STRESS-CRACK RESISTANT POLYARYLATES AND PROCESS FOR THE PREPARATION

Abstract: The invention deals with novel polyarylates and a pro­ cess for their preparation. Polyarylates derived from a mixture of iso and tereph­ thalic acids and 4,4′-biphenol and bisphenol A were found to afford melt stable polyesters having good solvent and stress crack resistance.

Description: STRESS-CRACK RESISTANT POLYARYLATES AND PROGRESS FOR THE FREPARATION BACKGROUND OF THE IWENTION This invention pertains to stress-crack resistant polyarylates and more particularly to bisphenol A iso/terephthalates modified with 4,4' -biphenol. Polyarylates or polyesters derived from bishenol A and iso/terephthalic acids are tough materials having a continuous use temperature of about 1400C. However, as with many other amorphous thermoplastics, they possess poor solvent and stress-crack resistance. Such polyesters may be represented as having repeating units as shown below EMI1.1 On the other hand, H. G. Weyland et al. reported in Euro. Poly J. 6, 1339 (1970) that a 4,4' -biphenol iso/terephthalate prepared by interfacial polymerization was both insoluble and infusible. Isophthalates of 4,4' -biphenol modified with hydroquinone are described in U.S. 3,036,991 and 3,160,602. These copolymers contain at least 40 mol percent of hydroquinone isophthalate and were prepared via the reaction of the di-functional phenols with isophthaloyl chloride in solvents boiling above 300 C. These polyesters are highly crystalline having melting points ranging from 350 to 4000C. SlowLy cooled moldings are crystalline and translucent while rapidly cooled or quenched moldings are amorphous and transparent. No mechanical data are revealed in these references. Linear co-polyesters have been prepared from terephthalic or isophthalic acid, a bizphenol and hydroquinone containing 5 to 35 mol percent of the hydroquinone. Bisphenol A polyesters of isophthalic acid, terephthalic acid or iso/terephthalic acid mixtures lack solvent and stress-crack resistance. 4,4' -Biphenol polyesters of iso/terephthalic acid mixtures are solvent resistant but are not melt processable. U.S. 3,939,117 discloses a method for producing a-polyarylene ester at temperatures of O to 1000C in an organic solvent for the polyarylene ester in the presence of solid Ca (OH)2 and a polymerization catalyst. One or more divalent phenols and aromatic dicarboxylic chlorides are used butthere is no appreciation of the use of a particular ratio of particular divalent phenols to afford polyarylates having enhanced solvent and stress crack resistance. SWtARY OF THE INVENTION It has now been unexpectedly found that polyarylate compositions that contain isophthalic acid moieties or a mixture of isophthalic and terephthalic acid moieties, and about 20 to about 80 mol percent of 4,4' -biphenol moieties and about 80 to about 20 mol percent of bisphenol A moieties based on total diphenol content of the polymer are solvent resistant, stress crack resistant and melt processable. The diacids and dlhydric phenols are in essentially stoichiometric quantities. The preferred polyarylate compositions consist of a dicarboxylic acid structure consisting essentially of isophthalic/terephthalic acid mol ratios of about 50/50 to about 100/0 together with a dihydric phenol mixture consisting es sentially of 4,4' -biphenol/bisphenol A mol ratios of about 20/80 to about 50/50. The more preferred composition consist of an isophthalic/terephthalic acid mol ratio of about 50/50 to about 75/25 and a dihydric phenol mixture consisting eo- sentially of a 4,4' -biphenol/bisphenol A mol ratio of about 30/70 to about 55/45. The resultant copolyarylates have both enhanced solvent resistance and stress crack resistance and