Vinyl polymerization. XCII. Polymerization of propenyl chloride isomers

The effect of the substituent on polymerization of isopropenyl chloride (IPC), cis ‐propenyl chloride (CPC), and trans ‐propenyl chloride (TPC) has been investigated. These monomers homopolymerized only very slightly in the presence of radical or ionic catalyst, and only a low molecular weight polymer of IPC was isolated. However, these monomers copolymerized with radical initiator with vinyl acetate, vinyl chloride, and acrylonitrile, and their reactivities towards the poly(vinyl acetate) radical decreased in order of IPC ≫ TPC ≥ CPC. The Q, e values for the monomers were estimated as follows: for IPC, Q = 0.06, e = −0.85; for CPC, Q = 0.005, e = −1.66; for TPC. Q = 0.009, e = −1.33. Further results on copolymerization with maleic anhydride indicated that the steric effect of the substituent for these monomers increased in order IPC ≪ TPC ≤ CPC. On radical polymerization of IPC, its degradative chain transfer reactivity was suggested to be also significant.