Synthesis of bromine‐functionalized polyolefins by scandium‐catalyzed copolymerization of 10‐bromo‐1‐decene with ethylene, propylene, and dienes

Abstract

By use of a THF‐containing trimethylsilylmethyl scandium catalyst system (C5Me4SiMe3)Sc(CH2SiMe3)2(THF)/[Ph3C][B(C6F5)4], the multi‐component copolymerization of 10‐bromo‐1‐decene (BrDC) with ethylene, propylene, and dienes has been achieved to afford a new family of bromine‐functionalized polyolefins with controllable composition and high molecular weight. The copolymerization of BrDC with ethylene afforded the well‐defined BrDC–ethylene copolymers with high BrDC incorporation (up to 12 mol%) and high molecular weight (Mw > 100 kg mol−1). The terpolymerization of propylene, ethylene with BrDC afforded random ethylene–propylene–BrDC terpolymers with controllable bromine content (2 ~ 11 mol%), high molecular weight (Mw > 100 kg mol−1) and low glass transition temperature (Tg = −51 °C ~ −67 °C). Moreover, the tetrapolymerization of ethylene, propylene, BrDC, and ethylidene norbornene or conjugated dienes such as isoprene and myrcene has been achieved for the first time to afford selectively the bromine‐functionalized ethylene–propylene–diene rubbers containing various types of double bonds.

Recent Advances in Nickel Catalysts with Industrial Exploitability for Copolymerization of Ethylene with Polar Monomers

“…Consequently, they are quite helpless in the copolymerization of ethylene with fundamental polar monomers (with polar groups directly linked to the C=C bond). Certain protective strategies have been developed to mitigate the poisoning effect, for example, the prior complexation of polar monomers with a large amount of strong Lewis (methylaluminoxane or alkyl aluminum) [ 23 , 24 ], using a bulky group to shield the polar group and ensure that the active center of the catalyst is blocked [ 25 ], and employing polar monomers with long methylene chains between the polar group and the C=C bond [ 26 ]. It is therefore early metal catalytic systems for ethylene–polar monomer copolymerization which still suffer from complex operations and confined comonomer scopes.…”

π-Carbazolyl supported bis(alkyl) complexes of Sc, Y and La for α-olefin polymerization and hydrogenation

“…7 Bis(alkyl) complexes are in special focus as potential catalysts for alkene homo- and copolymerization. 1 h ,2 b , c ,8–10…”