they possess excellent thermal properties, processability, toughness and flammability characteristics. This combination of properties was unexpected in view of the properties of the polyarylates prepared from either bisphenol A or 4,4' -biphenol alone. The polyarylates can be prepared by any of the polyester forming reactions known to those skilled in the art. Either of two additive sequences of reactants can be used. In the first procedure, diacid and the diphenol reactants are charged and polymerized simultaniously (hereinafter referred to as simultanious addition). In the second procedure one of the diphenol reactants is charged with the acid reactants, polymerization is initiated and then the other diphenol reactant is added and the reaction is allowed to progress (hereinafter referred to as sequential addition). The normally solid polyarylates have the following repeating units [(A)-(B)] [(A)-(D)] wherein A is a mixture of EMI3.1 in a mol ratio containing up to about 90 mol percent of the former; EMI3.2 wherein each of R1 and H2 are each H or alkyl groups having 1 to about 7 carbons, R3, R4, R5, and R6, are alkyl groups having 1 to about 18 carbons, and a and b are integers having values of O to 4 EMI4.1 wherein the mol ratio of [(A)(B)] to [(A)(D)] is in the range of about 20 to about 80 to about 80 to about 20 and the mole ratio of A to B and D is approximately stoichiometric. Exemplary 2,2-bis (p-hydroxyphenyl) alkanes include 2,2-bis-(4-hydroxyphenyl) 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-hydroxyphenyl)ethane, 1 , 1 -bis- (4-hydroxy-2-chlorophenyl) ethane, 1 , 1 -bis- (3-methyl-4-hydroxyphenyl) ethane, 1 ,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis-(2-isopropyl-4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxynaphthyl)propane, 2,2-bis-(4-hydroxyphenyl)pentane, 3,3-bis-(4-hydroxyphenyl)pentane, 2,2-bis-(4-hydroxyphenyl)heptane, and 1,2-bis-(4-hydroxyphenyl)-1,2-bis-(phenyl)-propane. Any known polyester forming reactions can be used to make the polyarylates, such as 1) The reaction of the acid chlorides of isophthalic and terephthalic acids with the diphenols. 2) The reaction of the aromatic diacids with diester derivatives of the diphenols EMI5.1 where R=C1 to C20 aliphatic skeletons, hereinafter referred to as the Diacetate Process. 3) The reaction of the diaryl esters of the aromatic diacids EMI5.2 where Ar can be a phenyl, o-tolyl, m-tolyl,-tolyl, or like residues, with the diphenols, hereinafter referred to as the Diphenate Process. Two procedures can be used for the preparation of the polyarylates via the acid chloride route. One is carried out at low temperature and the other at high temperature. In the low temperature technique polycondensation of the acid chlorides derived from terephthalic and isophthalic acid with the dihy dric phenols is effected at ambient temperatures in an inert solvent, such as methylene chloride, in the presence of a basic catalyst and an acid acceptor. A second immiscible solvent, e.g., water, may be present. In the high temperature technique, polycondensation of acid chlorides with the dihydric phenols is effected in a high boiling solvent, such as, 1,2,4-trichlorobenzene, at temperatures above about 1500C and preferably at about 200 to about 22000. Other suitable inert organic solvents useful for low temperature polycondensation include halogenated aliphatic com pounds, such as, chloroform, methylene bromide, 1,1,2-trich- loroethane as well as methylene chloride mentioned above and the like; and cyclic ethers such as tetrahydrofuran, dioxane, and the like. For the high temperature polycondensation, suitable solvents include halogenated aromatic compounds such as, o-dichlorobenzene, 1 ,2,4-trichlorobenzene, diphenyl