CA1264891A - 5-keto-bis(hydroxyphenyl)anthracene polyarylate copolymers and alloys - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Polyarylate polymers derived from (A) mixtures of 5-keto bis(hydroxyphenyl)anthracene compounds with other bisphenols and (B) a mixture of isophthalic and terephthalic acid. Also disclosed are polyarylate alloy compositions comprising a 5-keto-bis(hydroxyphenyl)-anthracene polyarylate and a polymer resin selected from polybisphenol A carbonate and polystyrene.

Description

` l 5-KETO-BIS(HYDROXYPHENYL~ANTHRACENE
POLYARYLATE COPOLYMERS AND ALLOYS

BACKGROUND OF THE INVENTION

The present invention relates to polyarylate copolymers and alloys. More particularly, this invention relates to 5-keto-bis~hydroxyphenyl)anthracene polyarylate copolymers and alloys having superior thermal properties.
Polyarylates are defined as aromatic polyester polymers derived ~rom dihydroxy aromatic compo~lnds ~diphenols) and aromatic dicarboxylic acids.
In general, aro~atic polyesters prepared from bisphenols or functional derivatives thereof and a tere-phthalic acid-isophthalic acid mixture or a mixture of the functional derivatives thereof, i.e., bisphenol tere-phthalate-bisphenol isophthalate polyesters, have excellent mechanical properties, such as tensile strength, bsnding strength, bending recovery or impact strength, ~(~
excellent thermal properties, such as deflection tempera-ture under load or degradation temperature, excellent electrical properties, such as resistivity, electric breakdown 0ndurance, arc resistance, dielectric constant or dielectric loss and low flammability, ~ood dimensional stability, and the like.
; These aromatic polyesters are thus useflll in ; many ~ields. Aromatic polyesters find special use as plastics for injection molding, extrusion molding, press 0 molding, and the like, as monofilaments, fibexs, films and coatings.
U.S. Patent No. 3,216,970 describes polyarylates which include polymers of bisphenol A and isophthalic acid or a mixture of isophthalic acid and terephthalic acid.
These polyarylates are prepared by converting the phthalic acid component to the diacid chloride which is then reacted with the bisphenol A or its sodium salt.
U.S. Patent No. 3,884,990 describes a blend of various bisphenol polyarylates and poly(ethylene oxybenzo-ate), which is useful for producing molded articles having :a2~
J

~1 2-improved cracking and crazing resistance. Similarly,U.S. Patent No. 3,946,091 describes a blend of bisphenol D5 polyarylates and poly(ethylene terephthalate) which pro-vides molded articles of reduced crazing.
U.S. Patent No. 3,792,118 describes a styrene resin composition resistant to heat deformation which comprises a blend of polyarylene esters and various styrene resins.
SUMMARY OF THE INVENTION
The present invention provides a polyarylate copolymer derived from ~A) A mixture of a 5-keto-bis~h,ydroxyphenyl) anthracene compound oE the formula R~ R3 HO~H

wherein Rl, R2, R3 and R4 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl;
and a bisphenol compound selected from the group consist-ing of ~_C~<

~0 Ol -3-wherein R5, R6, R7 and R8 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl;

HO~ ~O

ID ~

rein Rg, Rlo' Rll and R12 are independently hydrogen, lower alkyl o 1 to 4 carbon atoms or phenyl; and ~
R~ Rl 5 HO~C~OH

21~ R14 ~ R16 wherein R13, R14, R15 and R16 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; and wherein the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol is from 20:1 to 1:20; and (B) a mixture of isophthalic and terephthalic acid in a molar ratio of 9:1 to 1:9, respectively.
The present invention is further concerne~ with a polyarylate alloy composition comprising (A) 10 to 90% by weight of a polyarylate of the formula ~ - C ~

O n ~6~

01 _4_ wherein Rl, R2, R3 and R4 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; n is the 05 degree of polymerization; and wherein O ..
-C~
is an isophthalic or terephthalic acid moiety present in a molar ratio of 9:1 to 1:9, respectively; and (B) 10 to 90% by weight of a polymer resin selected from the grc~up consisting of polybisphenol A carbonate and polystyrene.
Also contemplated by the present invention is a polyarylate alloy composition comprising (A) 10 to 90~ by weight of a polyarylate copolymer derived from (1) a mixture of a 5-keto-bis(hydroxyphenyl)-anthracene compound of the formula ;~ () HO~OH

2 5 R2 R4 Il o wherein Rl, R2, R3 and R~ are independently hydrogen,lower alkyl of 1 to 4 carbon atoms or phenyl;
and a bisphenol compound selected from the group consist-ing Of HO~)-C~--OH

wherein R5, R6, R7 and R8 are independently hydrogen, ~ lower alkyl of 1 to 4 carbon atoms or phenyl;

~Zi~4~9~

01 _~_ 10~ R12 ~-/o o n Rg, Rlo, Rll and Rl2 are independently hydrogen, lower alkyl of l to 4 carbon atoms or phenyl; and ~ ~ RlS
HO~-C~-OH

