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Radical Polymerization Behavior of 4‐Monosubstituted and 2,4‐Disubstituted Enynes
Author(s) -
Ochiai Bungo,
Tomita Ikuyoshi,
Endo Takeshi
Publication year - 2001
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20011101)202:16<3099::aid-macp3099>3.0.co;2-i
Subject(s) - monomer , chemistry , polymerization , polymer chemistry , reactivity (psychology) , copolymer , methyl methacrylate , radical polymerization , polymer , organic chemistry , medicine , alternative medicine , pathology
The radical polymerization of 4‐mono‐ and 2,4‐disubstituted enyne monomers (CH 2 =CH—C≡C—R and CH 2 =C(CH 3 )—C≡C—R, respectively; R = Ph, n ‐Bu, t ‐Bu, and (CH 3 ) 3 Si—) was carried out to elucidate the polymerizability of the monomers and the effect of substituents on the structure of the resulting polymers. The polymerization of 4‐monosubstituted monomers proceeded in a specific 1,2‐fashion to give polymers having acetylene moieties as pendent groups. In contrast, that of 2,4‐disubstituted monomers accompanied ca. 10% of the 1,4‐polymerization to give allenic main chain structures. The monomer reactivity ratios of monosubstituted monomers were estimated from the copolymerization system with methyl methacrylate, from which the Q and e values were estimated as Q = 1.52–2.11 and e = –0.63 to –0.73, respectively. The Q and e values demonstrated that the resonance stabilizing character of the substituents on the 4‐position affects the reactivity of the monomers.