated herein in their entirety by reference); color stabilizers such as U.S. patents! No. 3305520 and jFJ
No. 4118730 (these are incorporated herein by reference)
organophosphites; flame retardants; and equivalents.

Some particularly useful flame retardants are alkali and alkaline earth metal salts of sulfonic acids. These types of flame retardants are described in U.S. Pat.
No. 90, No. 3953396, No. 3931100, No. 3978024, No. 3953399, No. (35) No. 3917559, No. 3951910 and No. 394
No. 0366 (incorporated herein by reference).

Another embodiment of the present invention provides (1) at least one dihydric phenol of formula +11 based on carbonate precursor-1;
and at least one general formula (in the formula, R2 is each independently) selected from a rogene group, a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, and a is each independently an integer having a value of 0 to 4. , b is 0 or 1, and A is a carbonate copolymer obtained by reacting a dihydric phenol represented by an alkylene group, an alkylidene group, or -8-1-〇-11.

Preferred halogen groups represented by R2 are chlorine and bromine.

The monovalent hydrocarbon group represented by R2 is an alkyl group,
They are an aryl group, an aralkyl group, an alkaryl group, an aralkyl group, and a cycloalkyl group. Preferred alkyl groups represented by H are those containing 1 to 8 carbon atoms. Some non-limiting examples of these alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, and the like.

Preferred aryl groups represented by R2 include 6 to 1
There are those containing two carbon atoms, namely phenyl, naphthyl and biphenyl. Preferred aralkyl and alkaryl groups represented by R2 include 7
Contains ~14 carbon atoms. Some non-limiting examples of these aralkyl and alkaryl groups include hahenzyl, 1-IJ, ethylphenyl, and the like. Preferred cycloalkyl groups represented by R2 contain from 4 to about 6 ring carbon atoms (37) and include cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, and the like.

Preferably, the monovalent hydrocarbon oxy group represented by R2 is selected from an alkoxy group and an aryloxy group. Preferred alkoxy groups represented by R2 are 1-
It contains about 8 carbon atoms. Some non-limiting examples of these alkoxy groups include methoxy, butoxy, impropoxy, propoxy, and the like. A preferred aryloxy group is a phenoxy group.

Preferably, each R2 is independently selected from monovalent hydrocarbon groups, preferably an alkyl group or a monovalent hydrocarbon group.

Preferred alkylene groups represented by A are from 2 to about 6
is an alkylene group containing 5 carbon atoms. Some non-limiting examples of these alkylene groups include ethylene, propylene, butylene, and the like. Preferred alkylidene groups represented by A are those containing (38) from 1 to about 6 carbon atoms. Some non-limiting examples of these alkylidenes include ethylidene, 1.1-7'ropylidene, 2,2-propylidene, and the like.

A preferred dihydric phenol of the formula (Vll) is a dihydric phenol in which b is 1 and λ is selected from an alkylene group or an alkylidene group.

More than one R2 in the dihydric phenol of formula (■l)
When substituents are present on an aromatic core residue, they may be the same or different.

A more preferred dihydric phenol of formula fl is 4,4I-bisphenol.

Dihydric phenols of formula M) are well known to those skilled in the art;
They are generally commercially available and can be easily made by known methods. These phenols are commonly used to make prior art polycarbonate resins.

Some non-limiting examples of dihydric phenols of formula (Vll) include 2,2-bis(4-hydroxyphenyl)propane (
Bisphenol-A): 1,1-bis(39)s(3-methyl-4-hydroxyphenyl)ethane; 2
,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; 2,2-bis(3,5-dibromo-4-
hydroxyphenyl)propane; bis(4-hydroxyphenyl)sulfone; 3,3-bis(3-methyl-4-
(hydroxyphenyl)pentane; Contains 3,3'-diethyl-4,4'-dihydroxydiphenyl and the like.

The amount of dihydric phenol of formula (II) utilized in this embodiment is an amount effective to improve the heat resistance, e.g., glass transition temperature, of the copolymer. From about 5 to about 90% by weight, preferably from about 10 to about 80% by weight, based on the total amount of dihydric phenols in Vll.
% by weight.

