The role of monomer in the chain transfer reaction in cobaloxime‐mediated free‐radical polymerization

The role of monomer in catalytic chain transfer polymerization was studied by determination of the chain transfer constants of the tetraphenyl derivative of cobaloxime boron fluoride (COPhBF) in methyl methacrylate at 60°C varying the monomer concentration instead of the COPhBF concentration as is common practice. Toluene and tert‐butyl acetate were used as diluents in these studies and it was found that the chain transfer constants obtained in the present studies were not significantly different from those observed in conventional experiments. These results suggest the absence of a direct participation of monomer molecules in the hydrogen abstraction step in catalytic chain transfer.     

Molecular aspects of polymer network deformation - small angle neutron scattering and NMR studies

Poly(1,4-butadiene) networks obtained by a 4-functional random cross-linking reaction over a broad range of polymer concentration were studied by small angle neutron scattering(SANS), ²H NMR and Monte Carlo(MC) simulation in the isotropic and uniaxially deformed state. The defect structure of the networks has been characterized by MC simulation of the cross-linking reaction. The anisotropy of the radius of gyration in deformed networks determined from SANS has been analyzed by the theory of Ullman. It was found that the number of active cross-links per chain is in agreement with MC and that the chain deformation follows phantom behaviour. The local orientation as measured by ²H NMR is related to the global anisotropy of the network by a MC calculation of oriented chains. The ²H NMR line shape of the deformed network is analyzed in terms of two relaxation processes arising from interior parts of the chains and from segments at chain ends. The mobility of both decrease with strain. It was found that the orientation connected to the first process shows the classical strain dependence of rubber elasticity, whereas the second exhibits a weaker dependence on strain.