Citation: Qing-yuan Li, Yi-xian Wu, Wen-yan Ma, Ri-wei Xu, Guan-ying Wu, Wan-tai Yang. SYNTHESIS OF GRAFT COPOLYMERS WITH POLYISOBUTYLENE BRANCH CHAINS[J]. Chinese Journal of Polymer Science, ;2010, 28(3): 449-456. doi: 10.1007/s10118-010-9092-z shu

SYNTHESIS OF GRAFT COPOLYMERS WITH POLYISOBUTYLENE BRANCH CHAINS

Received Date: 23 June 2009
Revised Date: 13 August 2009

The copolymerization of 4-vinylbenzyl chloride (VBC) and vinyl acetate (VAC) was carried out in toluene at 75C via radical polymerization using 2,2-azo-bis-(isobutyronitrile) (AIBN) as an initiator. The random copolymers of poly(4-vinylbenzyl chloride-co-vinyl acetate) (P(VBC-co-VAC)) with number average molecular weight (Mn) from 2000 to 6900, relatively narrow molecular weight distribution (MWD, Mw/Mn ca. 2.0) and with different copolymer composition of 4-vinylbenzyl chloride (VBC) from 17 mol% to 62 mol% could be obtained. The P(VBC-co-VAC) copolymers with an average number of 7 to 13 initiating sites of benzyl chloride per macromolecule could be used for the cationic polymerization of isobutylene (IB). The cationic polymerizations of IB were further conducted by using P(VBC-co-VAC) copolymers as macroinitiators in conjunction with TiCl4 at-40C in CH2Cl2. The effects of VBC/TiCl4 (molar ratio) on monomer conversion, Mn and MWD of the resultant copolymers were investigated under 3 sets of conditions. It is found that P(VBC-co-VAC)-g-PIB copolymers with relatively narrow MWD (Mw/Mn ca. 2.0) and with terminal tert-chlorine functional groups in branched PIB chains could be successfully synthesized when VBC/TiCl4 (molar ratio) was set in the range from 0.10 to 1.12. The unimodal GPC curve of the P(VBC-co-VAC)-g-PIB copolymers by RI detector was almost in harmony with the GPC curve by UV detector. The TEM image of the P(VBC-co-VAC)-g-PIB copolymer stained by RuO indicated that the copolymer formed a two-phase morphology with P(VBC-co-VAC)-rich domains of 20-100 nm in size tethered by PIB branch segments.
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