GRAFT CO-POLYMERIZATION OF STYRENE ONTO POLY(PARA-NITROPHENYL ACRYLATE) BY CHAIN TRANSFER-REACTION

Styrene (St) was polymerized in the presence of poly(p‐nitrophenyl acrylate) (PNPA) with azobisisobutyronitrile as an initiator to prepare graft copolymers through the chain transfer reaction of growing polystyrene (PSt) radicals to the aromatic nitro groups on PNPA. The maximum number of branches attained was 16.4 (Pn of PNPA was 1780), which corresponds to 108 monomer units per PSt branch. This is far less than the value of 43, previously obtained for poly(vinyl p‐nitrobenzoate) as a trunk polymer. Therefore, several model compounds for trunk polymers were prepared, and the chain transfer constants of PSt radicals to these model compounds were determined. As a result of the Hammett plot, it is concluded that higher electron attracting property of the substituents increases the reactivity of nitro groups to the growing PSt radicals, resulting in more highly branched graft copolymers. Copyright © 1979 John Wiley & Sons, Inc.