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Synthesis and Characterization of Amphiphilic Copolymer Acrylic Acid-co-p-Chloromethylstyrene

The free radical copolymerization of acrylic acid (M1) with p-chloromethylstyrene (M2) in dioxane and in the presence of α,α′-azobisisobutyronitrile (AIBN) at 65°C is reported. Copolymer compositions of six copolymer samples obtained from feed ratios of M1:M2 = 95.2:4.8 to 21.4:78.6 were determined by 1H-NMR. The reactivity ratios of AA/p-CMS copolymerization system calculated by the F-R method were r 1 = 0.50 ± 0.06 and r 2 = 1.52 ± 0.15, almost the same as r 1 = 0.43 ± 0.21 and r 2 = 1.31 ± 0.14 by the extended K-T method. On the basis of the reactivity ratios of two monomers, the sequence length distribution in the AA/p-CMS copolymers was obtained. For f2 = 4.77%, the monomer unit of p-CMS is individually separated in the chain of AA; for f2 = 35.53%, the alternating tendency prevails and a large number of mono-sequences are formed. The number-average ( n) and weight-average ( w) molecular weights were determined by gel permeation chromatography. The effect on molecular weights of feed composition is also discussed. In the presence of constant initiator concentration, the gradual increase in the ratio of M2:M1 (from14.7:85.3 to 78.6:21.4) was accompanied by a decrease in molecular weights ( n from 11907 to 3961).