Synthesis and Cross-linking of Copolymers Containing Dithiocarbonate and Phenol Moieties

抄録

Radical copolymerization of 5-(methacryloyloxy)methyl-1,3-oxathiolane-2-thione (DTC) and styrene derivatives such as 4-(t-butoxy)styrene, 4-(t-butyldimethylsiloxy)styrene, and 4-trimethylsiloxystyrene were carried out in tetrahydrofuran using 2,2’-Azobis(isobutyronitrile) (AIBN) as a radical initiator. The copolymerization proceeded smoothly to give the corresponding polymers in high yield. The copolymer composed of DTC and 4-trimethylsiloxystyrene was deprotected by addition of 1M HCl aq. in ethyl acetate to give the corresponding copolymer having DTC and phenol structures. Thermal properties of the obtained polymers were evaluated by thermal gravimetric analysis (TGA) and differential scanning calorimetry Synopsis (DSC). These polymers showed 10 wt % loss temperatures (T_d10) in the range from 191 to 234 ℃. The polymers obtained here exhibited glass transition temperature (T_g) in the range from 105 to 139 ℃. Furthermore, cyclic dithiocarbonate moieties in the copolymers underwent a ring-opening polymerization by heating in the presence of 4-hydroxyphenylbenzylmethylhexafluorophosphate as a thermally latent cationic initiator to give the corresponding ross-linking polymer.