Patent Publication Number: US-4731433-A

Title: Aromatic copolyester derived from aromatic dicarboxylic acid component and aromatic diol component

Description:
This invention relates to an aromatic copolyester derived from an aromatic dicarboxylic acid component and an aromatic diol component, which is not described in the known literature and has excellent heat resistance and hydrolysis resistance. 
     More specifically, this invention relates to an aromatic copolyester comprising substantially equimolar proportions of [A] units derived from an aromatic dicarboxylic acid having 8 to 16 carbon atoms, and [B] units derived from an aromatic diol component; characterized in that 
     (I) the diol component [B] is composed of 20 to 95 mole%, based on the total moles of compounds (a) and (b) below, of 
     (a) a bisphenol compound represented by the formula ##STR2##  wherein X represents a direct bond, or a divalent group selected from the class consisting of C 1  -C 8  alkylidene groups, O, S, SO, SO 2  and CO, and 
     (b) 5 to 80 mole%, based on the total moles of the compounds (a) and (b), of a compound selected from the group consisting of 
     (b-1) a divalent phenolic compound represented by the formula ##STR3##  wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  represents a hydrogen atom or a lower alkyl group, 
     (b-2) a dihydric phenol compound represented by the formula ##STR4##  wherein each of R 9  and R 10  represents a lower alkyl group, and each of R 11  and R 12  represents a hydrogen atom or a lower alkyl group, 
     (b-3) a divalent phenol compound represented by the formula ##STR5##  wherein each of R 13  and R 14  represents a hydrogen atom, a lower alkyl group or a phenyl group, 
     (b-4) a dihydric phenol compound represented by the formula ##STR6##  wherein each of R 15 , R 16 , R 17  and R 18  represents a lower alkyl group, and each of R 19 , R 20 , R 21  and R 22  represents a hydrogen atom, a lower alkyl group or a phenyl group, and 
     (b-5) a dihydric phenol compound represented by the formula ##STR7##  wherein each of R 23 , R 24 , R 25  and R 26  represents a hydrogen or a lower alkyl group provided that at least one of R 23  to R 26  is a lower alkyl group, and X&#39; represents O or S, and 
     (II) the aromatic copolyester has an intrinsic viscosity [η], determined at 60° C. in pentafluorophenol, of at least 0.4 dl/g. 
     Many proposals have heretofore been made on heat-resistant aromatic polyesters or copolyesters derived from an aromatic dicarboxylic acid component such as terephthalic acid or isophthalic acid and an aromatic diol component such as bisphenols, for example in J. Polymer Science, 40, 399 (1959), Visokomol. Soyed, 1, 834 (1959), Japanese Patent Publication No. 15247/1963 (corresponding to British Pat. No. 924,607), British Pat. No. 897,640, Japanese Patent Publication No. 5599/1962 (corresponding to U.S. Pat. No. 3,133,898), and Japanese Laid-Open Patent Publications Nos. 73021/1982, 96019/1982, 111317/1982, and 180525/1983. These known aromatic polyesters or copolyesters have the defect of inferior hydrolysis resistance at high temperatures. For example, poly(isopropylidene-4,4&#39;-diphenylene isophthalate terephthalate) which has already come into commercial production readily undergoes hydrolysis in an atmosphere where water is present at high temperatures, for example in boiling water, and are drastically reduced in performance. Thus, the conventional aromatic polyesters or copolyesters have the defect that they have inferior hydrolysis resistance at high temperatures, and are susceptible to hydrolysis during molding or during use at high temperatures. 
     The present inventors have made extensive investigations in order to provide an aromatic copolyester which can overcome the aforesaid technical trouble or defect. These investigations have now led to the discovery that an aromatic copolyester comprising substantially equimolar proportions of [A] units derived from an aromatic dicarboxylic acid component having 8 to 16 carbon atoms and [B] units derived from an aromatic diol wherein the aromatic diol component consists essentially of at least two specific aromatic diol components (a) and (b) in specified proportions exhibit excellent heat resistance and hydrolysis resistance. 
     It is an object of this invention therefore to provide a novel aromatic copolyester having excellent heat resistance and hydrolysis resistance and derived from an aromatic dicarboxylic acid component and an aromatic diol component. 
