PREPARATION AND CHARACTERIZATION OF COPOLYMERS OF MODIFIED STARCHES AND POLYACRYLONITRILE

Starch graft polyacrylonitrile (S-g-PAN) copolymers were prepared from a commercial unmodified cornstarch and from three chemically modified commercial cornstarch products including Amaizo 395 (highly acid modified, HAM), Amaizo 590 (highly hypochlorite oxidized, HHO) and Amaizo 791D (hydroxyethyl, highly acid modified, HEHAM). Using similar reaction conditions and ratio of monomer to starch (1:1), the percentages of PAN in the copolymers ranged from 39% for the unmodified starch to 48% for the modified starches. Only 5% of the PAN of the copolymer prepared from unmodified starch could be extracted by dimethylformamide (DMF) treatments compared to 22-28% for copolymers prepared from the modified starches. However, copolymers from the modified starches apparently contained relatively high proportions of low-molecular-weight copolymer along with homopolymer. Acid hydrolysis treatment of the DMF insoluble and DMF soluble fractions to remove starch from the various copolymers gave essentially quantitative yields of PAN. However, these PAN samples exhibited large differences in DMF solubility. The copolymer from the HHO starch was by far more soluble in DMF, had the lowest number average molecular weight. and had a grafting frequency of 2.5-3 times greater than those of the other copolymers. This study indicated that hypochlorite modified starch substrates may be particularly suitable for obtaining copolymers with widely different properties than copolymers having the acid modified starch substrates.