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Free‐radical polymerization with long‐chain branching: Batch polymerizations of vinyl acetate in t ‐butanol
Author(s) -
Chatterjee A.,
Kabra K.,
Graessley W. W.
Publication year - 1977
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1977.070210703
Subject(s) - branching (polymer chemistry) , vinyl acetate , solvent , polymerization , monomer , polymer chemistry , butanol , chemistry , chain transfer , radical polymerization , reaction rate constant , bulk polymerization , polymer , solution polymerization , kinetics , organic chemistry , ethanol , copolymer , physics , quantum mechanics
Vinyl acetate was batch polymerized at 60°C in t ‐butanol solution. Conversion and molecular weights were measured as functions of time for several initiator and solvent concentrations. Although the overall rate constant depends somewhat on solvent concentration, the reaction is first order in monomer concentration up to at least 60% conversion and one‐half order in the concentration of initiator. Molecular weights were independent of initiator concentration, confirming that the polymerization is transfer dominated. Measurements of M̄ w and M̄ w versus conversion were used to establish the individual transfer constants. All are independent of solvent concentration, except C p , the polymer transfer constant, which decreases systematically with increasing solvent concentration.