Material Properties of Functional Polyethylenes from Transition-Metal-Catalyzed Ethylene–Polar Monomer Copolymerization

Abstract

Polyethylenes enjoy wide applications due to their many superior properties. The incorporation of some polar functional groups into the otherwise nonpolar polyethylene backbone can significantly improve many important properties and further broaden their applications. During the past few decades, many catalyst systems have been demonstrated with the capabilities of copolymerizing ethylene with polar monomers. As a result, numerous polar functionalized polyethylenes have been prepared bearing various polar groups. However, the studies into material properties of functional polyethylenes from transitionmetal-catalyzed ethylene−polar monomer copolymerization have not received much attention until recently. After some brief discussions of selected examples of potent catalysts and suitable polar monomers, this Perspective summarizes some recent advances in the improvements in surface and compatibilities properties (hydrophilicity, adhesion, dyeability, and compatibility with other types of polymers) induced through polar group incorporation as well as some custom-made properties such as elastic, flameretardant, antibacterial, antioxidant, cross-linking, self-healing, light response, dynamic cross-linking, and photodegradation properties.

Tailor-Made Functional Polyolefins of Complex Architectures: Recent Advances, Applications, and Prospects

“…279 They copolymerized sugar-derived isohexide monoenes, including isomannide and isosorbide monoenes or methacryl-2,3,4,6-tetra-Oacetyl-D glucopyranoside with ethylene using Pd-phosphine sulfonate acetonitrile catalyst (catalyst activity = 0.1−1 kg mol −1 h −1 , M w = 13−28 kg mol −1 ). High-temperature 1 HNMR results revealed 1.45% of the biobased monomer enchainment where the comonomer incorporation slightly affected the crystalline structure of polyethylene and endowed copolymers with melting temperatures in the range of 117−126 °C.…”

Ruthenium-catalyzed diazoacetate/cyclooctene metathesis copolymerization

“…The introduction of small amounts of polar func-tional groups into non-functionalized polyolefins can greatly improve many properties and broaden their applications. In addition to the transition metal catalyzed copolymerization of olefins with polar comonomers, [42][43][44][45][46][47][48][49][50] ROMP-mediated copolymerization represents another powerful strategy. 17,51 More importantly, ROMP is capable of producing functionalized high-density polyethylene containing polar functional groups in the main chain, which is not accessible through traditional olefin copolymerization.…”

Molecularly Defined Polyolefin Vitrimers from Catalytic Insertion Polymerization

“…Unlike traditional olefin polymerization catalysts based on d 0 metal active sites, these catalysts are not detrimentally deactivated by the functional groups of the monomers or the forming polymers. The mechanism and scope of these polymerizations have been studied extensively, and a fairly comprehensive picture exists. − More recently, examples of how this functional group tolerance can translate into desirable material properties have emerged. − …”