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Photocrosslinking of polymers has played an important role in regions of coatings, inks, and photoresists. In these regions, photo-initiated cationic polymerization is worthy of note, because many monomers such as vinyl ethers and epoxides can be polymerized in the presence of 02. In a previous paper[1], we have reported the synthesis and photo-initiated cationic crosslinking of polymers bearing pendant B-ketosulfone (B-KS) units as photo-acid generating groups, that is , terpolymers of 2-vinyloxyethyl methacrylate (VEM), methyl methacrylate (MMA), and p-phenacylsulfonylstyrene (PSSt). The photocrosslinking was induced not only by sulfinic and sulfonic acid , but also radicals generated in the photolysis of pendant B-KS units as shown in Scheme 1. The photocrosslinking rate was much greater than that of VEM and MMA copolymers with low molecular-weight Q-KSs. In this paper, we report the mechanistic feature i n the photocrosslinking of the terpol ymers. Syntheses of PSSt and the terpolymers were described in the previous paper.[1] Mesitylphenacylsulfone(MPS) (mp. 143-145 °C)[2] was used as a low molecular-weight BKS. Structure of polymers and a model compound, and composition of polymers are shown in Fig. 1. Polymer films (ca. 1 pm thick) were prepared by casting a tetrahydrofuran (THF) solution of polymers on a quartz plate. The films were irradiated at a distance of 10 cm from a low pressure mercury lamp (Ushio, ULO-6-DQ, 6W) ( 0.36 mJ/cm2 ) at room temperature.

Highly efficient photocrosslinking by the use of pendant photo-acid generating groups.