A preferred dihydric phenol of the formula (Vll) is 2,2-bis(
4-hydroxyphenyl)propane.

(1) Carbonate precursor-1 (11) The carbonate copolymer obtained by reacting at least one dihydric phenol of the formula (11) and at least one dihydric phenol of the formula (Vl) is at least the following: Contains a repeating structural unit (Vl; and

In practicing this embodiment of the invention, only one type of dihydric phenol of the formula fl may be used, or alternatively, the formula
A mixture of two or more different dihydric phenols may also be used.

The method of making the copolymer of this embodiment is generally similar to the method used to make the polycarbonates of the invention described above. This carbonate copolymer can be mixed with the various additives mentioned above, if desired.

Yet another embodiment of the present invention provides at least one polycarbonate resin derived from fil(al) at least one dihydric phenol of formula (II) and (bl) carbonate precursor (hereinafter referred to as Resin A). and (II) at least one dihydric phenol of formula (VI);
There is a polycarbonate resin blend consisting of at least one conventional polycarbonate resin (hereinafter referred to as Resin B) derived from Polycarbonate.

These blends contain an effective amount of Resin A to improve the heat resistance of the blends. Generally, this amount will range from about 5% to about 90% Resin A, preferably from about 10% to about 80% Resin A, based on the total amount of Resins A and B present in the blend.
% by weight.

Blends of the present invention may optionally contain mixed additives as described above.

The blend is generally first preformed with resin and B;
These resins can then be made by physically mixing them. These blends can optionally contain the various additives mentioned above.

Yet another embodiment of the invention includes: (1) carbonate precursors - 1li 1 at least one dihydric phenol of the formula (11), and GIN at least one 2(42) functional carboxylic acid or reactive derivative thereof; There are copolyester-carbonates derived from.

Generally speaking, copolyester-carbonates contain repeating carbonate groups, carboxylate groups, and aromatic carbocyclic groups in a linear polymer chain, where at least some carboxylate groups and at least some carbonate groups The group is bonded directly to a ring carbon atom of an aromatic carbocyclic group.

These copolyester-carbonates contain ester bonds and carbonate bonds in the polymer chain, with the amount of ester bonds ranging from about 25 to about 90 mole percent, preferably about 35
to about 80 mol%. For example, 5 moles of bisphenol-A reacting completely with 4 moles of inphthaloyl dichloride and 1 mole of phosgene gives a copolyester-carbonate with 80 mole percent ester linkages.

Generally conventional cobolyester-carbonates (43) and methods for their preparation are described in US Pat. No. 3,169,121, which is incorporated herein by reference.

Generally, any difunctional carboxylic acid conventionally used in making linear polyesters can be utilized in making the copolyester-carbonate resins of the present invention. The carboxylic acids used include aliphatic carboxylic acids, aliphatic-aromatic carboxylic acids, and aromatic carboxylic acids. These acids are described in US Pat. No. 3,169,121 mentioned above.

The difunctional carboxylic acids that can be used in the production of the copolyester-carbonate resins of the present invention generally have the general formula % (wherein R' is an alkylene group, an alkylidene group, an aralkylene group, an aralkylidene group, or an alicyclic group; ethylene alkylene group, alkylidene group or alicyclic group containing a system unsaturated bond; aromatic group such as phenylene group, biphenylene group, substituted phenylene water, etc.; R11 is a carboxyl group or a hydroxyl group, 9 represents 1 when R8 is a hydroxy group, and 0 or 1 when Ha is a carboxyl group).

Preferred bifunctional carboxylic acids are aromatic difunctional carboxylic acids, i.e., q is 1, R8 is a carboxyl group or a hydroxyl group, and R4 is an aromatic group, such as a phenylene group, a naphthylene group, a biphenylene group, and tfflta. It is an aromatic difunctional carboxylic acid of formula (■) which is a phenylene group or the like. A preferred aromatic bifunctional carboxylic acid has the general formula (wherein R3 is as described above, R11 is each independently selected from a halogen group, a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, and P is 0 to 4 (45) (representing an integer having a value).

