Effect of feed rate of monofunctional monomers on structure of hyperbranched copolymers formed by self-condensing vinyl copolymerization in semibatch reactor

• Hyperbranched copolymers (HBPs) prepared under semibatch process were studied.
• The molecular structure of the HBP was calculated by a generating function method.
• A higher degree of branching could be obtained at a slower feed rate of monomers.

Hyperbranched polymers (HBPs) formed by a self-condensing vinyl copolymerization, SCVCP, of monofunctional monomers M gradually fed into a reactor containing inimers AB*, which had been charged initially, were investigated using a kinetic model. Under the assumption that no cyclization occurred during polymerization, changes in the average degree of polymerization (DP), the degree-of-polymerization dispersity, the degree of branching (DB), and the number of structural units in the hyperbranched copolymers at different feed rates of monomers M were calculated by a generating function method. The distribution of the degree of polymerization could be narrowed with the addition of monomers M, and the degree-of-polymerization dispersity was increased slightly at a slower feed rate parameter of M, ϕ. A higher DB of the HBPs could be obtained at a slower feed rate and a specific stopping ratio of M, θ. For instance, a final DB of approximately 0.62 was attained at ϕ = 0.2 and θ = 1.2, which was higher than the maximum DB of 0.5 attained in a batch system with monomers M at θ = 0.6.

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