Copolymerization of Ethylene with Functionalized 1,1-Disubstituted Olefins Using a Fluorenylamido-Ligated Titanium Catalyst.

Considering the sustainability of material development, coordination polymerization catalysts effective for 1,1-disubstituted olefins are receiving a great deal of attention because they can introduce a variety of plant-derived comonomers, such as β-pinene and limonene, into polyolefins. However, due to their sterically encumbered property, incorporating these monomers is difficult. Herein, we succeeded in the copolymerization of ethylene with various hydroxy- or siloxy-substituted vinylidenes using a fluorenylamido-ligated titanium catalyst-MMAO system. This is the first example of ethylene/polar 1,1-disubstituted olefins' copolymerization using an early transition metal catalyst system. The polymerization proceeded at room temperature without pressurizing ethylene, and high-molecular-weight, functionalized polyethylene was obtained. The obtained copolymer showed a reduced water contact angle compared with that of the ethylene/isobutene copolymer, demonstrating the increment in hydrophilicity by hydroxy groups.