Olefins and Vinyl Polar Monomers: Bridging the Gap for Next Generation Materials

Abstract

The inherent differences in reactivity between activated and non‐activated alkenes prevents copolymerization using established polymer synthesis techniques. Research over the past 20 years has greatly advanced the copolymerization of polar vinyl monomers and olefins. This Review highlights the challenges associated with conventional polymerization systems and evaluates the most relevant methods which have been developed to “bridge the gap” between polar vinyl monomers and olefins. We discuss advancements in heteroatom tolerant coordination–insertion polymerizations, methods of controlling radical polymerizations to incorporate olefinic monomers, as well as combined approaches employing sequential polymerizations. Finally, we discuss state‐of‐the‐art stimuli‐responsive systems capable of facile switching between catalytic pathways and provide an outlook towards applications in which tailored copolymers are ideally suited.

Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

“…In this work, we pursued a more efficient method for PS chain growth from (polyolefinyl) 2 Zn with an additional aim to expand the scope of the chains that can be grown from (polyolefinyl) 2 Zn (Scheme 1). Recently, syntheses of functionalized POs are a topical issue [36][37][38].…”

Tailoring polymer dispersity and shape of molecular weight distributions: methods and applications

“…[15][16][17][18][19][20][21][22][23] In fact, the high end-group delity and the controlled nature of the polymerisation is typically conrmed by low dispersity values and as such dispersities in the range of Đ z 1.01-1.20 are routinely targeted. [24][25][26][27][28][29][30][31][32] Conversely, broader molecular weight distributions (Đ > 1.4) are oen considered to be a sign of uncontrolled or "failed" polymerisation and necessitate additional optimisation to reduce the dispersity. [33][34][35][36][37][38] However, the dispersity is a key parameter that impacts the physical properties of polymers, since low and high dispersity polymers can exhibit complementary properties and functions.…”

Recent Advances in Coordination‐Insertion Copolymerization of Ethylene with Polar Functionalized Comonomers

“…The introduction of polar functional groups into polyethylenes is challenging, but it can endow the nonpolar materials with valuable properties, such as adhesiveness, compatibility, and printablity. [ 1 ] The coordination‐insertion copolymerization of ethylene with polar comonomers provides a direct and economic approach to the controlled synthesis of polar functionalized polyethylenes. The past two decades have witnessed the success in controlled copolymerizations accomplished by the design and development of catalysts based on transition metals and rare earth metals, which show high tolerance to the heteroatoms and high activity to incorporate the polar comonomers.…”