Direct Synthesis of Functionalized High‐Molecular‐Weight Polyethylene by Copolymerization of Ethylene with Polar Monomers

Abstract

The introduction of even as mall amount of polar functional groups into polyolefins could excise great control over important material properties.A st he most direct and economic strategy,t he transition-metal-catalyzed copolymerization of olefins with polar,f unctionalized monomers represents one of the biggest challenges in this field. The presence of polar monomers usually dramatically reduces the catalytic activity and copolymer molecular weight (to the level of thousands or even hundreds Da), rendering the copolymerization process and the copolymer materials far from ideal for industrial applications.I nt his contribution, we demonstrate that these obstacles can be addressed through rational catalyst design. Copolymers with highly linear microstructures,h igh melting temperatures,a nd very high molecular weights (close to or above1000 000 Da) were generated. The direct synthesis of polar functionalizedh igh-molecular-weight polyethylene was thus achieved.

Structural analysis of linear/branched ethylene block copolymers

“…This could give the current system a lot of flexibilities to tune the microstructures of the resulting polymeric products . The α‐diimine type catalyst has been also extensively studied for its capability to copolymerize ethylene with various polar monomers . It would be a great breakthrough if the copolymerization could be applied to this chain shuttling system.…”

Strategies in catalysts and electrolyzer design for electrochemical CO2reduction toward C2+products

“…C 2+ hydrocarbons, such as C 2 H 4 , are nexus chemicals for a variety of chemical industries, such as polyethylene production (62,63). Besides, it could be directly used as the fuel for welding or a mixed component in natural gas (12).…”

Facile Access to Polar-Functionalized Ultrahigh Molecular Weight Polyethylene at Ambient Conditions

“…[54][55][56][57][58] To date, the example for producing ultrahigh molecular weight polar functionalized polyethylenes also occurred at high pressure. [102] Using an extremely bulky -diimine precious palladium catalyst, copolymerization of ethylene with methyl 10-undecenoate (UCOOMe) under 8 bar at 25 o C for a very long 12 h gave copolymers with M n of > 105 × 10 4 g mol -1 and incorporation of 0.06-0.35 mol%; however, when ethylene pressure fell from 8 bar to 1 bar, two orders of magnitude lower copolymer molecular weights (M n = 1.7~2.1 × 10 4 g mol -1 ) were obtained under otherwise identical conditions. [102] This event again confirmed the difficulty of generating polar functionalized UHMWPE at ambient conditions.…”

“…We were interested in the copolymerization of ethylene with biomass-derived polar monomers using transition metal catalysts, [102][103][104][105][106][107][108][109] and thus methyl 10-undecenoate (UCOOMe), 10-undecen-1-ol (UOH) and 10-undecenoic acid (UCOOH)…”