Journal of Polymer Science Part A: Polymer Chemistry

Radical polymerization of methyl trans‐β‐vinylacrylate

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Methyl trans‐β‐vinylacrylate (MVA) undergoes radical polymerization with α,α′‐azobis(isobutyronitrile) (AIBN) in bulk and solution. The polymer obtained consists of 85% trans‐1,4 and 15% trans‐3,4 units. Poly(MVA) (PMVA) is readily soluble in common organic solvents, but insoluble in n‐hexane and petroleum ether. PMVA exhibits a glass transition at 60°C, and loses no weight up to 300°C in nitrogen. The kinetics of MVA homopolymerization with AIBN was investigated in benzene. The rate of polymerization (Rp) can be expressed by Rp = k[AIBN]0.5[MVA]1.0, and the overall activation energy has been calculated to be 94 kJ/mol. The propagation radical of MVA at 80°C was detected by ESR spectroscopy, which indicated that the unpaired electron of the propagating radical was completely delocalized over the three allyl carbons. Furthermore, the steady‐state concentration of the propagating radical of MVA at 60°C was determined by ESR spectroscopy, and the propagation rate constant (kp) was calculated to be 1.25 X 102 L/mol ·s. Monomer reactivity ratios in copolymerization of MVA (M2) with styrene (M1) are r1 = 0.16 and r2 = 4.9, from which Q and e values of MVA are calculated as 4.2 and ‐0.32, respectively. © 1995 John Wiley & Sons, Inc. Copyright © 1995 John Wiley & Sons, Inc.