Difunctionalized polyarylene polyethers and process for preparat

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate

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Details

528212, 528219, 528373, 528374, 528375, 528376, 525534, C08G 6548, C08G 7523

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active

047015144

ABSTRACT:
Oligomers of polyarylene polyethethers (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=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. Illustrated are APS oligomers having BPA-DPS repeating units. The BPA moiety may be replaced with other diphenols. The synthesis of PAPE oligomers with terminal double bonds is carried out with a fast and quantitative modified Williamson etherification of the PAPE with an electrophilic haloalkyl reactant ("HAR") such as chloromethylstyrene ("CIMS") in the presence of a major molar amount (more than 50 mol% based on the number of moles of OH or SH groups originally present in the APS) of a phase transfer catalyst ("PTC") such as tetrabutylammonium hydrogen sulfate ("TBAH"). The vinyl groups at each end of the oligomer may then be converted to ethynyl groups by bromination of the DAPS in CH.sub.2 Cl.sub.2 or CHCl.sub.3, followed by dehydrobromination in the presence of potassium-tertbuoxide (K--t--Bu"). The glass transition temperature (T.sub.g) of the di(styrenated)APS after thermal curing is unexpectedly much higher than that of the APS from which it is derived.

REFERENCES:
patent: 4562243 (1985-12-01), Percec

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