R14 ~?J R16 rein Rl3, Rl4, Rl5 and Rl6 are independently hydrogen, lower alkyl of l to 4 carbon atoms or phenyl;
and wherein the molar ratio of 5-keto-bis(hydroxyphenyl)-anthracene to bisphenol is from 20:1 to 1:20; and (2) a mixture of isophthalic and terephthalic acid in a molar ratio of 9:l to l:9, respectively; and (B) l0 to 90% by weight of a polymer resin selected from the group consisting of polybisphenol A carbonate and polystyrene.
Among other factors, the present invention is based on the discovery that certain polyarylate copoly-mers, derived from mixtures of 5-keto-bis(hydroxyphenyl)-anthracene compounds with other bisphenols, have been found to possess superior thermal properties~ In addi-tion, it has been found that 5-keto-bis(hydroxy-phenyl)anthracene polyarylates provide alloy compositionswith polystyrene and polybisphenol A carbonate which also exhibit excellent thermal properties.
DETAILED DESCRIPTION OF THE INVENTION
For purposes of the present invention, those polyarylates derived from a single 5-keto-bis(hydroxy-phenyl)anthracene compound shall be referred to as "homo-polymers" and those polyarylates derived from a mixture of 05 5-keto-bis(hydroxyphenyl)anthracene and other bisphenol compounds shall be referred to as "copolymers~. It is, of course, understood that 5-keto-bis(hydroxyphenyl)anthracene may be characterized as a type of bisphenol compound.
Furthermore, the term "alloy" as used herein is meant to define an intimate physical mixture or blend of two or more polymers.
The 5-keto-bis(hydroxyphenyl)anthracene com-pounds which are useful for conversion into the instantpolyarylate homopolymers and copolymers may be represented lS by the ~ollowing formula R~ R3 HO~ ~OH

R2 ~ R4 o wherein Rl, R2, R3 and R4 are independently hydrogen, lower alkyl of l to 4 carbon atoms or phenyl.
Preferred examples of 5-keto-bis(hydroxyphenyl)-anthracene compounds include the unsubstituted compound and the tetraalkyl derivative. Particularly pre~erred compounds are those wherein Rl, R2, R3 and R4 are hydro-gen; i.e., 5-keto-lO,lO-bis(4'-hydroxyphenyl)anthracene, and wherein Rl, R2, R3 and R4 are rnethyl, i.e , 5-keto-lO,lO-bis(31,5'-dimethyl-4'-hydroxyphenyl)anthracene.
The 5-keto-bis(hydroxyphenyl)anthracçne com-- 35 pounds used in the invention are prepared by reacting an unsubstituted or ortho-substituted phenol with anthra-quinone in the presence of a Friedel-Crafts catalyst. A
typical substituted phenol is 2,6-dimethylphenolc Suit-able Friedel-Crafts catalysts include tin tetrachloride, aluminum trichloride, and the like.

~1 -7-The instant polyarylate hoMopolymers and copoly-mers are prepared from the above-described 5-keto-05 bis~hydroxyphenyl)anthracenes or from mixtures of thesecompounds and other bisphenols~ The instant polyarylate homopolymers are prepared from a single 5-keto-bis-(hydroxyphenyl~anthracene compound or a functional deriva-tive thereof. Similarlyl the instant polyarylate copolymers are prepared from a mixture of a 5-keto-bis~hydroxyphenyl)anthracene compound or functional derivative thereof and a bisphenol compound, or functional derivative ~hereof, selected from the group consisting of ~ CH~

R6 R~

~U wherein R5, R6, R7 and R~ are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl;

R~ Rll 25 HO ~ ~ R12 ~/
o in Rg, Rlo, Rll and R12 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; and R~ ~ R15 HO~>-C~-OH

