| Abstract: | High-molecular-weight copolymers of vinyl chloride and ethyl or butyl acrylate were prepared in high conversion and yield in the presence of boron trifluoride as the acrylate ester complexing agent. When the vinyl chloride monomer is in excess of equimolar amounts, the resulting copolymers are alternating; and when the alkyl acrylates are in excess, acrylate-rich copolymers are obtained. Ethylene–vinyl chloride–ethyl acrylate and propylene–vinyl chloride–ethyl acrylate terpolymers were also obtained with an ethyl acrylate content of 50 mole %. The relative reactivities of propylene, vinyl chloride, and ethylene in these polymerizations were 5.4, 3.8, and 1.0, respectively. Vinylidene chloride–ethyl acrylate copolymers that are nearly alternating and rich in acrylate or in vinylidene chloride have also been prepared. The monomer reactivity ratios for vinylidene chloride and ethyl acrylate in the presence of boron trifluoride are considerably lower than in its absence. |
