Copolymerization of Alkenes and Polar Monomers by Early and Late Transition Metal Catalysts

Achieving high molecular weight alternating copolymers of 1-octene with methyl acrylate via Lewis acid catalyzed copolymerization

“…The consequence of this is the incapacity to generate high molecular weight polymers. Although poly(α-olefins) can be synthesized through coordination polymerization, such as homo-polymerization for isotactic polypropylene or copolymerization for functional polyolefins, 17,18 the simultaneous improvement of catalytic efficiency and copolymer molecular weight remains an unattained goal. 13,19 Furthermore, the incorporation of functional monomers, particularly polar monomers, into olefin copolymers is restricted by the limited tolerance of coordination polymerization catalysts towards polar monomers.…”

Synthesis of Aminopolyolefins with Tunable Hydrophilicity and Chain Flexibility for Application as Binders in Aqueous Rechargeable Batteries

“…Various types of polyetheramines or JEFFAMINE have been used as composite polymer electrolytes, binders, and interfacial layers in batteries due to the improved charge carrier properties of the amines. , The limited application of amine-functionalized materials in electrochemical applications could be attributed to the challenges associated with the controlled and selective synthesis of these materials. Amine-containing monomers are known to inhibit efficient polymerization while traditional multistep synthetic routes are required for their preparation, making their mass production expensive. − Limited synthetic access to such materials impedes the exploration of aminopolyolefins (APOs) as an important class of responsive materials that shows promise for battery applications.…”

Syndiospecific Polymerization of o-Methoxystyrene and Its Silyloxy or Fluorine-Substituted Derivatives by HNC-Ligated Scandium Catalysts: Synthesis of Ultrahigh-Molecular-Weight Functionalized Polymers

“…The coordination (co)­polymerization of polar olefins to prepare high functional polyolefins having superior surface properties, adhesion properties, and compatibility with other types of materials has always been a challenging and high-profile issue in academia and industry. − The most serious difficulty lies in the fact that the high oxyphilic early transition metal catalysts can be easily poisoned by polar olefins because the stronger Lewis basic heteroatom groups of polar olefins have more preferential coordination ability than the weaker Lewis basic double bond to the strong Lewis acidic metal centers. − Subsequently, the low oxyphilic late transition metal catalysts, which are more tolerant of heteroatom functionalities in the monomer and the polymer, have ascended on the history stage and gradually began to open up new areas for the coordination (co)­polymerization of polar olefins such as polar norbornene, acrylates, vinyl ethers, vinyl acetate, vinyl halides, acrylonitrile, CO, etc. − Recently, a significant breakthrough in the coordination (co)­polymerization of polar olefins has been made by the high oxyphilic rare-earth metal catalysts. − Activated by a catalytically equimolar amount of cocatalyst borate and/or an excess of AlR 3 , rare-earth metal alkyl cations [LLnR] + generated from a series of rare-earth metal dialkyl complexes LLnR 2 L' n (Ln is a rare earth metal center, L is a negative monovalent multi-dentate supporting ligand, R is a negative monovalent alkyl ligand, L' n is a neutral ligand like tetrahydrofuran (THF) solvent molecules with a number in the range of 0–2) exhibit high activities and stereoselectivities in the coordination (co)...…”