Tailoring Glass Transition Temperature in a Series of Poly(methylene-1,3-cyclopentane- stat -cyclohexane) Statistical Copolymers.

A systematic investigation of the synthesis and characterization of a new class of amorphous atactic cis , trans poly(methylene-1,3-cyclopentane- stat -cyclohexane) statistical copolymers ( I ) is reported. Production of different grades of I that vary with respect to the ratio of 5- and 6-membered cycloalkane repeat units was achieved through the living coordinative chain transfer cyclopolymerization of different initial feed ratios of 1,5-hexadiene and 1,6-heptadiene comonomers. It was determined that the glass transition temperature, T g , of I can be systematically increased from -16 to 100 °C as a function of increasing 6-membered ring content, although not in a strictly linear fashion. It was further determined that a small level of 6-membered ring content is sufficient to disrupt the crystallinity of the limiting atactic cis , trans poly(methylene-1,3-cyclopentane) (PMCP) homopolymer that possesses a melting temperature, T m , of 98 °C. These results establish a foundation for future potential technological applications of this unique class of polyolefin copolymers.