Preferred halogen groups represented by R6 are chlorine and bromine. The monovalent hydrocarbon group represented by R8 is selected from alkyl, aryl, alkaryl, aralkyl, and cycloalkyl groups. Preferred alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups are the same as defined for R above. The monovalent hydrocarbon oxy group represented by R5 is selected from alkoxy and aryloxy groups. Preferred alkoxy and aryloxy groups represented by R5 are the same as defined for H above.

Preferred groups represented by R6 are monovalent hydrocarbon groups, with alkyl groups being preferred monovalent hydrocarbon groups.

Mixtures of two or more -H different difunctional carboxylic acids can be used as well as a single difunctional carboxylic acid. Therefore, when using the term difunctional carboxylic acid (46) here, it refers not only to a single difunctional carboxylic acid but also to a difunctional carboxylic acid.
It is meant to include a mixture of two or more different difunctional carboxylic acids.

Particularly useful aromatic difunctional carboxylic acids are isophthalic acid,
Terephthalic acid and mixtures thereof. Particularly useful mixtures of isophthalic acid and terephthalic acid are those in which the isophthalic acid to terephthalic acid weight ratio ranges from 1:10 to 10:J.

Rather than utilizing difunctional carboxylic acids themselves, their reactive derivatives such as acid halides can be used, and are sometimes even preferred. Particularly useful acid halides are acid chlorides. For example, instead of isophthalic acid, terephthalic acid or mixtures thereof, inphthaloyl dichloride, terephthaloyl dichloride or mixtures thereof can be used.

One method of making the copolyester-carbonates of the present invention is to use an aqueous caustic solution, an organic water-immiscible solvent, formula (I
A heterogeneous interfacial polymerization method utilizing at least one divalent phenol (47) represented by l, at least one difunctional carboxylic acid or a reactive derivative thereof, a catalyst, a molecular weight modifier, and a carbonate precursor. including.

A preferred heterogeneous interfacial polymerization method uses carbonate precursors.
This method uses phosgene as the solvent and methylene chloride or chlorobenzene as the organic solvent.

The reaction conditions, catalyst 8 and chain terminators or molecular weight regulators utilized are generally the same as those described above for the preparation of the polycarbonates of the present invention.

The copolyester-carbonate of the present invention can also contain, if desired, the various additives mentioned above in admixture therewith.

Another embodiment of the present invention provides carbonate precursor-1 (111 at least one difunctional carboxylic acid or reactive derivative thereof, at least one of the formula (11
dihydric phenol of the formula (VO), and (1v) less than (1v) is a relcopolyester-carbonate derived from a dihydric phenol of the formula (VO). The amount of is an amount effective to improve the heat resistance of the resin.

Generally, this amount will range from about 5 to about 90 ffiM%, preferably from about 10 to about 80% by weight, based on the amount of dihydric phenol of formula (1 and (1) present. It can be mixed with the additives mentioned above.

Yet another embodiment of the invention provides (1) at least one copolyester-carbonate resin of the invention, namely (-
1 carbonate precursor-1 (bl) at least one difunctional carboxylic acid or its reactive derivative and (c
) a copolyester-carbonate resin derived from at least one dihydric phenol of formula [11 (hereinafter referred to as copolyester-carbonate resin C), and (i
ll (al carbonate precursor-1 (bl) at least one difunctional carboxylic acid or reactive derivative thereof, and (O1 at least one dihydric phenol (49) of the formula (■l) Conventional copolyester-carbonate (hereinafter referred to as copolyester-carbonate D)
It is a copolyester-carbonate resin blend consisting of

The blend of this embodiment contains an effective amount of Resin C to improve the heat resistance of the blend.

Generally, this amount ranges from about 5 to about 90 weight percent, preferably from about 10 to about 80 weight percent, based on the amounts of copolyester-carbonate resins C and D present in the blend.

These blends can also contain the various additives mentioned above, if desired.

