Photocationic crosslinking of poly(2,3-epithiopropyl methacrylate) and photo-initiated cationic polymerization of its model compounds

Photocationic crosslinking of a poly(2,3-epithiopropyl methacrylate) (PETMA) film containing 4-N,N-diethylaminobenzene diazonium tetrafluoroborate (DAC) was investigated. Very rapid photocrosslinking of PETMA was observed and the rate was greater than that of poly(glycidyl methacrylate) with DAC. Post-heating of the irradiated PETMA film resulted in a decrease of the insoluble fraction. This decrease was explained by scission of crosslinking points by the BF₃. In the present conditions, more than 0.3 wt % of DAC was required to insolubilize the PETMA film. Photopolymerizations of propylene sulfide (PS) and 2,3-epithiopropyl pivalate (ETPP) in the presence of DAC were investigated. The polymerization of PS proceeded smoothly but addition of ethyl acetate to PS depressed the rate and the degree of polymerization. ETPP could not be polymerized but copolymerized with PS by this method. Addition of ETPP to PS depressed both the rate of the polymerization and the degree of polymerization. From these results, it is deduced that the photocrosslinking of a PETMA film is caused by a cationic polymerization of episulfide groups but the chain length is not large.