Thermoplastic aromatic polyetherketones

Abstract

Tough crystalline thermoplastic aromatic polyetherketones containing the repeat units ##STR1## alone or in conjunction with other repeat units especially ##STR2## and having an inherent viscosity IV of at least 0.7, preferably at least 0.8. The polymers may be made by condensation of hydroquinone, 4,4'-difluorobenzophenone and an alkali metal carbonate or bicarbonate in the presence of an aromatic sulphone solvent, e.g. diphenylsulphone, at 150°-400° C. The polymers are very useful for wire coating.

We claim: 
     
       1. A tough crystalline thermoplastic aromatic polyetherketone containing the repeat unit I ##STR23## alone or in conjunction with other repeating units selected from the group consisting of the repeating units IV ##STR24## where A is a direct link, oxygen, sulphur, --SO 2  --, --CO--, or a divalent hydrocarbon radical, the oxygen atoms in the sub-units ##STR25## are ortho or para to the groups Q and Q', Q and Q' which may be the same or different are --CO-- or --SO 2  --, Ar' is a divalent aromatic radical, and n is 0, 1, 2 or 3, said polymer having an inherent viscosity IV, as measured at 25° C. on a solution of the polymer in concentrated sulphuric acid of density 1.84 g.cm 3  said solution containing 0.1 g of polymer in 100 cm 3  of solution, of at least 0.7 (which corresponds to a reduced viscosity RV, as measured at 25° C. on a solution of the polymer in concentrated sulphuric acid of density 1.84 g.cm 3  said solution containing 1 g of polymer in 100 cm 3  of solution, of at least 0.8. 
     
     
       2. A polyetherketone according to claim 1 having IV of at least 0.8 (which corresponds to RV of at least 0.9). 
     
     
       3. A polyetherketone according to claim 1 which contains only repeating units I and repeating units IX ##STR26## 
     
     
       4. A polyetherketone according to claim 1 which contains only repeating units I and repeating units VIII ##STR27## .[. 
     
     
       5.  A process for the production of a tough crystalline thermoplastic polyetherketone containing the repeat unit I ##STR28## alone or in conjunction with other repeating units selected from the group consisting of the repeating units IV ##STR29## where A is a direct link, oxygen, sulphur, --SO 2  --, --CO--, or a divalent hydrocarbon radical, the oxygen atoms in the sub-units ##STR30## are ortho or para to the groups Q and Q', Q and Q' which may be the same or different are --CO-- or --SO 2  --, Ar' is a divalent aromatic radical, and n is 0, 1, 2 or 3, which process comprises polycondensing, under substantially anhydrous conditions, at least one bisphenol which is hydroquinone or hydroquinone and at least one other bisphenol of formula ##STR31## where A is as defined above and at least one aromatic dihalide which is 4,4'-difluorobenzophenone or 4,4'-difluorobenzophenone and at least one other aromatic dihalide of formula ##STR32## where X and X' which may be the same or different are halogen atoms and are ortho or para to the groups Q and Q', and Q, Q', Ar' and n are as defined above, there being substantially equimolar amounts of bisphenol and aromatic dihalide, in the presence of at least one alkali metal carbonate or bicarbonate used in an amount providing at least 2 gram atoms of alkali metal per mole of bisphenol, the alkali metal or metals being selected from sodium, potassium, rubidium, and caseium provided that the sole use of sodium carbonate and/or bicarbonate is excluded, and in the presence of a solvent having the formula ##STR33## where Y is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and Z and Z' are hydrogen or phenyl groups, within the temperature range 150° to 140° C., the final temperature level during the polycondensation being sufficiently high to maintain the final polymer in solution, such that a polymer having IV of at least 0.7 (which corresponds to RV of at least 0.8) is obtained..]. 
     
     
       6. A process according to claim .[.5.]. .Iadd.12 .Iaddend.wherein the solvent is diphenylsulphone. 
     
     
       7. A process according to claim .[.5.]. .Iadd.12 .Iaddend.wherein the monomers for the polycondensation are solely hydroquinone and 4,4'-difluorobenzophenone. 
     
     
       8. A process according to claim .[.5.]. .Iadd.12 .Iaddend.wherein said at least one alkali metal carbonate or bicarbonate is a mixture of sodium carbonate or bicarbonate with a carbonate or bicarbonate of an alkali metal of higher atomic number, the amount of higher alkali metal carbonate or bicarbonate being such that there are 0.001 to 0.2 gram atoms of the higher alkali metal per gram atom of sodium. 
     
     
       9. A process according to claim 8 wherein said at least one alkali metal carbonate is a mixture of sodium carbonate with potassium carbonate. .[.10. A fabricated structure comprising a tough crystalline thermoplastic polyetherketone containing the repeat unit I ##STR34## alone or in conjunction with other repeating units selected from the groups consisting of the repeating units IV ##STR35## where A is a direct link, oxygen, sulphur, --SO 2  --, --CO--, or a divalent hydrocarbon radical, the oxygen atoms in the sub-units ##STR36## are ortho or para to the groups Q and Q', Q and Q' which may be the same or different are --CO-- or --SO 2  --, Ar' is a divalent aromatic radical, and n is 0, 1, 2 or 3, said polymer having IV of at least 0.7 
     