In order to more clearly and completely illustrate the invention, the following examples are presented. These examples are to be considered illustrative rather than limiting. In the examples, all parts and percentages are on a relative basis unless otherwise specified.

The following examples demonstrate the preparation of the novel bisphenols of the present invention.

Example 1 (50) This example demonstrates the production of 4,4'-cyclododecylidene bisphenol.

In a 32 round bottom flask equipped with a stirrer, reflux condenser, temperature needle and gas inlet tube were added 1647r (17,5 mol) of phenol, 478t (2,62 mol) of cyclododecanone and 15-n-butyl mercaptan. I prepared it. Heat was applied by a heating mantle and when the reaction mixture became liquid at 58°C, anhydrous hydrogen chloride was introduced until the solution was saturated. Stirring was continued for several hours at 52-60°C, during which time a white solid began to separate from the reddish-orange reaction mixture. When gas chromatographic analysis of a sample taken from the slurry showed the absence of macrocyclic ketones, the hot reaction mixture was filtered under suction and the filter cake formed was washed with methylene chloride to remove excess phenol. The filter cake was then slurried with fresh methylene chloride, filtered, and washed again with more solvent. The dried filter cake was 849.8F (2.41 mol) in 92% yield and melted at 207.0-208.5°C. Analysis of this by gas chromatography showed that it was 99.8F (2.41 mol). 9
% purity, it flows out in 1391 min.
Regarding cumylphenol, it was shown to have a retention time of 26.07 minutes.

Example 2 This example is based on 4, 4. '-cyclooctylidene bis(2
, 6-dimethylphenol).

6.3F (0.05 mol) cyclooctanone, 122
．． Hydrogen chloride gas was introduced into the molten mixture from 1r (1,0 mol) of 2,6-xylenol and 5fnt of mercaptoacetic acid until a saturated solution was obtained, during which time about 26
The temperature was maintained at 50-78°C for a period of time. By the end of this time a solid had formed in the molten xylenol, which was filtered off, washed with methylene chloride, washed with methanol,
Air dried. The new white crystalline diphenol obtained with a yield of 9.11 melts at 253-254°C and has a yield of 98.
5% purity was determined by gas chromatography (elution time was 24.3 minutes versus 13.5 minutes for P-cumylphenol).
5 minutes). The structure was confirmed by 13ONMR spectroscopy and proton analysis.

The following examples demonstrate the preparation of polycarbonate resins of the present invention.

Example 3 352.2f (1.0 mol) of 4,4'-cyclododecylidene bisphenol, 2052y (9.0 mol)
bisphenol-A, 7fi methylene chloride,
6.52 water, 28-triethylamine and 104
．． 2r (3,5 mol%) mixture of Chroman I (10%
1180 at room temperature for 97 minutes while maintaining the pH of the two-phase system at approximately 11 to 11.2 by adding a 25% aqueous sodium hydroxide solution to
1 of phosgene was introduced. After the phosgene addition is complete, the methylene chloride phase is separated from the aqueous phase and treated with excess dilute hydrochloric acid (0
,0IN) and then three times with deionized water. The polymer was precipitated with steam and (53) dried at 95°C. The polycarbonate formed is 25
It had an intrinsic viscosity of 0.475 a/f in methylene chloride at °C. This was fed to an extruder operating at about 550 Hz and the extrudate was cut into pellets.

The pellet is then approximately 5'X 0.5''X1 under approximately 600mm
/16" test bars. The heat deflection temperature under load (DTUL) of the test bars was measured in accordance with ASTM D-648 at 264 P81. The DTUL of the test bars was 1
The temperature was 42.5°C.

Example 4 42,1 f (0,125 mol) of 4,4'-cyclododecylidene bisphenol, 28.5 t (0,1
25 mol) of bisphenol-A, 0.7 ml. triethylamine, 0.12 F (0.5 mol%) phenol, 400-methylene chloride and 300 m
By adding a 25% aqueous sodium hydroxide solution to a mixture of
．． 1f for 27 minutes while keeping it at 4! Phosgene was introduced at room temperature at a rate of /min.