ether, diphenyl sulfone, benzoic acid alkyl esters wherein the alkyl group contains 1 to about 12 carbon atoms, phenolic ethers, suc as, anisole, and the like. Preferred acid acceptors for use in the low temperature polycondensation are alkali metal and alkaline earth hydro xides including sodium, potassium, barium, calcium, strontium magnesium, and beryllium hydroxide. Useful basic catalysts for use in the low temperature polycondensation include tertiary amines such as alkyl amines, including trimethylamine, triethylamine, triporpylamine, tributylamine, and the like; where the alkyl group contains from 1 to about 10 carbon atoms; alkaryl amines such as, N,N-dimethylaniline, N, N-diethylaniline, N,N-dimethylnaphthylamine, b enzyl dimethylamine, alpha-methylb enzyl dimethylamine, pyridine, cyclic diazo compounds, such as, diazobicyclooctane (DABCO), diazo bicyclononene (DUN) and diazobicycloundecene (DBU) and the like. Polymerizations using the Diacetate Process can be carried out in the melt at between 2600C and 3400C, preferably between 2750C and 32000. They can also be carried out either as a solution reaction at those temperatures or a suspension reaction also at those temperatures. The solvent(s) or suspending agent(s) can be one of any number of organic compounds boiling between 1400C and 34000. They can be chosen from hydrocarbons, ketones, ethers, or sulfones which are inert under the reaction conditions. These polymerizations may or may not be run in the presence of a catalyst. Typical solvents are tetramethylene sulfone, diphenyl ether, substituted diphenyl ether, and the like. Typical catalysts include Na, Li, K salts (organic and inorganic), transition metal salts, alkaline earth metal salts, e.g., Mg acetate, and the like. They may be performed at atmospheric pressure, supra atmospheric pressure, or under vacuum. Polymerizations carried out using the Diphenate Process can be carried out in the melt at between 2850C and 35000. The preferred temperature range is about 3000C to 34000. In general reduced pressure for the final portions of the reaction is used. They can also be carried out either as a solution reaction or suspension reaction under those conditions. The solvent(s) or suspending agent(s) are the same as those described above. Typical catalysX include tin compounds and generally those mentioned above for the diacetate process. Particularly preferred catalysts are Ti and tin salts, Mg acetate, and alkali metal salts, alkoxides and phenoxides. Mechanical properties of the subject polyarylates were determined as a function of monomer content and mode of addition. As shown in Tables I and II, excellent toughness, measured by pendulum impact values of " 1,110 kg-m/dm5, was acid eved for compositions containing less than 50 mol percent of 4,4'-biphenol and less than 50 mol percent of terephthalic acid. Polyarylates obtained via the acid chloride route using either the simultaneous or sequential addition methods gave approximately the same values. Examples of the thermal properties of 4,4-biphenol modified polyarylates are delineated in Table III. These data show that the high second order glass transition temperatures (Tg) are characteristic of the materials of this invention. In the acid chloride route the mode of addition of reactants (simultaneous vs. sequential) appears to have a slight effect on the Tg. However, a significant difference in the flow temperatures was noted under the same experimental conditions. In all cases, the temperature at which the sequentially prepared materials flow is significantly higher (greater than 3400C as opposed to 2900C to 31000). The 4,4?biphenol modified polyarylates showed improvement in stress crack resistance when the amount of 