R14 1~3 R16 wherein R13~ R14~ R15 and R16 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl.
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When R5, R6, R7 and R8 above are all hydrogen,the compound obtained, 2,2-bis(4-hydroxyphenyl)propane, is 05 generally referred to as bisphenol A. When R5, R6, R7 and R8 are not all hydrogen, the compound obtained will herein be referred to as a substituted bisphenol A. Preferred examples of substituted bisphenol A include tetraalkyl bisphenol A and diphenyl bisphenol A. A particularly preferred substituted bisphenol A is tetramethyl bis-phenol A or 2,~-bis(4-hydroxy-3,5-dimethylphenyl)propane.
The various bisphenol A compounds are prepared by reacting an appropriately substituted phenol, such as 2,6-dimethyl-phenol, with acetone in the presence of a Friedel-Crafts catalyst, Moreover~ when R~, Rlo~ Rll and R12 in the above formula are all hydrogen, the compound obtained, 1,1-bis(4'-hydroxyphenyl)phthalide, is commonly referred to as phenolphthalein. When Rg, Rlo, Rll and R12 a all hydrogen, the compound obtained will herein be referred to as a substituted phenolphthalein. Preferred examples of substituted phenolphthalein include the tetra-alkyl derivatives, that is, wherein Rg, Rlo, Rll and R12 are independently lower alkyl of 1 to 4 carbon atoms. A
5 particularly preferred substituted phenolphthalein is that n Rg, Rl~, Rll and R12 are methyl, that is, 1,1-bis(3',5'-dimethyl-4'-hydroxyphenyl)phthalide or, commonly, tetramethylphenolphthalein. The substituted phenolphthalein compounds are prepared by reacting an appropriate ortho-substituted phenol with phthalic anhydride in the presence of a Friedel-Crafts catalyst, such as zinc chloride.
Further, when R13, R14~ Rls and R16 above all hydrogen, the compound obtained, bis(4-hydroxy-phenyl)diphenylmethane, is conveniently referred to asdihydroxytetraphenylmethane- When R13~ R14~ Rls a~d R16 are not all hydrogen, the compound obtained will herein be referred to as a substituted dihydroxytetraphenylmethane.
Preferred examples of dihydroxytetraphenylmethane compounds include the unsubstituted compound and the ~Z6~
o~ g tetraalkyl derivative. A particularly preferred sub-stituted dihydroxytetraphenylmethane is that wherein R13, Rl~, R15 and R16 are methyl, that is, bis(3,5-dimethyl-4-hydroxyphenyl)diphenylmethane.
The dihydroxytetraphenylmethane compounds are prepared by reacting an appropriately substituted phenol with dichlorodiphenylmethane, preferably in the presence of a Friedel-Crafts catalyst. Typical substituted phe~ols include 2,6-dimethylphenol and 2-phenylphenol. Suitable Friedel-Crafts catalysts include aluminum chlorider ferric chloride, stannic chloride, boron trifluoride, zinc chloride, hydro~en fluoride, hydrogen chloride, sulfuric acid, phosphoric acid, and the like.
Typical functional derivatives of the above-described 5-keto-bis(hydroxyphenyl)anthracenes and bis-phenols include the metal salts and the diesters with monocarboxylic acids having 1 to 3 carbon atoms. Pre-ferred functional derivatives are the sodium salts, potassium salts and diacetate esters.
For the polyarylate copolymers of the present invention, the mixture of 5-keto-bis(hydroxyphenyl)-anthracene and bisphenol will have a molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol of about 20:1 to 1:20. Preferably, the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol will be about 9:1 to 1:9, more preferably, about ~:1 to 1:4.
The acid component which is reacted with the 5-keto-bis(hydroxyphenyl)anthracene or 5-keto-bis(hydroxy-phenyl)anthracene-bisphenol mixture to prepare the poly-arylates of the invention is a mixture of isophthalic and terephthalic acid or functional derivatives thereof in a molar ratio of about 9:1 to 1:9, respectively. Prefer-

3~ ably, the molar ratio of isophthalic to terephthalic acidwill be about 3:1 to 1:3, more preferably, about 1:1.
Preferred functional derivatives of isophthalic or terephthalic acid include acid halides, such as iso-phthaloyl or terephthaloyl dichloride and isophthaloyl or ~o terephthaloyl dibromide, and diesters, such as dialkyl ~Z~8~.

esters or diaryl esters, having from 1 to 6 carbon atoms per ester group. Examples of suitable diesters include 05 diphenyl isophthalate and diphenyl terephthalate.
The polyarylate homopolymers used in the present invention can be generally represented by the formula ' ~ c~l o n wherein Rl, R2, R3 and R4 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; and n is the degree of polymerization. Generally, n will be adjusted to provide a polymer having an average molecular weight greater than about 15,000.
In the case of the polyarylate copolymers derived from a 5-keto-bis(hydroxyphenyl)anthracene-bis-phenol mixture, the 5-keto-bis(hydroxyphenyl)anthracene and bisphenol moieties will normally occur in random order throughout the polyarylate.
The polyarylates of this invention can be pre-pared by several methods. For example, an interfacial polycondensation process can be used. In this case an aqueous alkaline solution of a bisphenol or mixture of bisphenols and a terephthaloyl dihalide-isophthaloyl dihalide mixture dissolved in an organic solvent which is immiscible with water are mixed and reacted. Suitable interfacial polycondensation processes which can be used are disclosed, for example, in ~O M. Eareckson~ J. Polymer Sci., XL 399 (1959) and Japanese Patent Publication No. 1959/65.

