Well‐defined low‐molecular‐weight polystyrene was grafted onto cellulose acetate in a homogeneous solution. The grafting was performed by esterifying the free hydroxyls in the cellulose acetate (acetyl DS 2.5) with anionically prepared polystyrene having a carboxylic acid group at one end of the chain. The carboxylic acid end group of the polystyrene was activated by either conversion to the corresponding acid chloride, or by reaction with trifluoroacetic anhydride. Pyridine and the more active 4‐dimethylaminopyridine were used as catalysts in the esterifications. The polystyrene contents of the copolymers varied between 10 and 80% and the molecular weights of the polystyrene grafts were 2500, 12,100 and 17,100 (M̄w/M̄n = 1.1).
The cationic polymerization of p‐chloro‐α‐methylstyrene was investigated for the effect of initiator and solvent on polymer tacticity, molecular weight, and molecular weight distribution. The products were generally crystalline polymers of 80–90% syndiotactic content with fairly high molecular weights and broad molecular weight distributions. Tacticities and molecular weight distributions followed similar patterns suggesting that the effect of reaction conditions on ionpair end‐group structures was the dominant factor.
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