Non-catalytic process for the preparation of difunctionalized

Abstract

A non-catalytic process converts oligomers of polyarylene polyethers (PAPE) having a mol wt Mn in the range from 1000 to about 10,000 to difunctionalized oligomers so as, in the first instance, to provide a reactive double bond (for example, a vinylbenzyl group) at each end of the PAPE; and, in the second instance to provide a triple bond (benzylethynyl group) at each end of the PAPE. The solubility of intermediate bisphenolates of (i) a dihydric phenol, and of (ii) the PAPE oligomer in particular solvents which allow (a) water of reaction to be removed without being degraded, and (b) essentially complete end-capping of the oligomer chains with vinyl chain ends, are the keys to the novel process. The PAPE most preferably has a repeating unit which is the residuum of two dihydric phenols or thiophenols ('DHP') linked through a C.dbd.O, --S--S--, or --SO.sub.2 - group, or a Si or C atom, and/or ether O, or thioether S atoms. The preferred repeating unit is formed by reaction of a DHP such as bisphenol A (BPA) with a halogenated DHP such as dichlorophenyl sulfone (DCPS) so as to provide an alternating configuration. The repeating unit may also include a linking residue of a reactive solvent which residue provides chain extension in the backbone. An oligomer which is a homopolymer having a repeating unit in which at least four benzenoid rings are connected through ether O atoms, may also be difunctionalized. In particular, .alpha..omega.-di(phenol)aromatic polyether sulfone oligomers ('APS') are esterified so as to have terminal methacrylyl groups; and, etherified so as to have styryl end groups which are thermally crosslinkable.