Journal
POLYMER
Volume 45, Issue 19, Pages 6533-6537Publisher
ELSEVIER SCI LTD
DOI: 10.1016/j.polymer.2004.07.028
Keywords
beta-pinene; isobutylene; living cationic random copolymerization
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The first example of living cationic random copolymerization of beta-pinene and isobutylene was achieved with 1-phenylethyl chloride/TiCl4Ti(OiPr)(4)/nBu(4)NCl (TiCl4/Ti(OiPr)(4) mole ratio: 3/1) initiating system in CH2Cl2 at -40 degreesC. beta-Pinene and isobutylene was consumed at almost the same rate, suggesting that the two monomers exhibit almost equal reactivity. At any monomer feed ratio, the numberaverage molecular weight (M-n) of the copolymers increased in direct proportion to the total monomer conversion, and the molecular weight distribution was relatively narrow (M-W/M-n = 1.1-1.2) throughout the reaction. The reactivity ratios determined by the Kelen-Tudos method were r(beta-pinene) = 1.1 and r(isobutylene) = 0.89, Which indicated that the composition of copolymer is approximately identical to the monomer feed ratio. The analysis of the structure and sequence distribution of the copolymers by H-1 NMR spectroscopy further confirmed that perfectly random copolymers were obtained by this living cationic polymerization system. The glass transition temperatures of the copolymers obtained with varying monomer compositions were also determined by DSC method. (C) 2004 Elsevier Ltd. All rights reserved.
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