Abstract: A process is disclosed for converting .alpha.,.omega.-bis(2,6-dimethylphenol)poly(2,6-dimethyl-1,4-phenylene oxide) ("PPO--2OH" for brevity), and the corresponding thiophenol-poly(phenylene sulfide) ("PPS--2SH"), by the oxidative copolymerization of 2,6-dimethylphenol (DMP) with 2,2'-di)4-hydroxy-3,5-dimethylphenyl propane ("TMBPA"), or, of 2,6-dimethylthiophenol (DMTP) with 2,2-di(4-thiol-3,5-dimethylthiophenyl propane ("TMBTPA") respectively. Specifically, a mixture of water-methanol or chlorobenzene-methanol is used as the medium in which the reaction of DMP with TMBPA is carried out. By using a particular range of ratios of DMP to TMBPA and different solvent mixtures, the molecular weight of the PPO--2OH is tailored to be in the range from about 1000 to about 5000.

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.

Abstract: A modified Williamson etherification in the presence of phase transfer catalyst is used to synthesize alternating block copolymers and regular copolymers. Unsaturated polyethers of a polynuclear dihydric phenol containing chloroallylic (electrophilic) end groups (prepared from cis- or trans-1,4-dichloro-2-butene and Bisphenol A) and aromatic poly(ether sulfone)s containing terminal phenol (nucleophilic) groups are polycondensed in the presence of tetrabutylammonium hydrogen sulfate as phase transfer catalyst to give alternating block copolymers. The same telechelic polymers were chain-extended with dinucleophilic or dielectrophilic monomers under similar reaction conditions. Both the regular copolymers and the alternating block copolymers were characterized by gel permeation chromatography and DSC.

Abstract: A method for the synthesis of polyarylene polyether (PAPE) oligomers with pendant vinyl groups is presented. Aromatic polyether sulfone (APS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) backbones are used for specific examples. Terminal vinyl groups may also be provided on the APS by forming the .alpha., .omega.-di(benzyl)APS before the first step of a synthesis to form pendant groups which step involves the chloromethylation of APS and PPO to provide oligomers with chloromethyl groups. PPO containing bromomethyl groups was obtained by radical bromination of the PPO methyl groups. Both chloromethylated and bromomethylated starting materials are converted to their phosphonium salts, and then subjected to a phase transfer catalyzed Wittig reaction to provide the pendant vinyl groups. An APS containing pendant ethynyl groups is prepared by bromination of the APS with pendant vinyl groups, followed by a phase transfer catalyzed dehydrobromination.

Abstract: Oligomers of polyarylene polyethers (PAPE) having a mol wt Mn in the range from 1000 to about 10,000 are converted 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 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.