     The above and other objects of this invention along with its advantages will become apparent from the following description. 
     In the present invention, aromatic dicarboxylic acids having 8 to 16 carbon atoms are used as the aromatic dicarboxylic acid component [A]. These ester-forming aromatic dicarboxylic acids are well known per se, and can be used in the production of the aromatic copolyester of this invention. The component [A] may be aromatic dicarboxylic acids having 8 to 16 carbon atoms, and functional derivatives thereof such as acid halides and aryl esters (e.g., phenyl or triphenyl esters). Specific examples include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, mixtures of at least two of these acids, and the functional derivatives thereof. Preferred units [A] derived from the aromatic dicarboxylic acid component are those derived from a component selected from the group consisting of terephthalic acid, isophthalic acid and a mixture of both. The units derived from a mixture of both are especially preferred. 
     In the present invention, the aromatic diol component [B] is composed of 20 to 95 mole% of the bisphenol compound (a) and 5 to 80 mole% of the dihydric phenol compound (b), the proportions being based on the total moles of the bisphenol compound (a) and the dihydric phenol compound (b) selected from the compounds (b-1) to (b-5) mentioned above. Preferably, it is composed of 25 to 90 mole%, more preferably 30 to 80 mole%, of the bisphenol compound (a) and 10 to 75 mole%, more preferably 20 to 70 mole%, of the dihydric phenol compound (b). 
     The bisphenol compound (a) is represented by the following formula ##STR8## wherein X represents a direct bond or a divalent group selected from the class consisting of alkylidene groups having 1 to 8 carbon atoms, O, S, SO, SO 2  and CO. 
     Examples of the C 1  -C 8  alkylidene groups are methylidene, ethylidene and propylidene. Specific examples of the bisphenol compound (a) are 
     4,4&#39;-dihydroxydiphenyl, 
     bis(4-hydroxyphenyl)methane, 
     2,2-bis(4-hydroxyphenyl)propane, 
     2,2-bis(4-hydroxyphenyl)butane, 
     4,4&#39;-cyclohexylidenediphenol, 
     1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 
     4,4&#39;-dihydroxybenzophenone, 
     4,4&#39;-dihydroxydiphenylether, 
     4,4&#39;-thiodiphenol, and 
     bis(4-hydroxyphenyl)sulfone. 
     The dihydric phenol compound (b) is selected from the compounds (b-1) to (b-5). 
     The dihydric phenol compound (b-1) is represented by the following formula ##STR9## wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  represents a hydrogen atom or a lower alkyl group. 
     In the above formula, the lower alkyl group may be an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl and isopropyl. Specific examples of the dihydric phenol compound (b-1) include 
     1,3-bis(4-hydroxycumyl)benzene, 
     1,4-bis(4-hydroxycumyl)benzene, 
     1,3-bis(3,5-dimethyl-4-hydroxycumyl)benzene, 
     1,4-bis(3,5-dimethyl-4-hydroxycumyl)benzene, 
     1,3-bis(3,5-dimethyl-4-hydroxycumyl)benzene, and 
     1,4-bis(3,5-dimethyl-4-hydroxycumyl)benzene. 
     The dihydric phenol compound (b-2) is represented by the following formula ##STR10## wherein each of R 9  and R 10  represents a lower alkyl group and each of R 11  and R 12  represents a hydrogen atom or a lower alkyl group. 
     The lower alkyl group in the above formula may be an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or isopropyl. Specific examples of the dihydric phenol compound (b-2) include 
     2,5-dimethylhydroquinone, 
     2,6-dimethylhydroquinone, 
     2-ethyl-5-methylhydroquinone, 
     2,4,6-trimethylresorcinol, 
     2,3,5,6-tetramethylhydroquinone, 
     2-isopropyl-5-methylhydroquinone, 
     2-ethyl-3,5,6-trimethylhydroquinone, 
     2,5-di-n-propylhydroquinone, and 
     2-n-propyl-3,5,6-trimethylhydroquinone. 
     The dihydric phenol compound (b-3) is represented by the following formula ##STR11## wherein each of R 13  and R 14  represents a hydrogen atom, a lower alkyl group or a phenyl group. 
