| Abstract: | Poly-S-vinyl-O-tert-butylthiocarbonate is an excellent precursor to poly(vinyl mercaptan) because the tert-butyloxycarbonyl blocking group can be removed by either acid hydrolysis or thermolysis under conditions which minimize the oxidation of the liberated mercaptan to disulfide. Dilatometric studies of the homopolymerization of S-vinyl-O-tert-butylthiocarbonate demonstrated that the polymerization rate was directly proportional to the concentration of free-radical initiator; no thermal initiation was observed. The molecular weight of the homopolymers and copolymers ranged from 30,000 to 50,000 (GPC). Copolymerization of S-vinyl-O-tert-butylthiocarbonate (M2) with styrene, (r1 = 3.0, r2 = 0.2), methyl methacrylate (r1 = 1.40, r2 = 0.17) and vinyl acetate (r1 = 0.04, r2 = 11.0) indicated that a sulfur atom adjacent to the vinyl group increases the resonance stability (Q2 = 0.5) and the electron density (e2 = ?1.4) of the double bond and the corresponding radical. Water-soluble copolymers could be prépared by incorporating either N-vinylpyrrolidone (r1 = 0.12, r2 = 3.94) or N-isopropylacrylamide (r1 = 1.17, r2 = 0.3) with M2. The water solubility of the copolymers decreased markedly when the tert-butyloxycarbonyl group was removed. Copolymers of M2 with N-vinyl-O-tert-butylcarbamate (r1 = 0.13, r2 = 5.10) were utilized to prepare crosslinked poly(vinyl amine–vinyl mercaptan); the crosslinking resulted from urea linkages formed during thermolysis of the copolymer. |