4,4'-bi- phenol was equal to or greater than 20 mol percent based on the total diphenol content. These data are presented in Table IT. Table IV also demonstrates the superior stress crack resistance of a copolymer derived from a 60/40 mol percent mixture of bisphenol A and 4,4'-biphenol and a 75/25 mol percent mixture of isophthalic acid and terephthalic acid over a polyarylate derived from bisphenol A alone and a 75/25 mol percent mixture of isophthalic acid and terephthalic acid. Compositions containing ) 20 biphenol are preferred. Those > 30 and < 55 are particularly preferred. The preferred isophthalic/terephthalic acid ratio is 50:50 to 100:0 while the most preferred is 50:50 to 75:25. Polyarylates modified with 4,4'-biphenol also display excellent flammability characteristics. This was demonstrated with a 60/40 mol ratio bisphenol A, 4,4'-biphenol copolymer (isophthalic acid/terephthalic acid mol ratio of 75/25) prepared by the simultaneous addition route and evaluated by the Underwriters 'laboratory1s Bulletin 94, Test Procedure (UI-94). The test results obtained with films ranging in thickness from 1.19 to 1.35 mm showed superior flammability characteristics as delineated in Table V. If desired a chain stopper can be used to control the molecular weight of the polyarylates obtained. Suitable agents include monohydric phenols or their derivatives, such as, p pnenyl-ohenol, and the like and monofunctional carboxylic acid or their derivatives, such as benzoic or naphthoic acids, and the like. The invention is further described in the Examples which follow. All partz and percentages are by weight unless otherwise specified. EXAMPLE 1 Preparation of Copolyarylates by the Simultaneous Addition Procedure via the Acid Chloride Route A two-liter resin kettle equipped with a paddle stirrer, reflux condenser leading to a caustic scrubber, thermometer and nitrogen inlet tube was charged with Ingredients Amounts Bisphenol A 68.49 g. (0.300 mol) 4,4'-Biphenol 37.24 g. (0.200 mol) Isophthaloyl Chloride 76.13 g. (0.375 mol) Terephthaloyl Chloride 25.38 g. (0.125 mol) p-Phenylphenol 1.55 g. (0.009 mol) 1,2,4-Trichlorobenzene 1200 ml. The reaction mixture was sparged with nitrogen for 20 minutes and then immersed in a hot oil bath at about 17000. It was heated at reflux (2150C) for 20 hours. The hot hazy yellow polymer solution was filtered through a medium frit sintered glass funnel and then poured into 3500 ml. of toluene. On cooling this solution became cloudy. After 3 to 4 hours at room temperature, the obtained suspension of fine polymer particles in toluene/trichlorobenzene was coagulated in methanol using a Waring Blender (500 ml of susr,ension/3000 ml methanol). The coagulated polymer was washed t'nree times in 3000 ml of methanol (2 minutes of stirring in the Waring Blender) and air dried for 3 hours. Further drying for 1 day at 1200C (under a vacuum of 20-30 mm) and 2 days at 1200C (under 0.5 mm vacuum) yielded melt stable material. EXiPLE 2 Preparation of Polyarylates Using the Sequential Addition Procedure via the Acid Chloride Process A 1000 ml four-necked round bottom flask equipped with a paddle stirrer, reflu: condenser leading to a caustic scrubber, thermometer, and N2 inlet was charged with Biphenol A 18.24 g. (0.080 mol) Isophthaloyl Chloride 15.23 g. (0.075 mol) Tetraphthaloyl Chloride 5.08 g. (0.025 mol) 1,2,4-Trichlorobenzene 200 ml The reaction mixture was sparged with N2 for 20 minutes and then immersed in a hot ( 1700C) oil bath. It was heated at reflux (2150C) for six to eight hours (till no HC1 was being evolved). The oil bath was removed and the following was added 4,4'-Biphenol 3.72 g. (0.020 mol) p-Phenylphenol .225 g. (0.0015 mol) 1,2,4-Trichlorobenzene 65 ml The flask was reimmersed in the hot oil bath and heated at reflux for an additional 16 hours. The hot yellow polymer solution was filtered through a medium frit sintered glass filter, poured into 1500 ml toluene and then worked up as described in Example 1 to yield a melt stable material RV= 0.72, MF10 min=17.8 dg/min. and MF30 min.