Synthesis of silicon-containing vinyl ether monomers and oligomers and their photoinitiated polymerization

Silicon-containing divinyl ether monomers were synthesized by the addition reaction of glycidyl vinyl ether ( 1 ) with various silyl dichlorides using tetra-n-butylammonium bromide (TBAB) as a catalyst. The reaction of 1 with diphenyl dichlorosilane gave bis-1-(chloromethyl)-2-(vinyloxy)-ethyl]diphenyl silane ( 3a ) in 89% yield. Polycondensations of 3a with terephthalic acid were also carried out using 1,8-Diazabicyclo5.4.0]-7-undecene (DBU) to afford silicon-containing polyfunctional vinyl ether oligomers ( 5 ). A multifunctional Si-monomer with both vinyl ether and methacrylate groups ( 7 ) was prepared by the reaction of 3a with potassium methacrylate using TBAB as a phase transfer catalyst. Photoinitiated cationic polymerizations of these vinyl ether compounds proceeded rapidly using the sulfonium salt, bis-4-(diphenyl-sulfonio)phenyl]sulfide-bis-hexafluorophoshate (DPSP), as the cationic photoinitiator in neat mixtures upon UV irradiation. Multifunctional monomer 7 with both vinyl ether and methacrylate groups showed “hybrid curing properties” using both DPSP and the radical photoinitiator, 2,4,6-trimethylbenzoyl diphenylphoshine oxide (TPO). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3217–3225, 1997