     The lower alkyl group may be an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or isopropyl. Specific examples of the dihydric phenol compounds (b-3) includes 
     3,6-dihydroxyxanthene, 
     3,6-dihydroxy-9-methylxanthene, 
     3,6-dihydroxy-9,9-dimethylxanthene, 
     3,6-dihydroxy-9-methyl-9-ethylxanthene, 
     3,6-dihydroxy-9-methyl-9-isobutylxanthene, and 
     3,6-dihydroxy-9-methyl-9-phenylxanthene. 
     The dihydric phenol compound (b-4) is represented by the following formula ##STR12## wherein each of R 15 , R 16 , R 17  and R 18  represents a lower alkyl group, and each of R 19 , R 20 , R 21  and R 22  represents a hydrogen atom, a lower alkyl group or a phenyl group. 
     The lower alkyl group in the above formula may, for example, be an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or isopropyl. Specific examples of such dihydric phenol compound (b-4) include 
     9,10-dihydro-2,4,5,7-tetramethyl-3,6-dihydroxyanthracene, 
     9-hydro-2,4,5,7,10,10-hexamethyl-3,6-dihydroxyanthracene, 
     2,4,5,7,9,10-hexamethyl-3,6-dihydroxyanthracene, 
     2,4,5,7,9,9,10,10-octamethyl-3,6-dihydroxyanthracene, 
     2,4,5,7,9,10,10-heptamethyl-9-ethyl-3,6-dihydroxyanthracene, 
     2,4,5,7,9,10-hexamethyl-9,10-diethyl-3,6-dihydroxyanthracene, 
     2,4,5,7,9,10,10-heptamethyl-9-phenyl-3,6-dihydroxyanthracene, and 
     2,4,5,7-tetraethyl-9,9,10,10-tetramethyl-3,6-dihydroxyanthracene. 
     The dihydric phenol compound (b-5) is represented by the following formula ##STR13## wherein each of R 23 , R 24 , R 25  and R 26  represents a hydrogen atom or a lower alkyl group provided that at least one of R 23  to R 26  is a lower alkyl group, and X&#39; represents O or S. 
     The lower alkyl group may be an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or isopropyl. Specific examples of the dihydric phenol compound (b-5) are bis(3,5-dimethyl-4-hydroxyphenyl)ether and bis(3,5-dimethyl-4-hydroxyphenyl)sulfide. 
     The aromatic copolyesters of this invention consists of the units [A] derived from the aromatic dicarboxylic acid component and the units [B] derived from the aromatic diol component condensed in the alternately arranged state, and is a substantially linear high polymer as a result of formation of ester linkages. The molecular end of the copolyester may be a carboxyl group, or a hydroxyl group. Alternatively, the terminal carboxyl group may be esterified with a lower alcohol, or the terminal hydroxyl group may be esterified with a lower carboxylic acid. 
     The aromatic copolyester of this invention has an intrinsic viscosity [η], measured at 60° C. in pentafluorophenol, of at least 0.4 dl/g, preferably at least 0.5 dl/g, and a glass transition temperature of preferably at least 130° C., for example 130° to 300° C., more preferably 150° to 280° C. In addition to excellent heat resistance shown by the above glass transition temperature, the aromatic copolyester of this invention has an excellent hydrolysis resistance of, for example, at least 60%, preferably at least 65%, especially preferably at least 70%. 
     Means of producing polyesters from aromatic dicarboxylic acids and aromatic diols by utilizing known polyester-forming reactions such as solution polymerization, melt polymerization and interfacial polymerization are well known and established in the art, and can be utilized in the production of the aromatic copolyesters of this invention. They are briefly described below. 
     Melt-polymerization: 
     The aromatic dicarboxylic acid or its ester-forming derivative and the aromatic diol or its ester-forming derivative are reacted in the molten state at a high temperature, and low-boiling compounds formed as by-products by the reaction are removed from the reaction system by, for example, distillation under reduced pressure (see, for example, Japanese Patent Publication No. 15247/1963 corresponding to British Pat. No. 924,607). The reaction conditions may, for example, include agitation, a reaction temperature of about 250° to 400° C. and a reaction pressure of atmospheric pressure to 0.1 mmHg. 
