Polymer Bulletin, Vol.49, No.1, 25-32, 2002
Initiation system effects in the cationic copolymerization of tetrahydrofuran (THF)
Macromonomeric peroxy initiator, poly tetrahydrofuran (poly-THF=inimer) were synthesized via cationic polymerization of THF by the mono- (t-BuBP) and tetra-bromo methyl benzoyl peroxides (BDBP)/ZnCl2 initiating system. The macromonomers were characterized by H-1-NMR, IR, and GPC techniques. Methyl methacrylate (MMA) polymerization initiated by poly-THF inimers at 80degreesC and different times in bulk gave crosslinked poly-THF-b-polymethyl methacrylate block copolymers. Swelling ratios of the crosslinked block copolymers obtained by taking in same amounts of poly-THF inimer and MMA monomer in CHCl3 were decreased versus time. It was compared the results obtained from t-BuBP-, BDBP-ZnCl2 initiating systems with t-BuBP-, BDBP-AgSbF6 initiating systems for THF monomer. Poly(THF-b-MMA) crosslinked block copolymers containing undecomposed peroxide groups initiated the thermal polymerization of styrene, S, were used to obtain poly(THF-b-MMA-b-S) crosslinked multicomponent copolymers at 90degreesC. The crosslinked multi component copolymers were investigated sol-gel analysis and swelling ratios in CHCl3. "Active" poly(THF-b-MMA) having peroxygen group were used in the free radical coupling reaction of poly butadien (Poly Bd). Poly(THF-b-MMA)-polybutadien crosslinked blend soluble graft copolymers were obtained.