=23.5 dg./min. The RV value (reduced viscosity) was obtained with solution of 0.2. of polyarylate in 100 ml.of P-chloroohenol at 490C. The MF (melt flow) values were obtained at 3550C and ten times the load specified in ASTI D-1238 for the Melt Index Test. EXAMPLE 3 Preparation of Copolyarylates using Calcium Hydroxide as the Acid Acceptor In a 500 ml four-necked round bottom flask equipped with a paddle stirrer, thermometer, a claisen adapter with a dropping funnel (200ml) and a reflux condenser, and a nitrogen inlet is charged with Bisphenol A 11.42 g. (0.05 mol) 4,4'-13iphenol 9.30 g. (0.05 mol) Calcium Hydroxide 17.81 g. (0.24 mol) Chloroform 200 ml The reaction mixture is sparged with nitrogen for 20 minutes and then triethylamine (70m1, 1 mol percent) is added; then a solution of Isophthaloyl chloride 15.23 g. (0.075) Terephthaloyl chloride 5.08 g. (0.025) Chloroform 50 ml is added over 12 minutes. The reaction temperature rises to 550 C, at which time the mixture is cooled in a water bath (30 O Temperature is stabilized at 320C after 10 minutes. Reaction mixture becomes thicker rapidly and the color slowly changes from blue to tan. The reaction mixture is stirred at room temperature for 4 hours, at which time terminator is added (p-phenyl phenol, .250 g. 0.0015 mol) and stirring continued for an additional hour. The reaction mixture is diluted with 750 ml of chloroform and filtered through a celite cake. The pale yellow solution is washed with acid (1000 ml 0.5 percent HC1) under high shear for 20 minutes and then 4 times with water (till neutrality), also under high shear. Solve-nt was removed to approximately half volume and the polymer is coagulated in 7000 ml methanol, and is worked up as described in Example 1. EXMiE 4 Preparation of Copolyarylates via the Diacetate Route A stirred 1 gallon stainless steel reactor (oil heated) fitted with a packed column and distillation head, nitrogen inlet tube and hydraulically driven agitator is charged with: 2,2-(4,4'-Diacetoxyphenyl)propane 840.0 g. (2.69 mol) 4,4'-Diacetoxybiphenyl 311.54 g. (1.15 mol) Isophthalic acid 319.1 g. (1.92 mol) Tenephthalic acid 319.1 g. (1.92 mel) Acetic Anhydride 19.6 g. (.192 mol) Magnesium acetate 0.14 g. (.000192 mol) Diphenyl ether 740 g. The reaction mixture is sparged with nitrogen for 30 minutes and then the oil heater is turned on. The reaction is heated to 2750C over the period of 1 hour and then the reaction is allowed to proceed at 275-2850C. Acetic acid begins to distill off when the reaction mixture reaches 2600C. The acetic acid is collected and the reaction system is maintained such that the diphenyl ether is refluxing in the column. After 4 to 5 hours the desired molecular weight is achieved, as evidenced by the power draw on the agitator. EXAMPLE 5 Preparation of Polyarylates by a One Pot Diacetate Route In the same equipment described in Example 4 is charged Bisphenol A 613.3 g. (2.69 mol) 4,4 -Biphenol 215.9 g. (1.15 mol) Acetic Anhydride 852.8 g. (8.45 mol) Isophthalic acid 319.1 g. (1.92 mol) Terephthalic acid 319.1 g. (1.92 mol) Magnesium acetate 0.14 g. (.192 mol) Diphenyl ether 740 g. The reaction mixture is sparged with nitrogen for 20 minutes and then the reaction mixture is heated to 1700C. The reaction is held at 17O0C for 1.5 hours and then the reaction mixture is heated to 2750C. The reaction then proceeds as des cribci in Example 4. EXAMPLE 6 Pren. ration