8g~L

The following is a typical polycondensation process. An aqueous alkali solution of a bisphenol or 05 mixture of bisphenols is added to a terephthaloyl dihalide-isophthaloyl dihalide mixture, more preferably, a terephthaloyl dichloride-isophthaloyl dichloride mixture, dissolved in an organic solvent, or an organic solvent solution of a terephthaloyl dihalide-isophthaloyl dihalide mixture is added to an aqueous alkaline solution of a bisphenol or mixture o~ bisphenols. Alternatively, an aqueous alkaline solution of a bisphenol or mixture of bisphenols and an organic solvent solution of a terephtha-loyl dihalide-isophthaloyl dihalide mixture can be simul-taneously added to a reaction vessel. Interfacialpolycond~nsation takes place near the interface of the aqueous phase and the organic phase. However, since the aqueous phase and the organic phase essentially are not miscible, it i5 necessary to mutually disperse the phases.
For this purpose an agitator or a mixer such as Homo-mixer can be used.
The concentration of the terephthaloyl dihalide-isophthaloyl dihalide mixture dissolved in the organic solvent is usually from about 2 to 25 weight %, more preferably, from 3 to 15 weight %. The concentration of the bisphenol or mixture of bisphenols in the aqueous alkaline solution i5 also usually from about 2 to 25 weight ~, more preferably, from 3 to 15 weight ~.
The amount of the bisphenol or mixture of bis-phenols and of the terephthaloyl dihalide-isophthaloyl dihalide mixture used (molar ratio) is preferably main-tained equivalent. An excess of the terephthaloyl dihalide-isophthaloyl dihalide mixture is not desirable in the preparation of the high molecular weight polyarylate.
Preferred alkalis are sodium hydroxide and potassium hydroxide. The concentration of the alkali in the aqueous solution can vary widely depending upon the reaction conditions, but is usually in the range from about 0.5 to 10 weight ~. It is advantageous if the quantity of alkali is nearly equivalent to the hydroxy ~26~1LI~..

groups o the bisphenol or bisphenols used or is presentin a slight excess. The preferred molar ratio of the 05 alkali to the hydroxy group of the bisphenol or bisphenols is from 1:1 to 2:1, most preferably, from 1:1 to lol l~
As organic solvents which can be used for dis-solving the terephthaloyl dihalide-isophthaloyl dihalide mixture, hydrocarbons or halogenated hydrocarbons are used. For example, methylene dichloride, chloroform, tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloro-ethane, tetrachloroethane, benzene and methylbenzene can be employed~ Especially preferred are those solvents which also dissolve the aromatic copolyesters produced.
The most preferred solvent is 1,1,2-trichloroethane.
The reaction temperature is not strictly limited, and depends on the solvent used. For example, in the case o~ methylene dichloride, the reaction temperature is usually preferably below 40C, with from 5 to 30C
being especially preferred.
Interfacial polymerization is usually conducted at normal pressure and is completed in about 1 to 4 hours.
Antioxidants, dispersing agents, catalysts and viscosity stabilizers can be added to the aqueous alkaline solution or to the reaction mixture, if desired. Typical examples of such agents are as follows. As antioxidants, sodium hydrosulfite or sodium bisulfite can be used. As dispersing agents, anionic surface-active agents, such as sodium lauryl sulfate and octadecyl benzene sulfonate, cationic surface-active agents, such as cetyl trimethyl ammonium chloride, and nonionic surface-active agents such as polytethylene oxide) adducts can be used. As cata-lysts, quaternary ammonium compounds, such as trimethyl benzyl ammonium hydroxide, trimethyl benzyl ammonium chlo-ride and triethyl benzyl ammonium chloride, tertiary sul-fonium compounds, such as dimethyl-2-hydroxyphenyl sulfonium chloride, quaternary phosphonium compounds, such as triphenyl methyl phosphonium iodide and trime~hyl octyl arsonium iodide can be used. Tertiary ammonium compounds, such as trimethyl amine, triethyl amine and benzyl ~211~489~

