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

✍ Scribed by Hideyuki Itoh; Atsushi Kameyama; Tadatomi Nishikubo

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 199 KB
• Volume: 35
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19971115)35:15<3217::aid-pola14>3.0.co;2-e

✦ Synopsis

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-Diazabicyclo[5.4.0]-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-(diphenylsulfonio)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).