     Solution polymerization: 
     A solution of the aromatic dicarboxylic acid or its ester-forming derivative or its acid halide and the aromatic diol or its ester-forming derivative is formed by using a high-boiling solvent such as diphenyl ether, benzophenone, meta-terphenyl, chlorinated biphenyl and brominated naphthalene. The solution is reacted at a high temperature, or if required in the presence of a basic compound such as a tertiary amine and N-methylpyrrolidone to promote the reaction (see, for example, Japanese Patent Publication No. 5599/1962 corresponding to U.S. Pat. No. 3,133,898 and British Pat. No. 966,483; Industrial and Engineering Chemistry, 51, 147 (1959)). The reaction conditions may, for example, include agitation, a reaction temperature of about 100° to 300° C., and a reaction pressure of atmospheric pressure to 0.1 mmHg. 
     Interfacial polymerization: 
     An acid halide of the aromatic dicarboxylic acid is dissolved in an organic solvent, and separately, the aromatic diol is converted to its metal salt such as sodium salt and dissolved in water. The two solutions are then brought into contact with each other to react on their interface the acid halide with the salt of the aromatic diol [see for example, J. Polym. Sci., 40, 399 (1959); British Pat. No. 897,640; Japanese Patent Publication No. 18399/1962; and Japanese Patent Publication No. 4996/1967). The reaction conditions include agitation, a reaction temperature of about 0° to 100° C., and a reaction pressure of atmospheric pressure. 
     Since the aromatic copolyesters of this invention have better heat resistance and hydrolysis resistance than conventional aromatic polyesters, their degradation during melt-molding and during use at high temperatures can be prevented. 
     The aromatic copolyesters of this invention can be used for example as component part of electrical and electronic instruments and appliances, automobiles, and precision instruments and appliances. 
     The following examples specifically illustrate the production of the aromatic copolyesters of this invention and their excellent properties. 
     In these examples, the amounts of the starting materials, solvents, catalysts and other materials used are indicated in parts by weight. 
     The glass transition point of the aromatic copolyester is determined by a differential scanning calorimeter. 
     The hydrolysis resistance of the aromatic copolyester is the percent retention of the intrinsic viscosity [η] of a molded article of the polyester immersed for 10 days in boiling water based on its initial intrinsic viscosity before immersion. 
     The heat distortion temperature of the aromatic copolyester was measured and determined in accordance with JIS K-6871. 
     The mechanical properties were measured and determined in accordance with the methods of JIS K-6745 and JIS K-6719. 
    
    
     EXAMPLE 1 
     A reactor was charged with 83 parts of terephthalic acid, 83 parts of isophthalic acid, 156 parts of 2,2-bis(4-acetoxyphenyl)propane, 243 parts of 1,4-bis(3,5-dimethyl-4-acetoxycumyl)benzene, 0.33 part of triphenyl phosphate and 0.1 part of tetrabutoxy titanate, and they were reacted at 250° at 270° C. under atmospheric pressure for about 2 hours with stirring in an atmosphere of nitrogen while distilling off acetic acid formed. Furthermore, over the course of about 2 hours, the pressure of the reaction system was gradually reduced, and its temperature was raised so that finally the pressure reached 0.7 mmHg and the temperature rose to 350° C. The resulting aromatic polyester had an intrinsic viscosity [η] of 0.75 dl/g, a glass transition temperature of 232° C., and a hydrolysis resistance of as high as 96%. 
     COMPARATIVE EXAMPLE 1 
     Example 1 was repeated except that 1,4-bis(3,5-dimethyl-4-acetoxycumyl)benzene was not used but 312 parts of 2,2-bis(4-acetoxyphenyl)propane was used. The resulting aromatic copolyesters had an intrinsic viscosity [η] of 0.68 dl/g, a glass transition temperature of 186° C., and a hydrolysis resistance of 48%. 
     EXAMPLES 2-8 
     Example 1 was repeated except that the aromatic dicarboxylic acids, aromatic binuclear bisphenol diacetates and aromatic trinuclear bisphenol diacetates indicated in Table 1 were used in the proportions indicated. The intrinsic viscosities, glass transition temperatures and hydrolysis resistances of the resulting aromatic polyesters are summarized in Table 1. 