of Pelyarylates via the Diphenate Process In the same equipment described in Example 4 is charged Bisphenol A 232.6 g. (1.02 mol) 4,4' -Biphenol 186.0 g. (1.00 mol) Diphenyl isophthalate 318.0 g. (1.00 mol) Diphenyl terephthalate 318.0 g. (1.00 mol) Magnesium (II) acetate .360 g. (100 ppm) Diphenyl Ether 214 g. The reaction is sparged with nitrogen for 40 minutes and then the reaction mixture is heated to 2800C for 2 hours. The temperature is increased to 3000C for 30 minutes and then a vacuum of 100 mm Hg is applied. The temperature of the reaction is increased to 3450C over a 2 hour period and simultaneously the vacuum is further reduced to approximately 1.0 mm Hg. The reaction vessel is then brought to atmospheric pressure under nitrogen and then discharged. The materials can be used alone or in admixture with inorganic fillers such as silica, calcium carbonate, glass fibers1 organic fibers, carbon fibers and others known to those skilled in the art. Moreover they are useful as constituents in polyblends (for instance with poly(ethylene) terephthalate, polycarbonates, (meth) acrylates, polystyrene, polymeric fluorinated hydrocarbons, elastomers, rubbers, polymethanes, and the like.) TABLE 1 MECHANICAL PROPERTIES OF 4,4'-BIPHENOL MODIFIED POLYARYLATES AT ISO/TEREPHTHALATE MOL RATIO OF 75/25 Bisphenol A/Biphenol Mol Ratio 100/0 80/20 80/20 60/40 60/40 50/50 40/60 30/70 Mode of Addition(1) A B B A B A A A Tensile modulus(2) (kg/cmê) 13,000 13,900 14,300 13,600 14,600 13,850 ----- 14,200 Tensile Strength(2) (kg/cmê) 552 531 581 541 519 541 ----- ---- Elongation at Break (2) (percent) 18 14 14 25 10 17 ----- 3 Pendulum Impact (kg-m/dm3) (3a) 1,330 1,320 1,440 2,070 1,560 1,380 Brittle 34 (3b) RV(4) 0.74 0.75 0.75 0.74 0.75 0.74 0.78 Insoluble (1) A-all reagents added simultaneously, B-reagents added using sequential addition method. (2) Measured by method described in ASTM D-638 (3a) Sampls were considered tough when Pendulum Impact was # 1,110 kg-m/dm (3b) Very brittle (4) At 49 C, in p-chlorophenol, 0.2 g/100 ml. (ASTM D-1238). TABLE II MECHANICAL PROPERTIES OF 4,4'-BIPHENOL MODIFIED POLYARYLATES : EFFECT OF ACID COMPOSITION Iso/terephthalate Mol Ratio 50/50 50/50 100/0 100/0 100/0 100/0 Bisphenol A/Biphenol Mol Ratio 70/30 50/50 70/30 57/30 60/40 50/50 Mode of Addition (1) A A A B A A Tensile Modulus(2) (kg/cmê) 13,800 13,850 12,500 14,600 13,300 14,900 Tensile Strength(2) (kg/cmê) 542 541 501 559 515 548 Elongation at Break (2) (percent) 10.5 11 26 8 18 13 Pendulum Impact (3a) (kg-m/dm3) 1,137 128(3b) 1,290 1,580 1,410 897 RV(4) 0.72 0.74 0.76 0.78 0.70 0.68 (1) A-all reagents added simultaneously, B-reagents added using sequential addition method. (2) Measured by method described in ASTM D-638 (3a) Sampls were considered tough when Pendulum Impact was # 1,110 kg-m/dm (3b) Very brittle (4) At 49 C, in p-chlorophenol, 0.2 g/100 ml. (ASTM D-1238). TABLE II THERMAL PROPERTIES OF 4,4'-BIPHENOL MODIFIED POLYARYLATES Iso/terephthalate Mol Ratio 75/25 75/25 75/25 75/25 75/25 50/50 50/50 100/0 100/0 100/0 100/0 Bisphenol A/Biphenol Mol Ratio 100/0 80/20 80/20 60/40 60/40 70/30 50/50 70/30 70/30 60/40 50/50 Mode of Addition(1) A A B A B A A A B A A Tg(2) (C ) 185 185 185 190 195 190 185 185 190 190 190 HDT (3) (C ) 170 170 170 175 180 175 170 170 175 175 175 Flow (4) (C ) --- 300 340 300 380 300 --- 290 370 290 300 (1) Cf Footnote 1, Table 1. (2) cf. "Second Order Transition Temperature and Fibre Properties" by A. Brown, Textile Research Journal 25, 891 (1955). (3) ASTN D-648-56. (4) ASTN D-1238. TABLE IV ENVIRONMENTAL STRESS RUPTURE RESULTS : 4,4'-BIPHENOL MODIFIED POLYARYLATES (a) Bisphenol A/ bisphenol Mol Ratio(RV) 80/20 (0.74) 80/20 (0.74) 60/40 (0.75) 100/0 (0.77) Preparative Method (b) A