Coordinative Chain Transfer and Chain Shuttling Polymerization

Abstract

Coordinative chain transfer polymerization, CCTP, is a degenerative chain transfer polymerization process that has a wide range of applications. It allows a highly controlled synthesis of polyolefins, stereoregular polydienes, and stereoregular polystyrene, including (stereo)block as well as statistical copolymers thereof. It also shows a green character by allowing catalyst economy during the synthesis of such polymers. CCTP notably allows the end functionalization of both the commodity and stereoregular specialty polymers aforementionned, control of the composition of statistical copolymers without adjusting the feed, and quantitative formation of 1-alkenes from ethene. A one-pot one-step synthesis of the original multiblock microstructures and architectures by chain shuttling polymerization (CSP) is also an asset of CCTP. This methodology takes advantage of the simultaneous presence of two catalysts of different selectivity toward comonomers that produce blocks of different composition/microstructure, while still allowing the chain transfer. This affords the production of highly performant functional polymers, such as thermoplastic elastomers and adhesives, among others. This approach has been extended to cyclic esters' and ethers' ring-opening polymerization, providing new types of multiblock microstructure. The present Review provides the state of the art in the field with a focus on the last 10 years.

Solution Structure and Dynamics of Hf–Al and Hf–Zn Heterobimetallic Adducts Mimicking Relevant Intermediates in Chain Transfer Reactions

“…Combinations of group IV transition metal complexes and main group metal alkyls and/or hydrides (such as AlR 3 or ZnR 2 ) are employed in several stoichiometric and catalytic transformations, including metalation of unsaturated substrates, − olefin oligomerization, − and olefin polymerization, − especially chain shuttling polymerization (CSP) − and coordinative chain transfer polymerization (CCTP). − …”

Ethylene-alt-α-Olefin Copolymers by Hydrogenation of Highly Stereoregular cis-1,4 Polydienes: Synthesis and Structural Characterization

“…A wide variety of catalysts and comonomers has been investigated for the ethylene/α-olefin copolymerization [ 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ]. Alternating or pseudo-alternating ethylene/α-olefin copolymers were obtained up to now only with metallocene-based catalysts, which, with respect to the classical heterogeneous ZN (Ziegler-Natta) catalysts, exhibit much smaller r e values and larger r α-olefin values, allowing indeed for a more uniform comonomer distribution.…”