     
                                           TABLE 1                                 
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   Aromatic dicarboxylic                                                  
                 Aromatic binuclear                                       
                               Aromatic trinuclear                        
                                                  Glass                   
Ex-                                                                       
   acid          bisphenol diacetate                                      
                               bisphenol diacetate                        
                                             Intrinsic                    
                                                  transition              
                                                         Hydrolysis       
am-         Amount        Amount        Amount                            
                                             viscosity                    
                                                  temperature             
                                                         resistance       
ple                                                                       
   Type     (parts)                                                       
                 Type     (parts)                                         
                               Type     (parts)                           
                                             [η] (dl/g)               
                                                  (°C.)            
                                                         (%)              
__________________________________________________________________________
2  Terephthalic acid                                                      
            83   2,2-bis(4-                                               
                          93.7 1,4-bis(3,5-Di-                            
                                        340.2                             
                                             0.75 236    98               
   Isophthalic acid                                                       
            83   Acetoxyphenyl)-                                          
                               methyl-4-acetoxy-                          
                 propane       cumyl)benzene                              
3  Terephthalic acid                                                      
            83   2,2-bis(4-                                               
                          249.6                                           
                               1,4-bis(3,5-Di-                            
                                        97.2 0.74 220    84               
   Isophthalic acid                                                       
            83   Acetoxyphenyl)-                                          
                               methyl-4-acetoxy-                          
                 propane       cumyl)benzene                              
4  Terephthalic acid                                                      
            149.4                                                         
                 2,2-bis(4-                                               
                          156  1,4-bis(3,5-Di-                            
                                        243  0.69 230    96               
   2,6-Naphthalene-                                                       
            21.6 Acetoxyphenyl)-                                          
                               methyl-4-acetoxy-                          
   dicarboxylic acid                                                      
                 propane       cumyl)benzene                              
5  Terephthalic acid                                                      
            83   2,2-bis(4-                                               
                          93.6 1,4-bis(4-Acetoxy-                         
                                        301  0.70 218    85               
   Isophthalic acid                                                       
            83   Acetoxyphenyl)-                                          
                               cumyl)benzene                              
                 propane                                                  
6  Terephthalic acid                                                      
            83   2,2-bis(4-                                               
                          93.6 1,3-bis(4-Acetoxy-                         
                                        301  0.75 215    82               
   Isophthalic acid                                                       
            83   Acetoxyphenyl)-                                          
                               cumyl)benzene                              
                 propane                                                  
7  Terephthalic acid                                                      
            16.6 1-Phenyl-1,1-                                            
                          187  1,4-bis(3,5-Di-                            
                                        243  0.71 236    96               
   Isophthalic acid                                                       
            149.4                                                         
                 bis(4-acetoxy-                                           
                               methyl-4-acetoxy-                          
                 phenyl)ethane cumyl)benzene                              
8  Terephthalic acid                                                      
            116.2                                                         
                 4,4&#39;-Diacetoxy-                                          
                          143  1,4-bis(3,5-Di-                            
                                        243  0.76 218    95               
   Isophthalic acid                                                       
            49.8 diphenyl ether                                           
                               methyl-4-acetoxy-                          
                               cumyl)benzene                              
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     EXAMPLE 9 
     A reactor was charged with 83 parts of terephthalic acid, 83 parts of isophthalic acid, 156 parts of 2,2-bis(4-acetoxyphenyl)propane, 243 parts of 1,3-diacetoxy-2,4,6-trimethylbenzene, 0.33 part of triphenyl phosphate and 0.1 part of tetrabutoxy titanate. They were reacted at 250° to 270° C. under atmospheric pressure for 2 hours with stirring in an amosphere of nitrogen while distilling off acetic acid formed. Furthermore, over the course of 2 hours, the pressure of the reaction system was gradually reduced, and the temperature was raised so that finally, the pressure reached 0.7 mmHg and the temperature rose to 350° C. The resulting aromatic polyester had an intrinsic viscosity [η] of 0.71 dl/g, a glass transition temperature of 190° C., and a hydrolysis resistance of 78%. 
