Polar, functionalized diene-based materials. V. Free-radical polymerization of 2-[(N-benzyl-N-methylamino)methyl]-1,3-butadiene and copolymerization with styrene

2-[(N-Benzyl-N-methylamino)methyl]-1,3-butadiene (BMAMBD), the first asymme tric tertiary amino-containing diene-based monomer, was synthesized by sulf one chemistry and a nickel-catalyzed Grignard coupling reaction in high pur ity and good yield. The bulk and solution free-radical polymerizations of t his monomer were studied. Traditional bulk free-radical polymerization kine tics were observed, giving polymers with <M-n> values of 21 x 10(3) to 48 x 10(3) g/mol (where M-n is the number average molecular weight) and polydis persity indices near 1.5. In solution polymerization, polymers with higher molecular weights were obtained in cyclohexane than in tetrahydrofuran (THF ) because of the higher chain transfer to the solvent. The chain transfer c onstants calculated for cyclohexane and THF were 1.97 X 10(-3) and 5.77 X 1 0(-3), respectively. To further tailor polymer properties, we also complete d copolymerization studies with styrene. Kinetic studies showed that BMAMBD incorporated into the polymer chain at a faster rate than styrene. With th e Mayo-Lewis equation, the monomer reactivity ratios of BMAMBD and styrene at 75 degreesC were determined to be 2.6 +/- 0.3 and 0.28 +/- 0.02, respect ively. Altering the composition of BMAMBD in the copolymer from 17 to 93% c aused the glass-transition temperature of the resulting copolymer to decrea se from 64 to -7 degreesC. (C) 2001 John Wiley & Sons, Inc.