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Synthesis of graft copolymers with polyisobutylene branch chains

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Abstract

The copolymerization of 4-vinylbenzyl chloride (VBC) and vinyl acetate (VAC) was carried out in toluene at 75°C 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 (M n) from 2000 to 6900, relatively narrow molecular weight distribution (MWD, M w/M n 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 −40°C in CH2Cl2. The effects of VBC/TiCl4 (molar ratio) on monomer conversion, M n 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 (M w/M n 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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Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing, 100029, China

    Qing-yuan Li, Yi-xian Wu  (吴一弦), Wen-yan Ma, Ri-wei Xu, Guan-ying Wu & Wan-tai Yang

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  1. Qing-yuan Li
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  2. Yi-xian Wu  (吴一弦)
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  3. Wen-yan Ma
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  4. Ri-wei Xu
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  5. Guan-ying Wu
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  6. Wan-tai Yang
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Corresponding author

Correspondence to Yi-xian Wu  (吴一弦).

Additional information

This work was financially supported by the National Natural Science Foundation of China (Nos. 20774008, 20934001), Program for Changjiang Scholars and Innovative Research Team in Universities (IRT0706).

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Li, Qy., Wu, Yx., Ma, Wy. et al. Synthesis of graft copolymers with polyisobutylene branch chains. Chin J Polym Sci 28, 449–456 (2010). https://doi.org/10.1007/s10118-010-9092-z

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  • DOI: https://doi.org/10.1007/s10118-010-9092-z

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