     EXAMPLES 10-13 
     Example 9 was repeated except that the aromatic dicarboxylic acids, aromatic binuclear bisphenol diacetates and alkyl-substituted aromatic dihydric phenol diacetates indicated in Table 2 were used in the proportions indicated. The intrinsic viscosities, glass transition temperatures and hydrolysis resistances of the resulting aromatic polyesters are summarized in Table 2. 
     
                                           TABLE 2                                 
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   Aromatic dicarboxylic                                                  
                 Aromatic binuclear                                       
                               Alkyl-substituted aromatic                 
                                                  Glass                   
Ex-                                                                       
   acid          bisphenol diacetate                                      
                               dihydric phenol diacetate                  
                                             Intrinsic                    
                                                  transition              
                                                         Hydrolysis       
am-         Amount        Amount        Amount                            
                                             viscosity                    
                                                  temperature             
                                                         resistance       
ple                                                                       
   Type     (parts)                                                       
                 Type     (parts)                                         
                               Type     (parts)                           
                                             [η] (dl/g)               
                                                  (°C.)            
                                                         (%)              
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10 Terephthalic acid                                                      
            83   2,2-bis(4-                                               
                          93.6 1,4-Diacetoxy-                             
                                        155.4                             
                                             0.73 189    79               
   Isophthalic acid                                                       
            83   Acetoxyphenyl)-                                          
                               2,6-dimethyl-                              
                 propane       benzene                                    
11 Terephthalic acid                                                      
            83   2,2-bis(4-                                               
                          249.6                                           
                               1,4-Diacetoxy-                             
                                        52.8 0.65 195    74               
   Isophthalic acid                                                       
            83   Acetoxyphenyl)-                                          
                               2,3,6-trimethyl-                           
                 propane       5-ethylbenzene                             
12 Terephthalic acid                                                      
            83   1-Phenyl-1,1-                                            
                          187  bis(3,5-Dimethyl-                          
                                        179  0.70 196    96               
   Isophthalic acid                                                       
            83   bis(4-acetoxy-                                           
                               4-acetoxyphenyl)-                          
                 phenyl)ethane sulfide                                    
13 Terephthalic acid                                                      
            83   4,4&#39;-Diacetoxy-                                          
                          143  bis(3,5-Dimethyl-                          
                                        171  0.73 180    87               
   Isophthalic acid                                                       
            83   diphenyl ether                                           
                               4-acetoxyphenyl)-                          
                               ether                                      
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     EXAMPLES 14-16 
     An aromatic copolyester was produced by using each of the diols, each of the aromatic dicarboxylic acid dichlorides indicated in Table 3 in the proportions indicated. 
     An aqueous solution prepared by dissolving the diol indicated in Table 3, sodium hydroxide (82.8 parts), sodium hydrosulfiate (2 parts) and triethylbenzyl ammonium bromide (1.8 parts) in water (5000 parts) and a solution of the aromatic dicarboxylic acid dichloride indicated in Table 3 in methylene chloride (3000 parts) were contacted at 10° to 20° C. with stirring at high speeds to perform interfacial polymerization. Acetone was added to the reaction mixture to precipitate the resulting aromatic polyester, and the precipitate was isolated and recovered. 
     Table 3 summarizes the intrinsic viscosities, glass transition temperatures, heat distortion temperatures, tensile strengths and Izod impact strengths of the resulting aromatic polyesters. 
     
                                           TABLE 3                                 
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                                         Heat                             
                              Intrin-    distor-                          
                              sic        tion                             
   Aromatic dicarboxylic                                                  
                aromatic trinuclear                                       
                              viscos-                                     
                                  Glass  tem-     Izod                    
Ex-                                                                       
   acid dichloride                                                        
                diol acetate  ity transition                              
                                         pera-                            
                                             Tensile                      
                                                  impact Hydrolysis       
am-        Amount        Amount                                           
                              [η]                                     
                                  temperature                             
                                         ture                             
                                             strength                     
                                                  strength                
                                                         resistance       
ple                                                                       
   Type    (parts)                                                        
                Type     (parts)                                          
                              (dl/g)                                      
                                  (°C.)                            
                                         (°C.)                     