(54) After stopping the addition of phosgene, the methylene chloride phase was separated from the aqueous phase and washed with excess dilute hydrochloric acid (0,0 IN) and then three times with deionized water. The polymer was then precipitated with methanol. The polymer formed had a secondary glass transition temperature of greater than 186°C.

The following examples illustrate the preparation of prior art polycarbonates outside the scope of the present invention. This example is presented for comparison only.

Example 5 (Comparative) This example illustrates the production of bisphenol-A type polycarbonate.

2283F pure 4,4'-isopropylidene bisphenol (bisphenol-A) (melting point 156-157°C:
10.0 moles? ), 57002 water, 9275y methylene chloride, 32, Or phenol and io,
A 25% aqueous sodium hydroxide solution was simultaneously added to the mixture of triethylamine to adjust the pH of the two-phase system to approximately 11.
That is, at room temperature for 97 minutes while maintaining the temperature between 10 and 12.5 (55
) 1180r of phosgene was introduced. At the end of the addition, the pH of the aqueous phase was 117; the content of bisphenol-A in this phase was less than 1 ppm as determined by UV analysis.

The methylene chloride phase was separated from the aqueous phase and washed with excess dilute hydrochloric acid (0.0 IN) and then three times with deionized water. The polymer was precipitated with steam and dried at 95°C. The pure bisphenol-A polycarbonate formed is 25
It had an intrinsic viscosity of 0.572 dl/f in methylene chloride at °C and was fed to an extruder operated at about 550 °C and the extrudate was LuJ cut into pellets.

The pellets are then approximately 5' x 1/2# x 1/16'
The test bar was injection molded under approx. Test bar DTU
L was measured and found to be 128°C. The T1 of this polycarbonate was 149°C.

The data for Examples 3-5 show that the polycarbonate resin of the present invention (Example 3), as measured by secondary glass transition temperature and heat deflection temperature, has a higher ~4) clearly show improved heat resistance.

The following examples demonstrate the preparation of copolyester-carbonate resins of the present invention.

Example 6 A reaction vessel was charged with 400 g of methylene chloride, 300 m of water, 35.2 f (D4, 4'-cyclododecylidene bisphenol, 0.09 f of phenol, and 0.0 m of phenol).
28 ml of triethylamine was added. This pH was maintained at approximately 11 by adding a 35% aqueous caustic solution.
5.1f of inphthaloyl dichloride was added over 15 minutes. After stopping the isophthaloyl dichloride addition, a 35% aqueous caustic solution was introduced and 8.9 f of phosgene was introduced for 15 minutes while keeping the H at about 11. The polymer mixture was diluted with methylene chloride and the brine phase was separated. The polymer-containing phase formed was washed with HCI and then water, and the polymer was recovered by methanol precipitation. The copolyester-carbonate polymer formed was heated to 25°C.
Methidi(57) had an intrinsic viscosity of 0.472 dt/f and a Ty of 240.0°C in the fuchloride.

The following examples illustrate the preparation of prior art copolyester-carbonate resins outside the scope of the present invention.

This example is shown for comparison only.

Example 7 (comparative example) Reaction vessel + 1400-methylene chloride, 300 m
Water of /, 34.2F (7) Bis7x/-Lou A.

Added 0.35r phenol and 0.42ml triethylamine. Inphthaloyl dichloride of 7,62 dissolved in 1o-methylene chloride was added over 15 minutes while the pH was maintained at about 11 by addition of 35% aqueous caustic solution. After the addition of inphthaloyl dichloride is complete, the pH is adjusted to approximately 1 by adding 35% aqueous caustic solution.
6f of phosgene was introduced in 15 minutes while controlling the amount of phosgene to 1.

The polymer mixture was diluted with methylene chloride and the brine phase was separated. The formed polymer-containing phase was washed with MCI and then water, and the polymer was recovered by methanol precipitation. The Kobo(58) ester-carbonate formed was found to have an intrinsic viscosity of 0.530 de/P and a T2 of 182.2°C.