dimethyl amine can also be used as catalysts. As vis-cosity stabilizers, mono-valent compounds, especially 05 mono-valen~ phenol compounds, such as p-cumyl phenol, o phenyl phenol, p-phenyl phenol, m-cresol and b-naphthol can be used, if desired.
Another useful method for forming the poly-arylates is melt polymerization, as disclosed, for exam-ple, in A~ Conix, Ind. Eng. Chem., 51 147 (1959), in Japanese Patent Publication 15,247/63 and in U.S. Patent No. 3,395,119.
Melt polymerization can be conducted, for exam-ple, by heating and reacting an aliphatic carboxylic acid diester of a bisphenol or mixture of bisphenols and a terephthalic acid-isophthalic acid mixture at reduced pressure. A preferred diester of a bisphenol is the diacetate. Melt polymerization can also be conducted by heating and reacting a bisphenol or mixture of bisphenols ~0 and a mixture of a diaryl ester of terephthalic acid and isophthalic acid. A typical diaryl ester is the diphenyl ester. The reaction temperature employed is in the range of from about 150 to 350~C, more preferably, from 180 to 320C. The reaction pressure is usually varied in the course of the reaction from atmospheric pressure at the early part of the reaction to reduced pressure, such as below about 0.02 mmHg, at the end of the reaction.
In melt polymerization, the molar ratio of the , bisphenol or mixture of bisphenols and the mixture of terephthalic acid-isophthalic acid components to prepare a high molecular ~eight polyarylate must be maintained exactly equivalent.
A number of catalysts can be used. Catalysts which are preferably used are titanium compounds, such as butyl orthotitanate and titanium dioxide. Other cata-lysts, such as zinc oxide, lead oxide and antimony dioxide can also be used.
Still another method for forming the poly-arylates is solution polymerization, in which the poly-arylates are prepared by reacting a bisphenol or mixture ~1 -14-of bisphenols with terephthaloyl dihallde and isophthaloyldihalide in an organic solvent solvenl:. Solution poly-05 merizations which can be used are disclosed, for example,in A. Conix, Ind. Eng. Chem., 51 147 (1959), and in U.S. Patent No. 3,133,898.
In solution polymerization, the bisphenol or mixture o~ bisphenols and the mixture of terephthaloyl dihalide and isophthaloyl dihalide, e.g., terephthaloyl dichloride and isophthaloyl dichloride, are usually mixed in equimolar proportions in an organic solvent, and the mixture is warmed gradually to high temperatures, such as about 2~0C~ As the organic solvent used, those solvents which also di~solve the polyarylates produced, such as dichloroethyl benzene, are preferred. ~sually, the reac-tion is carrled out in the presence of a base to neutralize the hydrogen halide, e.g., hydrogen chloride, formed.
The polyarylate alloy compositions of the present invention are obtained by mixing the above-described polyarylate homopolymers and copolymers with a polymer resin selected from the group consisting of poly-bisphenol A carbonate and polystyrene. In general, the alloy composition will contain about 10 to 90% by weight of polyarylate and about 90 to 20% by weight o~ polybis-phenol A carbonate or polystyrene. Preferably, the alloy composition will contain about 20 to 80% by weight of polyarylate and about 80 to 20% by weight of polybis-phenol A carbonate or polystyrene. The polystyrene will normally have an average molecular weight of about 100,000 to 1,000,000, preferably about 300,000. The polybis-phenol A carbonate will normally have an average molecular weight of about 20,000 to 50,000, preferably about 30,000.
To add polybisphenol A carbonate or polystyrene to the polyarylates o~ this invention, any well known mixing technique can be used. For example, grains or powders o~ these two components can be mixed and blended with a V-blender, Henschel mixer, Super mixer or Kneader, and then the mixture immediately molded. Alternatively, il9~

the mixture can be formed into pellets after melting with an extruder, a co-kneader, an intensive mixer, or the 05 like, and then molded. The pelletizing or molding temper-ature is generally in the range of from about 250 to 350C, more preferably, 260 to 320C.
Another addition method comprises adding the polybisphenol A carbonate or polystyrene to a solution of the polyarylate and then evaporating off the solvent. As the solvent r those which dissolve the polyarylate can be used, such as methylene dichloride, tetrachloroethane and chloroform. The preferred solvent is tetrachloroethane.
The solution of polymers in a solvent may be poured into a nonsolvent to precipitate the polymer and the precipitated alloy can be removed by filtration. Suitable nonsolvents are the lower alcohols, such as methanol, ethanol, pro-panol, butanol and the like. An especially preferred nonsolvent is ethanol.
The most suitable method for any particular system can be chosen according to the composition and the desired shape and properties of the molded articles to be produced therefrom.
In order to improve the heat resistance, light ~5 stability, weatherability or oxidation resistance of the composition or articles produced according to this inven-tion, agents preventing thermal degradation, antioxidants, ultraviolet absorbants, and the like, can be added there-to, if desired. For example, benzotriazole, aminophenyl benzotriazole, benzophenone, trialkyl phosphates, such as trioctyl phosphate and tributyl phosphate, trialkyl phos-phites, such as trioctyl phosphite, and triaryl phos-phites, such as triphenyl phosphite, can be used. These materials are conveniently added to the polyarylate copolymers and alloys of this invention at any time prior to molding. Known plasticizers, such as phthalate esters, e.g., dioctyl terephthalate, dioctyl orthophthalate and dioctyl isophthalate, and colorants, such as carbon black and titanium dioxide, may also be added i~ desired, in commonly used amounts as are known in this art.

91~89 ~

'~ 01 The polyarylate polymers and alloys of this invention can be used to form many useful articles using generally known molding methods, such as injection molding, extrusion molding, press molding, and the like. Typical examples of final products produced therefrom are films, monofilaments, fibers, injection molded materials, such as machine parts, automobile parts, electrical parts, vessels and springs. The polyarylate polymers and alloys of this invention find special use as engineering plastics for various uses which require good properties.
The following examples are provided to illustrate the invention in accordance with the principles of this invention but are not to be construed as limiting the invention in any way except as indicated by the appended claims. In the examples, the term "polycarbonate" refers to polybisphenol A carbonate.
EXAMPLES
2U Example 1 Preparation of 5-keto-10,10-bis(4'-hydroxyphenyl)anthracene A 500 ml round bottom, three-necked flask equipped with mechanical stirrer, water condenser, thermometer and nitrogen gas inlet tube was connected to a nitrogen supply line with a needle valve as a regulator. In the flask was placed 81.0 g (0.39 mole) of anthraquinone, 81.0 9 (0.86 mole) of phenol and 100 g (0.38 mole) of anhydrous stannic chloride. As the mixture was stirred and heated at 30 100 to 110C by an oil bath, 14.0 g (0.1 mole) of aluminum chloride was added in small portions. The mixture was then stirred and maintained at a temperature between 100 to 110~C over a period of 20 hours. The reaction mixture was a dark brown slurry.
Four hundred ml of hot water was then added to the flask. The product was filtered and washed with an addi-tional 2.5 liters of hot water. The crude product was dissolved in a 10% NaOH solution and filtered. The insol-uble portion was discarded. The filtrate portion was then