                                             (kg/cm.sup.2)                
                                                  (kg-cm/cm)              
                                                         (%)              
__________________________________________________________________________
14 Terephthaloyl                                                          
           203  3,6-Dihydroxy-                                            
                         121  0.83                                        
                                  231    198 730  19     81               
   dichloride   9,9-dimethyl-                                             
                xanthene                                                  
                2,2-bis(4-                                                
                         114                                              
                Hydroxyphenyl)-                                           
                propane                                                   
15 Terephthaloyl                                                          
           203  3,6-Dihydroxy-                                            
                         60.5 0.80                                        
                                  254    196 709  17     77               
   dichloride   9,9-dimethyl-                                             
                xanthene                                                  
                2,2-bis(4-                                                
                         171                                              
                Hydroxyphenyl)-                                           
                propane                                                   
16 Terephthaloyl                                                          
           101.5                                                          
                3,6-Dihydroxy-                                            
                         121  0.82                                        
                                  240    197 700  24     75               
   dichloride   9,9-dimethyl-                                             
                xanthene                                                  
   Isophthaloyl                                                           
           101.5                                                          
                2,2-bis(4-                                                
                         114                                              
   dichloride   Hydroxyphenyl)-                                           
                propane                                                   
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     EXAMPLES 17-21 
     Example 14 was repeated except that each of the diols and each of the aromatic dicarboxylic acid dichlorides indicated in Table 4 were used in the proportions indicated. 
     Table 4 summarizes the intrinsic viscosities, glass transition temperatures, heat distortion temperatures and hydrolysis resistances of the aromatic polyesters obtained. 
     
                                           TABLE 4                                 
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   Aromatic dicarboxylic                   Glass  Heat                    
Ex-                                                                       
   acid dichloride                                                        
                Diol                  Intrinsic                           
                                           transition                     
                                                  distortion              
                                                         Hydrolysis       
am-        Amount                Amount                                   
                                      viscosity                           
                                           temperature                    
                                                  temperature             
                                                         resistance       
ple                                                                       
   Type    (parts)                                                        
                Type             (parts)                                  
                                      [η] (dl/g)                      
                                           (°C.)                   
                                                  (°C.)            
                                                         (%)              
__________________________________________________________________________
17 Terephthaloyl                                                          
           203  3,6-Dihydroxy-9,9-dimethylxanthene                        
                                 121  0.72 248    203    73               
   dichloride   1-Phenyl-1,1-bis(4-hydroxyphenyl)-                        
                                 145                                      
                ethane                                                    
18 Terephthaloyl                                                          
           203  3,6-Dihydroxy-9,9-dimethylxanthene                        
                                 121  0.84 252    214    79               
   dichloride   bis(4-Hydroxyphenyl)sulfone                               
                                 125                                      
19 Terephthaloyl                                                          
           142.1                                                          
                3,6-Dihydroxy-9,9-dimethylxanthene                        
                                 121  0.84 246    206    84               
   dichloride                                                             
   2,6-Naphthalene                                                        
           75.9 2,2-bis(4-Hydroxyphenyl)propane                           
                                 114                                      
   dicarboxylic                                                           
   acid dichloride                                                        
20 Terephthaloyl                                                          
           203  3,6-Dihydroxyxanthene                                     
                                 107  0.79 227    190    77               
   dichloride   2,2-bis(4-Hydroxyphenyl)propane                           
                                 114                                      
21 Terephthaloyl                                                          
           202  3,6-Dihydroxy-9-methyl-9-phenyl-                          
                                 152  0.74 244    200    80               
   dichloride   xanthene                                                  
                2,2-bis(4-Hydroxyphenyl)propane                           
                                 114                                      
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     EXAMPLES 22-24 
     Aromatic copolyesters were produced by using the aromatic dicarboxylic acids and diol diacetates shown in Table 5 in the amounts indicated. 
     A reactor was charged with each of the aromatic dicarboxylic acids, each of the diol acetates, triphenyl phosphate (0.33 parts) and tetrabutoxy titanate (0.1 part), and they were reacted at 250° to 310° C. under atmospheric pressure for about 1.5 hours with stirring in an atmosphere of nitrogen while distilling off acetic acid. Then, over the course of about 2 hours, the pressure of the reaction system was gradually reduced, and the temperature was raised so that finally the pressure reached about 1 mmHg and the temperature rose to 355° C. 