A comparison of the data for Examples 6 and 7 shows that the copolyester-carbonate resin of the present invention (Example 6) or the prior art copolyester-carbonate resin (Example 7)
It can be easily seen that it has a much higher Ty than ['1].

Additionally, the 240.0°C Ty of the inventive copolyester-carbonate resin of Example 6 is higher than that of the prior art copolyester-carbonate resin derived from phosgene, isophthaloyl dichloride, and cyclohexylidene bisphenol. It is much higher than T1 of 199°C.

Claims (1)

[Scope of Claims] 1. (11-body) carbonate precursor; each independently selected from monovalent hydrocarbon groups, X represents a cycloalkylidene group containing 8 to 16 ring carbon atoms;
n is each independently selected from an integer having a value of 0 to 4, and m represents an integer having a value from 0 to the number of substitutable hydrogen atoms present on X). Thermoplastic polymer composition (2) exhibiting improved heat resistance, comprising one type of thermoplastic polymer (2). 2. The composition according to claim 1, wherein the monovalent hydrocarbon group represented by R1 is selected from an alkyl group, an aryl group, an alkaryl group, an aralkyl group, and a cycloalkyl group. 3. The composition according to claim 2, wherein the monovalent hydrocarbon group is selected from alkyl groups. 4. The composition of claim 3, wherein the alkyl group contains from 1 to about 8 carbon atoms. 5. The composition according to claim 2, wherein m is 0. 6. The composition according to claim 2, wherein the dihydric phenol is 4,4'-bisphenol. 7. The composition according to claim 2, wherein the monovalent hydrocarbon group represented by H is selected from an alkyl group, an aryl group, an aralkyl group, an alkaryl group and a cycloalkyl group. 8. A composition according to claim 2, wherein the halogen group represented by H is selected from chlorine and bromine. (3) 9. 3. A composition according to claim 2, wherein the monovalent hydrocarbon group represented by H is selected from alkoxy groups and aryloxy groups. 10. The composition according to claim 2, wherein the carbonate precursor is phosgene. 11. A composition according to claim 10, wherein the composition is selected from monovalent hydrocarbon groups or alkyl groups covered by 11, 8'. 12. The composition of claim 11, wherein R and R are each independently selected from alkyl groups. 13. The composition according to claim 12, wherein Iff is 0. 14. The composition according to claim 13, wherein n is O. 15. The composition according to claim 14, wherein X is a cyclododecylidene group. 16. The composition according to claim jlW15, wherein the dihydric phenol is 4,4'-cyclododecylidene bisphenol. 17, thermoplastic polymer (il is (-1: (bl: and (S) general formula (wherein R2 is each independently selected from a halogen group, a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, A The composition according to claim 2, which is derived from at least one dihydric phenol represented by an alkylene group, an alkylidene group, and an alkylidene group, each of which is independently selected from an integer having a value of 0 to 4. 18. The composition of claim 17 containing an effective amount of (bl) dihydric phenol to impart heat resistance. 19. The composition of claim 18, wherein the amount is from about 5 to about 90% by weight based on the amount of hydrophenol. 20. The composition of claim 18, wherein the amount is from about 10 to about 80% by weight. 21. The composition according to claim 19, in which either b or 1 is selected. 22. The composition according to claim 21, in which either A or A is selected from an alkylene group and an alkylidene group. 23. 23. The composition of claim 22, wherein the halogen group represented by R'' is selected from chlorine and bromine. 24. The composition of claim 22, wherein the monovalent hydrocarbonoxy group is selected from alkoxy and aryloxy groups. 22JJ4
Compositions as described. 5. Claim 22, wherein the monovalent hydrocarbon group represented by R2 is selected from an alkyl group, an aryl group, an alkaryl group, an aralkyl group, and a cycloalkyl group.
