Aromatic ketone and sulfone polymers and process for the preparation thereof

Claim 2

A polymer which comprises repeating units of the general formula: --M--Ar--D--Ar'-- wherein each of M and D, which may be the same or different, is ##STR22## or --SO 2 --, Ar is a group of the formula ##STR23## wherein L is ##STR24## phenyleneoxy, ##STR25## a covalent bond, --O--, --S--, a group of the formula --CR 2 -- wherein each of the R groups, which may be the same or different, is --H, alkyl, fluoroalkyl, phenyl or phenyl substituted by an electron-withdrawing group, or a group of the formula --O--Ar--O-- wherein Ar is as defined above; and Ar' is a group of the formula ##STR26## wherein T is --O--, --S--, phenyleneoxy, a group of the formula --CR 2 -- as defined above or a group of the formula --O--Ar--O-- as defined above; the polymer molecules being capped at each end by a capping group, each of the capping groups, which may be the same or different, being a group of the formula ##STR27## wherein X is a covalent bond --O--, --S--, or a group of the formula --CR 2 -- as defined above, and Y is --CN, --NO 2 , ##STR28## or, if X is a covalent bond, hydrogen; a group of the formula ##STR29## wherein Ar" is a phenyl, naphthyl, biphenyl or terphenyl group which is unsubstituted or substituted by at least one electron-withdrawing group which is substituted on the phenoxyphenyl group which is substituted on the phenoxy moiety by at least one electron-withdrawing group; or a group of the formula --SO 2 --AR" wherein Ar" is as defined above.

Claim 3

The polymer of claim 1 wherein D and M are ##STR30##

Claim 4

The polymer of claim 1 wherein D and M are --SO 2 --.

Claim 5

The polymer of claim 1 wherein Ar is phenylene.

Claim 6

The polymer of claim 1 wherein Ar is ##STR31##

Claim 7

The polymer of claim 5 wherein L is ##STR32##

Claim 8

The polymer of claim 5 wherein L is --O--.

Claim 9

The polymer of claim 1 wherein the T of Ar' is --O-- or phenyleneoxy.

Claim 10

The polymer of claim 1 wherein T is --O--.

Claim 11

The polymer of claim 1 wherein the capping groups are independently ##STR33##

Claim 12

The polymer of claim 1 wherein Y of both capping groups is ##STR34##

Claim 13

The polymer of claim 1 wherein one of the capping groups is ##STR35## and Y of the other is ##STR36##

Claim 14

In a process for the preparation of a polymer in accordance with claim 1 by the Friedel-Crafts catalyzed condensation polymerization of: (Type A) a first monomer of mixture of monomers comprising a diacid halide and a second monomer or mixture of monomers containing at least two aromatically bound hydrogen atoms displaceable in said condensation polymerization, or (Type B) a monomer or mixture of monomers each of said monomer or monomers having at least one aromatically bound hydrogen atom displaceable in said condensation polymerization and at least one acid halide group, the improvement comprising adding to the polymerization reaction in a Type A polymerization from about 0.002 to about 0.10 moles of a nucleophilic capping agent, as hereinafter defined, per mole of first monomer when said first monomer is present in molar excess; from about 0.002 to about 0.10 moles of an electrophilic capping agent, as hereinafter defined, per mole of second monomer when said second monomer is in molar excess; and from about 0.001 to about 0.05 moles of each of an electrophilic and a nucleophilic capping agent per mole of said first monomer when said first and second monomers are present in substantially equimolar amounts; and from about 0.001 to about 0.05 moles of each of an electrophilic and a nucleophilic capping agent per mole of monomer in a Type B polymerization, wherein said nucleophilic capping agent has the general formula ##STR37## wherein X is a covalent bond, --O--, --S--, or --CR 2 -- wherein each R is independently hydrogen, or an alkyl or fluoroalkyl group of 1 to 10 carbons, phenyl or an electron withdrawing group substituting phenyl and Y is ##STR38## or when X is a covalent bond Y is hydrogen, and wherein said electrophilic capping agent has the general formula Ar"COZ or Ar"SO 2 Z wherein Z is OH, halogen or OR wherein R is an alkyl group and wherein Ar" is phenyl, phenoxyphenyl, naphthyl, biphenyl or terphenyl either unsubstituted or substituted with at least one electron withdrawing substituent.

Claim 15

The process of claim 13 wherein said polymerization is catalysed by a mixture of hydrogen fluoride and boron trifluoride.

Claim 16

The process of claim 13 wherein said nucleophilic capping agent is biphenyl, 4-phenoxybenzophenone or an equimolar mixture of diphenyl ether and benzoic acid.

Claim 17

The process of claim 13 wherein said electrophilic capping agent is benzoic acid or benzene sulfonic acid.

Claim 18

The process of claim 13 wherein said capping agent is added at the beginning of said polymerization.

Claim 19

The process of claim 13 wherein said polymerization is a Type B polymerization and wherein said electrophilic and said nucleophilic capping agents are added in substantially equimolar amounts.

Claim 20

The process of claim 18 wherein said capping agents are each present in an amount equal to 0.002 to 0.01 moles per mole of monomer.

Claim 21

The polymer of claim 1 comprising recurring units of the structure ##STR39##

Claim 22

The polymer of claim 1 comprising recurring units of the structure ##STR40##

Claim 23

The polymer of claim 1 comprising recurring units of the structure ##STR41##

Claim 24

The polymer of claim 1 comprising recurring units of the structure ##STR42## wherein Q is ##STR43## or --SO 2 --.

Claim 25

The polymer of claim 1 wherein said polymr has an inherent viscosity ranging from about 0.5 to about 2.0 for a solution having a concentration of 0.1 g polymer per 100 ml. of concentrated sulfuric acid at 25° C.

Claim 26

The polymer of claim 1 comprising recurring units of the structure ##STR44##

Claim 27

The polymer of claim 1 comprising recurring units of the structure ##STR45##

Claim 28

The polymer of claim 1 comprising recurring units of the structure ##STR46##

Claim 29

The polymer of claim 1 comprising recurring units of the structure ##STR47##

Claim 30

The polymer of claim 1 comprising the recurring unit ##STR48##

Claim 31

The polymer of claim 1 comprising recurring units of the structure ##STR49##

Claim 32

The polymer of claim 1 comprising recurring units of the structure ##STR50##

Claim 33

The polymer of claim 1 comprising recurring units of the structure ##STR51##

Claim 34

The polymer of claim 1 comprising recurring units of the structure ##STR52##

Claim 35

The polymer of claim 1 wherein R is an alkyl or fluoroalkyl group of 1 to 10 carbon atoms.

Claim 36

The polymer of claim 1 wherein the number of repeating units is from about 5 to about 300.

Claim 37

A polymer according to claim 1 wherein the electron withdrawing groups are selected from members of the group consisting of halogen, nitro and cyano.

Claim 38

A process according to claim 13 wherein the electron withdrawing groups are selected from members of the group consisting of halogen, nitro and cyano.