     Table 5 summarizes the intrinsic viscosities, glass transition temperatures and hydrolysis resistances of the resulting aromatic polyesters. 
     
                                           TABLE 5                                 
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                                                  Glass                   
Aromatic dicarboxylic acid                                                
                  Diacetate of diol         Intrinsic                     
                                                  transition              
                                                         Hydrolysis       
             Amount                   Amount                              
                                            viscosity                     
                                                  temperature             
                                                         resistance       
Example                                                                   
     Type    (parts)                                                      
                  Type                (parts)                             
                                            [η] (dl/g)                
                                                  (°C.)            
                                                         (%)              
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22   Terephthalic acid                                                    
             83   2,4,5,7,9,9,10,10-Octamethyl-3,6-                       
                                      204   0.74  213    95               
                  diacetoxyanthracene                                     
     Isophthalic acid                                                     
             83   2,2-bis(4-Acetoxyphenyl)propane                         
                                      156                                 
23   Terephthalic acid                                                    
             83   2,4,5,7,9,9,10,10-Octamethyl-3,6-                       
                                      102   0.76  208    86               
                  diacetoxyanthracene                                     
     Isophthalic acid                                                     
             83   2,2-bis(4-Acetoxyphenyl)propane                         
                                      234                                 
24   Terephthalic acid                                                    
             166  2,4,5,7,9,9,10,10-Octamethyl-3,6-diacetoxy-             
                                      204   0.59  232    96               
                  anthracene                                              
                  2,2-bis(4-Acetoxyphenyl)octapropane                     
                                      156                                 
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     EXAMPLES 25-29 
     Example 22 was repeated except that the aromatic dicarboxylic acids and diol diacetates indicated in Table 6 were used in the proportions indicated. 
     Table 6 summarizes the intrinsic viscosities, glass transition temperatures and hydrolysis resistances of the resulting aromatic polyesters of the resulting aromatic copolyesters. 
     
                                           TABLE 6                                 
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                                                 Glass                    
Aromatic dicarboxylic acid                                                
                  Diacetate of diol        Intrinsic                      
                                                 transition               
                                                        Hydrolysis        
             Amount                  Amount                               
                                           viscosity                      
                                                 temperature              
                                                        resistance        
Example                                                                   
     Type    (parts)                                                      
                  Type               (parts)                              
                                           [η] (dl/g)                 
                                                 (°C.)             
                                                        (%)               
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25   Terephthalic acid                                                    
             83   2,4,5,7,9,9,10,10-Octamethyl-3,6-                       
                                     204   0.70  218    95                
                  diacetoxyanthracene                                     
     Isophthalic acid                                                     
             83   1-Phenol-1,1-bis(4-acetoxyphenyl)-                      
                                     187                                  
                  ethane                                                  
26   Terephthalic acid                                                    
             83   2,4,5,7,9,9,10,10-Octamethyl-3,6-                       
                                     204   0.73  223    94                
                  diacetoxyanthracene                                     
     Isophthalic acid                                                     
             83   bis(4-Acetoxyphenyl)sulfone                             
                                     167                                  
27   Isophthalic acid                                                     
             149.4                                                        
                  2,4,5,7,9,9,10,10-Octamethyl-3,6-                       
                                     204   0.75  210    94                
                  diacetoxyanthracene                                     
     2,6-Naphthalene-                                                     
             21.6 2,2-bis(4-Acetoxyphenyl)propane                         
                                     156                                  
     dicarboxylic acid                                                    
28   Terephthalic acid                                                    
             83   9,10-Dihydro-2,4,5,7-tetramethyl-                       
                                     176   0.75  210    90                
                  3,6-diacetoxyanthracene                                 
     Isophthalic acid                                                     
             83   2,2-bis(4-Acetoxyphenyl)propane                         
                                     156                                  
29   Terephthalic acid                                                    
             83   2,4,5,7,9,10,10-Heptamethyl-9-phenyl-                   
                                     235   0.67  219    95                
                  3,6-diacetoxyanthracene                                 
     Isophthalic acid                                                     
             83   2,2-bis(4-Acetoxyphenyl)propane                         
                                     156                                  
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