     
        (corresponding to RV of at least 0.8)..]. 11. A fabricated structure according to claim .[.10.]. .Iadd.13 .Iaddend.in the form of electrical 
     
     
        insulation. .Iadd.12.  A process for the production of a tough crystalline thermoplastic polyetherketone containing the repeat unit I ##STR37##.Iaddend. alone or in conjunction with other repeating units selected from the group consisting of the repeating units IV ##STR38## the repeat units V ##STR39## and the repeat units VI ##STR40## where A is a direct link, oxygen, sulphur, --SO 2  --, --CO--, or a divalent hydrocarbon radical, the oxygen atoms in the sub-units ##STR41## are ortho or para to the groups Q and Q', Q and Q' which may be the same or different are --CO-- or --SO 2  --, Ar' is a divalent aromatic radical, and n is 0, 1, 2 or 3, which process comprises polycondensing, under substantially anhydrous conditions, at least one bisphenol which is hydroquinone or hydroquinone and at least one other bisphenol of formula ##STR42## where A is as defined above and at least one aromatic dihalide which is 4,4'-difluorobenzophenone or 4,4'-difluorobenzophenone and at least one other aromatic dihalide of formula ##STR43## where X and X' which may be the same or different are halogen atoms and are ortho or para to the groups Q and Q', and Q, Ar' and n are as defined above, there being substantially equimolar amounts of bisphenol and aromatic dihalide, in the presence of at least one alkali metal carbonate or bicarbonate used in an amount providing at least 2 gram atoms of alkali metal per mole of bisphenol, the alkali metal or metals being selected from sodium, potassium, rubidium, and caesium provided that the sole use of sodium carbonate and/or bicarbonate is excluded, and in the presence of a solvent having the formula ##STR44## where Y is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and Z and Z' are hydrogen or phenyl groups, within the temperature range 150° C. to 400° C., the final temperature level during the polycondensation being sufficiently high to maintain the final polymer in solution, such that a polymer having IV of at least 0.7 (which corresponds to RV of at least 0.8) is obtained. 
     
     
        .Iadd.3.  A fabricated structure comprising a tough crystalline thermoplastic polyetherketone containing the repeat unit I ##STR45##.Iaddend. alone or in conjunction with other repeating units selected from the groups consisting of the repeating units IV ##STR46## the repeat units V ##STR47## and the repeat units VI ##STR48## where A is a direct link, oxygen, sulphur, --SO 2  --, --CO--, or a divalent hydrocarbon radical, the oxygen atoms in the sub-units ##STR49## are ortho or para to the groups Q and Q', Q and Q' which may be the same or different are --CO-- or --SO 2  --, Ar' is a divalent aromatic radical, and n is 0, 1, 2 or 3, said polymer having IV of at least 0.7 
     
     
        (corresponding to RV of at least 0.8).  .Iadd.14.  A tough crystalline thermoplastic aromatic polyetherketone consisting essentially of the repeat unit I ##STR50##.Iaddend. alone or in conjunction with at most 50 mole %, based on the total repeating units, of other repeating units selected from the group consisting of the repeating units IV ##STR51## the repeat units V ##STR52## and the repeat units VI ##STR53## divalent hydrocarbon radical, the oxygen atoms in the subunits ##STR54## are ortho or para to the groups Q and Q', Q and Q' which may be the same or different are --CO-- or --SO 2  --, Ar' is a divalent aromatic radical, and n is 0, 1, 2 or 3, said polymer having an inherent viscosity IV, as measured at 25° C. on a solution of the polymer in concentrated sulphuric acid of density 1.84 g.cm 3  said solution containing 0.1 g of polymer in 100 cm 3  of solution, of at least 0.7 (which corresponds to a reduced viscosity RV, as measured at 25° C. on a solution of the polymer in concentrated sulphuric acid of density 1.84 g.cm 3  of solution, of at least 0.8) said solution containing 1 g 
     
     
        of polymer in 100 cm 3 .  .Iadd.15.  A process for the production of a tough crystalline thermoplastic polyetherketone which process comprises polycondensing, under substantially anhydrous conditions, at least one bisphenol which is hydroquinone or hydroquinone and at least one other co-condensate bisphenol of the formula ##STR55##.Iaddend. where A is a direct link, oxygen, sulphur, --SO 2  --, --CO--, or a divalent hydrocarbon radical, and at least one aromatic dihalide which is 4,4'-difluorobenzophenone or 4,4'-difluorobenzophenone and at least one co-condensate aromatic dihalide of formula ##STR56## where X and X' which may be the same or different are halogen atoms and are ortho or para to the groups Q and Q', Q and Q, which may be the same or different are --CO-- or --SO 2  --, Ar' is a divalent aromatic radical at most 50 mole % of the total amount of bisphenol and/or aromatic dihalide being said co-condensates, there being substantially equimolar amounts of bisphenol and aromatic dihalide, in the presence of at least one alkali metal carbonate or bicarbonate used in an amount providing at least 2 gram atoms of alkali metal per mole of bisphenol, the alkali metal or metals being selected from sodium, potassium, rubidium, and caesium provided that the sole use of sodium carbonate and/or bicarbonate is excluded, and in the presence of a solvent having the formula ##STR57## where Y is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and Z and Z' are hydrogen or a phenyl group, within the temperature range 150° C. to 400° C., the final temperature level during the polycondensation being sufficiently high to maintain the final polymer in solution, such that a polymer having an IV of at least 0.7 (which corresponds to an RV of at least 0.8) is 
     
     
        obtained.  .Iadd.16.  A polymer which may be obtained by the process of claim 15. .Iaddend.