B A A Environment Stress Time to Rupture (Kg/cm2) Acetone 14 10 minutes C & 10 minutes NCNB -------- 3 seconds Rupture 69 ------- 10 seconds Rupture 10 minutes NCNB ------- Toluene 14 10 seconds Rupture 33 seconds Rupture 15 minutes C & 4 seconds Rupture 69 ------- 2 seconds Rupture 20 seconds Rupture ------- Trichloro- 14 ------- --------- 10 seconds Rupture 41 seconds Rupture ethylene 69 ------- --------- 3 seconds Rupture ------- Xylene 14 ------- --------- 1 hour NCNB 3 seconds Rupture 69 ------- --------- ------ ------- Carbon 69 10 minutes C & --------- 20 minutes NCNB 10 seconds Rupture Tetrachloride 138 ------- 30 minuten NCNB ------ ------- 276 ------- 15 seconds Rupture ------ ------- C & -crazed and brittle; NCNB-not crazed, not brittle a) Iso/terephthalate Mol Ratio For All Samples 75/25. b) As in Table II, Footnote (1). TBBLE V BISPHENOL A/BIPHENOL 60/40 POLYARYLATES RV-0.74 (ISO/TEREPHTHALATE RATIO 75/25) Additional Sample Thickness 30 Second N (mm) 1st Ignition 2nd Ignition Ignition 1 1.19 Out Instantly Out 2 Seconds Out 1 Second 2 1.19 Out Instantly Out 1 Second Out Instantly 3 1.35 Out 1 Second Out 1 Second Out Instantly 4 1.22 Out 2 Seconds Out 1 Second Out Instantly 5 1.22 Out 2 Seconds Out Instantly Out Instantly 6 1.22 Out 1 Second Out 2 Seconds Out Instantly Although the invention has been described in its preferred form with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example and that numerous changes can be made without departing from the spirit and scope of the invention.

Claims: CLAIMS 1. A normally solid polyarylate having the following repeating units [(A)(B)] [(A)(B)] wherein A is a mixture of terephthalic and isophthalic acid residues, viz., EMI20.1 in a mol ratio containing up to about 100 mol percent of the latter to a 50/50 mol ratio EMI20.2 wherein each of R1 and R2 are each H or alkyl groups having 1 to about 7 carbons, R3, R4, R5, and R6, are alkyl groups having 1 to about 18 carbons and a and b are integers having values of O to 4; EMI20.3 wherein the mol ratio of B to D is in the range of from about 20 mols of B to 80 mels of D to about 80 mols of B to about 20 mols of D and the mol ratio of A to B and D is approxima tely stoichiometric. 2. Polyarylate claimed in Claim 1 where 3 is a radical residuum of 2,2-bis(p-hydroxyphenyl) propane with both hydro- xyl E atom removed and D is the radical residuum of 4,4'-biphenol with both hydroxyl H atoms removed. Polyarylate claimed in Claim 1 wherein the mol ratio of the acid residues in A is about 50:50. 4. Polyarylate claimed in Claim 1 wherein A is a iso phthalic acid residue only. 5. Polyarylate claimed in Claim 1 wherein the mol ratio of B to D is from 70/30 to about 45/55. 6. Polyarylate claimed in Claim 1 wherein the mol ratio of the acid residues in A contain more than about 55 mols of isophthalic acid residues up to about 75 mols of isophthalic acid. 7. Polyarylate claimed in Claim 1 wherein R1,RR2, R3, and R4 are each methyl. 8. Polyarylate claimed in Claim 1 wherein R5 and R6 are each methyl and a and b are each 1. 9. Polyarylate claimed in Claim 1 wherein R1 and R2 are H or wherein R1 is methyl and R2 is butyl. 10. Process for preparing normally solid pelyarylates as claimed in anyone of the claims 1 to 9, characterized in that approximately stoichiometric proportionz of a mixture of terephthalic and isophthalic acid derivatives containing from 50 to 100 mol percent of the latter is reacted with a mixture containing 20 to 80 mol percent of 4,4'-biphenol reactant and 80 to 20 mol percent of biphenol-A reactant.

Inventors: BERGER, MITCHELL HARVEY, GARDNER, HUGH CHESTER, MATZNER, MARKUS
Applicants: UNION CARBIDE CORPORATION
Application year: 1980
Main classification: C08G63
IPC codes: C08G63