4~ acidified with a 10% HCl solution. A yellowish precipitate 9~

was formed. The solid product was filtered and washed with distilled water. The residual water was removed by drying 05 the product in a vacuum oven at 100C overnight with nitro-gen passing through slowly. The product was then recrys-tallized three times from a mixed solvent of ethanol, dimethylsulfoxide and water. Each time the crystals were collected by suction filtration and washed with a minimum amount of cold ethanol. The solvent was removed by drying in a vacuum oven at 100C in a nitrogen atmosphere overnight.
The yield was 110 g, 74~ of theory. The product WAS a color-less powd~r having a meltin~ point of 32~ to 330C. The product was analyzed for the percent of carbon and hydrogen.
IS Analytical calculated for C26H18O3: C, 82-52~ H, ~.7S.
Found: C, 82.43; H, 4.75. NMR(acetone-d6): ~ 8.2 - 8.0 (m, 2, Ar~), 7.0 - 7.6 (m, 6, ArH), 6.7 (s, 8, ArH), 2.8 (s, 2, ArOH).
Example 2 Preparation of

5-Keto-10,10-bis(4'-hydroxyphenyl)anthracene iso/terephthalate Polymer A 500-ml, three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen gas inlet and outlet was charged with 7.56 grams (0.02 mole) of 5-keto-10,10-bis(4'-hydroxyphenyl)anthracene, 0.20 gram (0.0009 mole) of triethylbenzyl ammonium chloride, 0.02 gram sodium bisulfite, 1.7~ grams (0.044 mole) of sodium hydroxide, 135 ml of water, and 30 ml of 1,1,2-trichloro-ethane. The reaction mixture was stirred at a motor speed of 1000 rpm under a nitrogen atmosphere at a temperature not exceeding 10C maintained by an ice water bath. The stirrer speed was checked by a photo tachometer. A mixed solution of terephthaloyl dichloride, 2.03 grams (0.01 mole), and isophthaloyl dichloride, 2.03 grams (0.01 mole), in 49 ml of 1,1,2-trichloroethane was added over a period of 30 minutes. ~t the same time, the mixture was vigorously cstirred. The ice water bath was then replaced with a room temperature water bath and stirring was con-~0 tinued for an additional four hours. Subsequently, the upper aqueous layer was decanted and replaced by 100 ml of ~26;~8~

distilled water and 30 ml of 1,1,2-trichloroethane. The mixture was again stirred for 3~ min~ltes. The resulting OS aqueous layer was decanted and removed. The organic layer was poured into 600 ml of 200-proof ethanol. A white polymer was precipitated which was collected by suction filtration. The polymer ~as washed four times with 200 ml ethanol. The yield of polymer was 8.40 grams. It was a 1~ 76.3% yield. The polymer was dissolved in a mixed solvent of 40/60 phenol and 1,1,2,2-tetrachloroethane by rotating it overnight. The Gardner viscosity of a 10% solution was 5.50 poises at 25C. The glass transition temperature, Tg, measured by differential scanning calorimetry (DSC), was 318C.
~.
Preparation of 5-keto-10,10-bis(4'-hydroxyphenyl)anthracene _ _b$sphenol A iso/terephthalate copolymer A 500 ml, three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen inlet and outlet was charged with 2.27 grams (0.006 mole, 20 mole ~) of 5-keto-10,10-bis(4'-hydroxyphenyl) anthracene, 5.~8 grams (0.024 mole, 80 mole ~) of bisphenol A, 0.20 gram (0.0009 mole) of triethylbenzyl ammonium chloride, 0.02 gram of sodium bisulfite, 2.84 grams (0.066 mole) of sodium hydroxide, 135 ml of water, and 30 ml of 1,1,2-trichloroethane. The reaction mixture was stirred at a motor speed of 1000 rpm under nitrogen atmosphere at a temperature not exceeding 10C monitored by an ice water bath. A mixed solution of terephthaloyl dichloride, 3.05 grams (0.015 mole), and isophtholoyl dichloride, 3.05 - grams (0.015 mole), in 40 ml of 1,1,2-trichloroethane was added over a period of 30 minutes. At the same time, the mixture was vigorously stirred. The ice water bath was then removed and replaced with a room temperature water bath. Stirring was continued for an additional Eour hours. Subsequently, the upper layer was decanted and replaced by 100 ml of distilled water and 30 ml of 1,1,2-trichloroethane. The mixture was again stirred for 30 minutes. The resulting aqueous layer was poured into I

