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Group Selective Linear Polymerization of Vinyl Acrylate Using19-Borabicyclo[3.3.1]nonane

✍ Scribed by Kanno, Shuichi; Syouji, Yasuyuki; Hosoi, Masayoshi; Sato, Rikiya; Takeishi, Makoto


Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
273 KB
Volume
42
Category
Article
ISSN
0959-8103

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✦ Synopsis


Vinyl acrylate (VA) was polymerized with 9-borabicyclo[3.3.1]nonane (9-BBN) in tetrahydrofuran under argon at low temperatures (to [60¡C). Hydroquinone and 2,6-di-tert-butyl-p-cresol had little e †ect on the polymerization. Addition of tetrachloromethane as a radical chain transfer agent did not lead to decrease in molecular weight of the polymer obtained. The initial rate of polymerization was proportional to [9-BBN]0Õ91 and [VA]1Õ37. The experimental results were indicative of non-radical properties of the propagating chain end. The polymer was soluble in organic solvents such as toluene, chloroform and N,N-dimethylformamide. The nuclear magnetic resonance measurements showed the presence of pendant vinyl groups in the polymer, indicating that only the acrylic double bond of VA reacted for polymerization to yield a linear polymer. Aniline retarded the polymerization and no polymer was formed in the presence of triethylamine. These inhibitory e †ects were explained on the basis of complex formation of 9-BBN with amines. This polymerization is discussed in terms of a non-radical mechanism.