Abstract
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 effect 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]0·91 and [VA]1·37. 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 effects were explained on the basis of complex formation of 9-BBN with amines. This polymerization is discussed in terms of a non-radical mechanism. © of SCI.
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