Compositions as described in Section. (6) The composition according to claim 25, wherein the monovalent hydrocarbon group represented by 26R2 is selected from alkyl groups. 27. The composition according to claim 22, wherein each of R2 and R2 is independently selected from monovalent hydrocarbon groups. 28. The composition of claim 27, wherein the 281-valent hydrocarbon group is selected from alkyl, aryl, aralkyl, alkaryl and cycloalkyl groups. 29. The composition according to claim 28, wherein the monovalent hydrocarbon group is an alkyl group. 30. The composition of claim 29, wherein R' is selected from alkyl groups. 31. The composition of claim 30, wherein R and R are each independently selected from monovalent hydrocarbon groups. 32. The composition of claim 31, wherein the monovalent hydrocarbon group is selected from alkyl, aryl, aralkyl, alkaryl, and cycloalkyl groups. 33. The composition of claim 32, wherein the 331-valent hydrocarbon group is selected from alkyl groups (7). 34. The composition according to claim 33, wherein the dihydric phenol of fbl is 4,4'-bisphenol. 35. The composition according to claim 34, wherein m is 0. 36. The composition according to claim 35, wherein n is 0. 37. The composition according to claim 36, wherein x is a cyclododecylidene group. 38. The composition according to claim 37, in which the dihydric phenol of (01) is 4,4'-bisphenol. 39. The composition according to claim 38, in which a is 0. 40, 39. The composition of claim 39, wherein the dihydric phenol is bisphenol-A. 41, further comprising (dicarbonate precursor; and (
In the formula, R2 is each independently selected from a halogen group, a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, A is an alkylene group, alkylidene 1, and a is each independently an integer having a value of O to 4. 3. A composition according to claim 2, comprising at least one thermoplastic polymer derived from at least one dihydric phenol selected from the group consisting of: 42. The composition according to claim 41 (10), which contains the polymer (1) in an amount effective to improve the heat resistance of the composition. 43. The composition of claim 42, wherein the amount ranges from about 5 to about 90% by weight, based on the total amount of polymer +i1 and (1:) present. 3. The composition according to claim 2, wherein the composition is a derivative of at least one of the following: (1) a polymer, (al: (bl:) and (f) a difunctional carboxylic acid or a reactive derivative thereof. 45. The composition of claim 44, wherein the monovalent hydrocarbon group represented by R' is selected from alkyl groups. 46. The composition of claim 44, wherein the alkyl group contains from 1 to about 8 carbon atoms. A composition according to claim 45. 47. A composition according to claim 46, wherein the dihydric phenol is 4,4'-bisphenol. 48. The halogen group represented by H is selected from chlorine and bromine. 49. A composition according to claim 47, wherein the monovalent hydrocarbon oxy group is selected from an alkoxy group and an aryloxy group. 5Q, 1 represented by H 48. The composition of claim 47, wherein the valent hydrocarbon groups are selected from alkyl groups, aryl groups, alkaryl groups, aralkyl groups and cycloalkyl groups. 51.1fiITi Hydrocarbon groups are selected from alkyl groups. 52. The composition of claim 51, wherein m is O. 53. The composition of claim 52, wherein n is 0. 54. The composition according to claim 53, wherein x is a cyclododecylidene group. 55. The composition according to claim 54, wherein the carbonate precursor is phosgene. 56. Bifunctional carboxyl. 56. The composition of claim 55, wherein the acid is selected from isophthalic acid, terephthalic acid, and mixtures thereof. 57. The reactive derivative of the bifunctional carboxylic acid is inphthaloyl dichloride, terephthalic acid (11 58. The composition of claim 55, wherein the polymer of (11) is selected from (al; (bl:
