期刊
MACROMOLECULES
卷 42, 期 5, 页码 1565-1573出版社
AMER CHEMICAL SOC
DOI: 10.1021/ma8024255
关键词
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资金
- National Science Foundation [0451490]
- NIH Research Resource [P41RR0954]
- Division Of Materials Research
- Direct For Mathematical & Physical Scien [0451490, 1032267] Funding Source: National Science Foundation
A facile synthetic strategy for the preparation of well-defined polymers hearing cycloalkenyl side groups has been established via selective reversible addition-fragmentation chain transfer (RAFT) polymerization of cycloalkene-functionalized asymmetrical divinyl monomers. Two representative monomers, 4-(6'-methylcyclohex-3'-enylmethoxy)-2,3,5,6-tetrafluorostyrene and 4-(cyclohex-3'-enylmethoxy)-2,3,5,6-tetrafluorostyrene, were synthesized. RAFT polymerizations of these bifunctional monomers, using S-1-dodecyl-S'-(alpha,alpha'-dimethyl-(alpha ''-acetic acid)trithiocarbonate as the chain transfer agent and 2,2'-azobis(isobutyronitrile) (AIBN) as the thermal initiator, exhibited superb selectivity toward the substituted styrenyl vinylic unit relative to the cyclohexenyl unit, even at high monomer conversions (>80%). The resulting polymers retained quantitative cyclohexenyl groups, while having predetermined molecular weights and narrow molecular weight distributions (PDI = 1.09-1.15). Well-defined block copolymers with pendent cyclohexenyl groups were also prepared by sequential RAFT chain extension polymerizations. A variety of functional polymers were further obtained by functional group transformations using the cyclohexene-functionalized polymers as precursors.
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