Properties of vinylpyrrolidone-tert-butylphenyl methacrylate copolymers in solution

Copolymers of vinylpyrrolidone-p-tert-butylphenyl methacrylate (VP-MBPh) of several compositions were prepared by polymerization in benzene at 50°C using α′α′-azobisisobutyronitrile as initiator. Three of the copolymers were fractionated. Number-average molecular weights of fractionated samples were determined by osmotic pressure in benzene or 2-propanol. Kuhn–Mark–Houwink relations were established in benzene, chloroform, and 2-propanol. From the relation between M _n and the intrinsic viscosity (η), it appears that these random copolymers behave as predicted by the theory for flexible polymers. Abnormal viscometric behavior shown by one of the copolymers in nitromethane at 29°C (the theta temperature) is discussed. The Stockmayer–Fixman semiempirical method was used for estimating unperturbed dimensions from viscosity data obtained in chloroform, a good common solvent. Values of the viscosity parameter K_θ increase with the content of p-tert-butylphenyl methacrylate. In general, experimental K_θ values are higher than those calculated for the homopolymers. Excluded-volume parameters are estimated and discussed in relation to repulsive interactions between unlike monomer units.