(fl: and (gl general formula (in the formula, R2 is each independently selected from a halogen group, a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, A is an alkylene group, an alkylidene group, Ia is each independently 0 45. The composition of claim 44, wherein the composition is derived from at least one dihydric phenol selected from the integers having a value of 59 to 4.59. 59. The composition of claim 58, wherein the composition of claim 58 contains from about 5 to about 90% by weight of dihydric phenol (based on the amount of bl and (gl) used). The composition according to claim 59. 61. The composition according to claim 60, wherein the monovalent hydrocarbon group represented by R' is selected from alkyl 8. 62. m or 0. The composition according to claim 60. 63. The composition according to claim 60, wherein A is selected from an alkylene group and an alkylidene group. 64. Claim 63, wherein b is 1. 65. The composition of claim 64, wherein the carbonate precursor is phosgene. 66. The bifunctional carboxylic acid is selected from isophthalic acid, terephthalic acid and mixtures thereof (13). ) The composition of claim 65. 67. The reactive derivative of the bifunctional carboxylic acid is selected from isophthaloyl dichloride, terephthaloyl dichloride and mixtures thereof. 68, further comprising (i++) (hl carbonate precursor; (1) at least one difunctional carboxylic acid or a reactive derivative thereof; and (jl) of the general formula (wherein R2 is each independently a norogen atom , a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, A is selected from an alkylene group, alkylidene 11 and -〇-, b is 0 or 1 (14), and a is each independently 45. The composition of claim 44, comprising at least one thermoplastic polymer derived from at least one dihydric phenol (selected from an integer having a value between O and 4). 69. The composition of claim 68, wherein the composition contains an effective amount of polymer (1) to improve its heat resistance. Ti
70. The composition of claim 69, from about 5 to about 90% by weight, based on the amount of +). 71. The composition of claim 70, wherein A is selected from alkylene groups and alkylidene groups. 72. The composition of claim 71, wherein b is 1. 73. The composition according to claim 72, wherein the dihydric phenol (j) is bisphenol-A. 74. The composition according to claim 73, wherein the carbonate precursor of (al and (hl) is (15) phosgene. 75. The 2'-functional carboxylic acid of (fl and (1) is isophthal K, terephthal 75. The composition of claim 74, wherein the reactive derivatives of difunctional carboxylic acids selected from acids and mixtures thereof are inphthaloyl dichloride, terephthaloyl dichloride and the like. 74. The composition according to claim 74, which is selected from a mixture of: 77.
- (wherein R is each independently selected from a halogen group, a monovalent hydrocarbon group, and a monovalent hydrocarbon oxy group, R1 is each independently selected from a monovalent hydrocarbon group, and X is 8 to about 16
represents a cycloalkylidene group containing ring carbon atoms, where n is independently selected from integers having a value of 0 to 4, and m is a value from 0 to the number of substituted hydrogen atoms present on X. (representing an integer with ) dihydric phenol. Claim 7, wherein the monovalent hydrocarbon group covered by 78R1 is selected from alkyl, aryl, aralkyl, alkaryl, and cycloalkyl groups.
Dihydric phenol according to item 7. 79. A dihydric phenol according to claim 78, wherein the monovalent hydrocarbon is selected from alkyl groups. 80. The dihydric phenol of claim 79, wherein the alkyl group contains from 1 to about 8 carbon atoms. 81. A dihydric phenol according to claim 79, wherein the halogen group represented by R is selected from chlorine and bromine. 82. A dihydric phenol according to claim 79, wherein the monovalent hydrocarbon oxy group is selected from an alkoxy group and an aryloxy group. (17) 83. The dihydric phenol according to claim 79, wherein the monovalent hydrocarbon group represented by H is selected from an alkyl group, an aryl group, an aralkyl group and a cycloalkyl group. 84. The dihydric phenol according to claim 83, which is selected from a monovalent hydrocarbon group and an argyl group. 85. The dihydric phenol according to claim 79, wherein the dihydric phenol is 4,4'-bisphenol. The dihydric phenol according to claim 85, which is 86, m or 0. 87. The dihydric phenol according to claim 86, wherein n is 0. 88. The dihydric phenol according to claim 87, wherein x represents a cyclododecylidene group. 89. The dihydric phenol according to claim 85, wherein x represents a cyclooctylidene group. 90. The dihydric phenol according to claim 89, wherein the dihydric phenol is a 4,4'-cyclooctylidene group (2,6-dimethylphenol) (18). 91. The dihydric phenol according to claim 88, wherein the dihydric phenol is 4,4'-cyclododecylidene bisphenol.