600 ml of 200-proof ethanol. A white polymer was pre-cipitated which was collected by suction filtration. The oS polymer was washed four times with 200 ml of ethanol. The product was placed in a vacuum oven at 100C overnight.
The yield of polymer was 10.7 grams. This was a 77.3%
yield. The polymer was dissolved for Gardner viscosity in a mixed solvent of 40/60 phenol and 1,1,2,2-tetrachloro-ethane by rotating it overnight. The Gardner viscosity of a 10% polymer solution was 3.70 poises at 25C. Reduced viscosity was measured at 0.25 g/100 ml in 1,1,2,2-tetra-chloroethane, Reduced viscosity was 0.64 dl/g at 25C.
The glass transition temperature, Tg, measured by di~Eer-ential scanning calorimetry, was 227C.
Following the above procedure, copolymers wereprepared using other bisphenol monomers in place of bis-phenol A. The glass transition temperature, Tg, of these copolymers at various mole ratios of bisphenols is shown in Table 1.

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5-Keto-10-,10-bis-~4'-hydroxyphenyl) 05Anthracene Copolyarylates With Various BisDIlenols and Iso/TereDhthalic Acid 1/1 Mole ~
Comonomer Bisphenol Comonomer Tg, C
Bisphenol A 20 215 ~0 238 2,2-Bis-(4-hydroxy-3,5-dimethylphenyl) 20 298 Propane 40 295 Bis-(4-hydroxyphenyl) Diphenylmethane 20 317 ~0 2~5 Bis-(3,5-dimethyl-4-hydroxyphenyl) 40 309 Diphenyl~ethane 60 271 ~U 80 264 1,1-Di-(3',5'-dimethyl-4'-hydroxyphenyl) 20 311 Phthalide 40 322 Example 4 Preparation of the Alloy of 5-Keto-10,10-bis-(4'-hydroxyphenyl) Anthracene Iso/Terephthalate With Polycarbonate In a 20-ml vial was placed 1.0 gram of 5-keto-10,10-bis(4'-hydroxyphenyl) anthracene iso/terephthalate, 1.0 gram of polycarbonate (Lexan 141~, and 18.0 grams of 1,1,2,2-tetrachloroethane. The vial was placed on a rotator and rotated until the mixture was completely dis-solved. This was now a 1:1 solution of polymers by weight. Two milliliters of the abo~e polymer solution was placed on 2.5 in. x 5 in. glass plate. A film was cast with a 0.02 in. thickness doctor blade. The cast film was first drîed at room temperature in the hood until most of the solvent had evaporated. The glass plate with film was transferred to a forced air oven at 40C for four hours *Trade Mark and at 75C for an additional four hoursO The glass with film was removed from the oven and examined for its com-patibility. The remainder of the po:Lymer solution was poured into 150 ml of 200-proof ethanol. A white polymer was precipiated which was collected by suction filtration.
The polymer was washed four times with 50 ml of ethanol.
The polymer was placed in a vacuum oven at 100C until the weight was constant.
Following the above procedure, various alloys were prepared having different weight ratios of polymers.
The glass transition temperature, Tg, for these alloys is shown in Table 2.

PoLyarylate, Wt % Polycarbonate, Wt ~ Tg, C

15~

Claims (50)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A polyarylate copolymer derived from (A) a mixture of a 5-keto-bis(hydroxyphenyl)-anthracene compound of the formula wherein R1, R2, R3 and R4 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl;
and a bisphenol compound selected from the group consist-ing of wherein R5, R6, R7 and R8 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl;

wherein R9, R10, R11 and R12 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; and herein R13, R14, R15 and R16 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; and wherein the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol is from 20:1 to 1:20; and (B) a mixture of isophthalic and terephthalic acid in a molar ratio of 9:1 to 1:9, respectively.

2. The copolymer according to Claim 1, wherein R1, R2, R3 and R4 are hydrogen.

3. The copolymer according to Claim 1, wherein R1, R2, R3 and R4 are independently lower alkyl of 1 to 4 carbon atoms.

4. The copolymer according to Claim 3, wherein R1, R2, R3 and R4 are methyl.

5. The copolymer according to Claim 1, wherein the bisphenol compound is wherein R5, R6, R7 and R8 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl.

6. The copolymer according to Claim 5, wherein R5, R6, R7 and R8 are hydrogen.

7. The copolymer according to Claim 5, wherein R5, R6, R7 and R8 are independently lower alkyl of 1 to 4 carbon atoms.

8. The copolymer according to Claim 7, wherein R5, R6, R7 and R8 are methyl.

9. The copolymer according to Claim 1, wherein the bisphenol compound is wherein R9, R10, R11 and R12 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl.

10. The copolymer according to Claim 9, wherein R9, R10, R11 and R12 are hydrogen.

11. The copolymer according to Claim 9, wherein R9, R10, R11 and R12 are independently lower alkyl of 1 to 4 carbon atoms.

12. The copolymer according to Claim 11, wherein R9, R10, R11 and R12 are methyl.

13. The copolymer according to Claim 1, wherein the bisphenol compound is wherein R13, R14, R15 and R16 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl.

