Synthesis and Properties of Periodic Copolymers: Alternating Copolymerization of Propylene with Methyl α-Chloroacrylate

Abstract

ABSTRACT:To synthesize a series of periodic copolymers containing simple ll(-olefins, the alternating copolymerization of propylene (P) with methyl ll(-chloroacrylate (MCA) was examined. An alternating P-MCA copolymer could hardly be obtained by conventional procedures where organoaluminium chlorides alone were used as complexing reagents. The addition of vanadium oxytrichloride or acetylacetonate as the second catalyst provided the well-defined alternating P-MCA copolymer. The P(P-alt-MCA) was found to have coisotacticity (a) of 0.67 by NMR analysis and glass transition temperature (T 8 ) of 56°C by DSC.KEY WORDS Propylene / Methyl ix-Chloroacrylate / Alternating Copolymerization / Poly(propylene-alt-methyl ix-Chloroacrylate) / Vanadium Oxytrichloride / Vanadium Acetylacetonate / Glass Transition Temperature / little studied. In order to study structure-property relationships, the authors synthesized copolymers well-designed with respect to sequence order, namely periodic copolymers.

Studies on binary copolymerization and glass transition temperatures of methyl methacrylate with ethyl methacrylate and n‐butyl methacrylate

“…This may be the case because the periodic copolymers usually have quite different glass transition characters in comparison with statistical copolymers. Yokota reported that the T g of poly[MCA‐Pr] (alternating copolymer of methyl α‐chloroacrylate with proplene) increased from 56 to 76°C when the propylene unit was substituted by more flexible units of EE (poly [MCA‐E‐E]) 15, 16. For statistical copolymers, it has also been reported that introducing a more flexible unit of vinylidene chloride could increase the T g of poly(methyl acrylate) as much as 32.5°C 17.…”