Non-catalytic process for the preparation of difunctionalized polyarylene polyethers
First Claim
1. A process for forming an α
- ,ω
-difunctionalized substantially linear crosslinkable thermoplastic polyarylene polyether oligomer, or polyarylene polythioether oligomer, (difunctionalized PAPE oligomer), from a PAPE oligomer, comprising,(a) reacting a first salt of said PAPE oligomer having a molecular weight Mn in the range from about 1000 to about 10,000, with a α
,β
-unsaturated haloacyl reactant ("HAR") essentially quantiatively in an aprotic solvent, in the absence of a phase transfer catalyst ("PTC") at an oligomerization temperature below that required to crosslink said HAR, so as to yield a functional head consisting of the residue of said HAR at each end of said PAPE oligomer;
(b) precipitating a second salt without simultaneously precipitating a substantial quantity of said difunctionalized PAPE oligomer; and
,(c) recovering said difunctionalized PAPE oligomer.
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Accused Products
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═O, --S--S--, or --SO2 - 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, αω-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.
83 Citations
9 Claims
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1. A process for forming an α
- ,ω
-difunctionalized substantially linear crosslinkable thermoplastic polyarylene polyether oligomer, or polyarylene polythioether oligomer, (difunctionalized PAPE oligomer), from a PAPE oligomer, comprising,(a) reacting a first salt of said PAPE oligomer having a molecular weight Mn in the range from about 1000 to about 10,000, with a α
,β
-unsaturated haloacyl reactant ("HAR") essentially quantiatively in an aprotic solvent, in the absence of a phase transfer catalyst ("PTC") at an oligomerization temperature below that required to crosslink said HAR, so as to yield a functional head consisting of the residue of said HAR at each end of said PAPE oligomer;(b) precipitating a second salt without simultaneously precipitating a substantial quantity of said difunctionalized PAPE oligomer; and
,(c) recovering said difunctionalized PAPE oligomer. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9)
- ,ω
Specification