Efficient Terpolymerization of Ethylene and Styrene with 1,7‐Octadiene by Aryloxo Modified Half‐Titanocenes–Cocatalyst Systems: Efficient Introduction of the Reactive Functionality

Abstract

Terpolymerization of ethylene and styrene (St) with 1,7‐octadiene (OD) using aryloxo‐modified half‐titanocenes, Cp′ TiCl2(O‐2,6‐iPr2C6H3) [Cp′ = Cp* (1), tBuC5H4 (2), 1,2,4‐Me3C5H2 (3)], proceeds with high catalytic activity and efficient comonomer incorporation, affording high‐molecular‐weight polymers with unimodal molecular‐weight distributions (uniform compositions). An efficient introduction of the reactive functionality, terminal olefinic double bonds, into the side‐chain is attained by adopting this method by incorporation of OD without cyclization: the comonomer contents (St, OD) can be controlled by varying the comonomer concentration charged. The resultant polymers possess negligible resonance, ascribed to St–OD repeated insertion.

A Greener Approach for Synthesis of Functionalized Polyolefins by Introducing Reactive Functionality into Ethylene Copolymers

“…Complex 6 showed the best catalyst performance in term of both the activity and the comonomer incorporation. The microstructure for poly(ethylenecostyrene-co-OD) showed the clear resonance ascribed to the vinyl carbon in the resultant polymers [37]. Moreover, no resonance ascribed to the cyclization of OD was observed, indicating that the polymerization proceeded with notable selectivity of OD repeated insertion, affording polymers containing terminal olefinic double bond in the side-chain, as demonstrated previously [35].…”

“…The initial comonomer concentration affected both the catalytic activity and the comonomer contents [37]. Complex 6 showed the best catalyst performance in term of both the activity and the comonomer incorporation.…”

“…Introduction of OD in ethylene/styrene copolymer could be achieved using aryloxo-modified half-titanocenes, Cp'TiCl 2 (O-2,6- Table 1) [37]. The initial comonomer concentration affected both the catalytic activity and the comonomer contents [37].…”

Synthesis of Ultrahigh Molecular Weight Polymers Containing Reactive Functionality with Low PDIs by Polymerizations of Long-Chain α-Olefins in the Presence of Their Nonconjugated Dienes by Cp*TiMe2(O-2,6-iPr2C6H3)–Borate Catalyst

“…An introduction of polar functionality and the subsequent grafting (by living ring opening polymerization of ε-caprolactone) was also demonstrated into poly(1-octene-co-OD)s under mild conditions [38]. The method introduced a possibility for synthesis of functionalized polyolefins by incorporation of reactive functionalities, as demonstrated in the ethylene/1-octene or ethylene/styrene copolymerization in the presence of OD (synthesis of copolymers containing terminal olefinic double bonds with uniform compositions), and subsequent chemical modification under mild conditions (Scheme 1) [39][40][41][42][43][44][45]. Scheme 1.…”

“…We thus, herein, wish to introduce our explored results for Scheme 1. Polymerization of 1,7-octadiene (OD) and ethylene copolymerizations in the presence of OD, using Cp'TiCl 2 (O-2,6-i Pr 2 C 6 H 3 ) (Cp' = Cp*, 1,2,4-Me 3 C 5 H 2 )-MAO catalysts [38,44].…”