Despite the well-developed stereoselective methods for the polymerization of propylene and other nonpolar α-olefins, stereoselective polymerization of polar vinyl monomers has proven more challenging. Ion dissociation into free ions lead to non-living polymerization. Jordan M. Kaiser, W. Curtis Anderson, Brian K. Long. Polymerization is typically initiated with Lewis acids such as boron trifluoride. Amazing achievements in vinyl ether (VE) chemistry, from the first example of VE polymerization to a plethora of recent research [2-10], facilitated enormous progress in VEs synthesis and in design of advanced polymer materials. This polymerization proceeds under mild conditions: a combination of a metal-free photocatalyst, a chain-transfer agent, and light irradiation enables the synthesis of various poly(vinyl ether)s with good control over molecular weight and dispersity as well as excellent chain-end fidelity. Organocatalyzed Photocontrolled Radical Polymerization of Semifluorinated (Meth)acrylates Driven by Visible Light. Mustafa Ciftci, Gorkem Yilmaz, Yusuf Yagci. Polymerizations with Diethylaluminium chloride rely on trace amounts of water. Photochemical regulation of a redox-active olefin polymerization catalyst: controlling polyethylene microstructure with visible light. Living cationic ring-opening polymerization, Mishra, Munmaya K.; Kennedy, Joseph P. (1987). In particular, the cationic polymerization of 2,4,6-trimethylphenyl vinyl ether proceeded in a living manner under the optimized conditions. The tacticity of vinyl polymers has a profound effect on their physical properties. With ethers and alcohols the true initiator is the chlorinated product. Photocontrolled Living Polymerization Systems with Reversible Deactivations through Electron and Energy Transfer. Highly efficient organic photocatalysts discovered via a computer-aided-design strategy for visible-light-driven atom transfer radical polymerization. Heteroatom-Doped Carbon Dots (CDs) as a Class of Metal-Free Photocatalysts for PET-RAFT Polymerization under Visible Light and Sunlight. The resultant isotactic PVEs are semicrystalline thermoplastics with intrinsic polarity. In addition, the copolymerization of PhVE with p-methoxybenzaldehyde occurred via vinyl- and carbonyl-addition reactions without Friedel–Crafts reactions, resulting in a polymer with an alternating sequence. Campus Box 3290 Initiators are strong electrophiles such as triflic acid. Journal of Photopolymer Science and Technology, Your Mendeley pairing has expired. Kennedy and Faust studied methylstyrene / boron trichloride polymerization (then called quasi-living) in 1982 [7] and that of isobutylene (system with cumyl acetate, 2,4,4-trimethylpentane-2-acetate and BCl3) in 1984 [8][9]

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