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

Abstract

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.

Combining Cyclic Units and Unsaturated Pendant Groups by Propene/1,5-Hexadiene Copolymerization Toward Functional Isotactic Polypropylene

“…Moreover, it is well attested that polymerization of some non-conjugated dienes, such as 1,5-hexadiene (1,5-HD) and 1,7-octadiene (1,7-OD), may also lead to their cyclization, resulting in the insertion of cyclic units and the formation of polymers potentially characterized by both cyclic and unsaturated units . Notably, the homopolymerization of 1,5-HD has been widely investigated through the employment of several catalytic systems. − Some of them afford polymers characterized by the presence of vinyl pendant units, − , which in some cases have been exploited for post-functionalization reactions. , …”

Ammonium Tetrakis(pentafluorophenyl)borate: Preparation and Application in Olefin Coordination Polymerization as the Cocatalyst Compound

“…The controllable "precision" polyolefin can help satisfy the technical needs of the future society. In 2023, Sita et al [106] reported that a systematic investigation about the synthesis and characterization a series of amorphous atactic cis, trans poly(methylene-1,3-cyclopentane-stat-cyclohexane) statistical copolymers was carried out innovatively. In this study, the copolymerization of 1,5-hexadiene and 1,6-heptadiene with different initial feed ratios was attempted, in order to produce different grades of products under the catalysis of Scheme 9.…”

“…This study lays the foundation for DMAB to participate in some specific polymerization reactions about 1, 6-heptadiene. Later, Kaitlyn E. Crawford and Lawrence R. Sita [105] reported another cooperation between DMAB and the transition metal complexes for synthesizing poly ( In 2023, Sita et al [106] reported that a systematic investigation about the synthesis and characterization a series of amorphous atactic cis, trans poly(methylene-1,3-cyclopentane-stat-cyclohexane) statistical copolymers was carried out innovatively. In this study, the copolymerization of 1,5-hexadiene and 1,6-heptadiene with different initial feed ratios was attempted, in order to produce different grades of products under the catalysis of Scheme 10.…”