14. The copolymer according to Claim 13, wherein R13, R14, R15 and R16 are hydrogen.

15. The copolymer according to Claim 13, wherein R13, R14, R15 and R16 are independently lower alkyl of 1 to 4 carbon atoms.

16. The copolymer according to Claim 15, wherein R13, R14, R15 and R16 are methyl,

17. The copolymer according to Claim 1, wherein the molar ratio of isophthalic to terephthalic acid is about 3:1 to 1:3.

18. The copolymer according to Claim 17, wherein the molar ratio of isophthalic to terephthalic acid is about 1:1.

19. The copolymer according to Claim 1, wherein the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol is about 9:1 to 1:9.

20. The copolymer according to Claim 19, wherein the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol is about 4:1 to 1:4.

21. A polyarylate alloy composition comprising (A) 10 to 90% by weight of a polyarylate of the formula wherein R1, R2, R3 and R4 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; n is the degree of polymerization; and wherein is an isophthalic or terephthalic acid moiety present in a molar ratio of 9:1 to 1:9, respectively; and (B) 10 to 90% by weight of a polymer resin selected from the group consisting of polybisphenol A carbonate and polystyrene.

22. The composition according to Claim 21, wherein R1, R2, R3 and R4 are hydrogen.

23. The composition according to Claim 21, wherein R1, R2, R3 and R4 are independently lower alkyl of 1 to 4 carbon atoms.

24. The composition according to Claim 23, wherein R1, R2, R3 and R4 are methyl.

25. The composition according to Claim 21, wherein the molar ratio of the isophthalic to terephthalic acid moiety is about 3:1 to 1:3.

26. The composition according to Claim 25, wherein the molar ratio of the isophthalic to terephthalic acid moiety is about 1:1.

27. The composition according to Claim 21, wherein component (B) is polystyrene. A carbonate.

28. The composition according to Claim 21, wherein component (B) is polystyrene.

29. A polyarylate alloy composition comprising (A) 10 to 90% by weight of a polyarylate copolymer derived from (1) a mixture of a 5-keto-bis(hydroxyphenyl)-anthracene compound of the formula wherein R1, R2, R3 and R4 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl;
and a bisphenol compound selected from the group consist-ing of wherein R5, R6, R7 and R8 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl;

wherein R9, R10, R11 and R12 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; and wherein R13, R14, R15 and R16 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl; and wherein the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol is from 20:1 to 1:20; and (2) a mixture of isophthalic and terephthalic acid in a molar ratio of 9:1 to 1:9, respectively; and (B) 10 to 90% by weight of a polymer resin selected from the group consisting of polybisphenol A carbonate and polystyrene.

30. The composition according to Claim 29, wherein R1, R2, R3 and R4 are hydrogen.

31. The composition according to Claim 29, wherein R1, R2, R3 and R4 are independently lower alkyl of 1 to 4 carbon atoms.

32. The composition according to Claim 31, wherein R1, R2, R3 and R4 are methyl.

33. The composition according to Claim 29, wherein the bisphenol compound is wherein R5, R6, R7 and R8 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl.

34. The composition according to Claim 33, wherein R5, R6, R7 and R8 are hydrogen.

35. The composition according to Claim 33, wherein R5, R6, R7 and R8 are independently lower alkyl of 1 to 4 carbon atoms.

36. The composition according to Claim 35, wherein R5, R6, R7 and R8 are methyl.

37. The composition according to Claim 29, wherein the bisphenol compound is wherein R9, R10, R11 and R12 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl.

38. The composition according to Claim 37, wherein R9, R10, R11 and R12 are hydrogen.

39. The composition according to Claim 37, wherein R9, R10, R11 and R12 are independently lower alkyl of 1 to 4 carbon atoms.

40. The composition according to Claim 39, wherein R9, R10, R11 and R12 are methyl.

41. The copolymer according to Claim 29, wherein the bisphenol compound is wherein R13, R14, R15 and R16 are independently hydrogen, lower alkyl of 1 to 4 carbon atoms or phenyl.

42. The copolymer according to Claim 41, wherein R13, R14, R15 and R16 are hydrogen.

43. The copolymer according to Claim 41, wherein R13, R14, R15 and R16 are independently lower alkyl of 1 to 4 carbon atoms.

44. The copolymer according to Claim 43, wherein R13, R114, R15, and R16 are methyl.

45. The composition according to Claim 29, wherein the molar ratio of isophthalic to terephthalic acid is about 3:1 to 1:3.

46. The composition according to Claim 45, wherein the molar ratio of isophthalic to terephthalic acid is about 1:1.

47. The composition according to Claim 29, wherein the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol is about 9:1 to 1:9.

48. The composition according to Claim 47, wherein the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to bisphenol is about 4:1 to 1:4.

49. The composition according to Claim 29, wherein component (B) is polybisphenol A carbonate.

50. The composition according to Claim 29, wherein component (B) is polystyrene.