期刊
POLYMER JOURNAL
卷 41, 期 1, 页码 26-33出版社
NATURE PUBLISHING GROUP
DOI: 10.1295/polymj.PJ2008174
关键词
Allyl Acetate; Allyl Radical; Allyl Polymerization; Degradative Monomer Chain Transfer; MALDI-TOF-MS; End-Group Determination
资金
- Ministry of Education, Culture, Sports, Science and Technology, 2005-2009
Allyl monomers polymerize only with difficulty and yield polymers of medium-molecular-weight or oligomers. This is attributable to degradative monomer chain transfer. However, the well-known allyl polymerization mechanism is based on only the kinetic data but any structural identification is not given. Allyl acetate (AAc), a most typical allyl monomer, was polymerized radically and the resultant oligomeric poly(AAc)s were characterized using MALDI-TOF-MS spectrometry in order to reassess the AAc polymerization mechanism proposed by Litt and Eirich. The induced decomposition of benzoyl peroxide by both growing polymer radical and monomeric allyl radical was presumed but it was never of importance. Then, the fate of resonance-stabilized monomeric allyl radical generated via monomer chain transfer of growing polymer radical was pursued in terms of the competition between the initiation of a new polymer chain and the chain stopping reaction of a growing polymer radical providing monomeric allyl groups as the initial and terminal end-groups, respectively. The monomer chain transfer constant was estimated to be 3.73 x 10(-2) from the P-n value of poly(AAc) obtained at a low initiator concentration where the coupling termination of growing polymer radical with monomeric allyl radical was negligible.
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