Rare-earth-metal-initiated polymerizations of (meth)acrylates and block copolymerizations of olefins with polar monomers

Copolymerization of polar monomers with olefins using transition-metal complexes.

Transition-metal catalysts long ago made it from the laboratory bench to the polymerization reactor. Indeed, they are being used around the world to make more than 70 million tons of polyethylene and polypropylene a year. Transition-metal catalysts give polyolefin producers unprecedented flexibility in process and polymer design. However, there are still new worlds for catalysts to conquer. One...

Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs.

This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)₃ (RE = Sc (1), Y (2), Sm (3), La (4), Ar = 2,6-tBu₂C₆H₃) and phosphines PR₃ (R = Ph, Cy, Et, Me). Catalytic activities of...

Enzyme Initiated Radical Polymerizations

Biocatalysis is propagating into practically every area of organic chemistry, amongst them radical polymerizations. A review of the recent developments of this dynamic and quickly evolving area of research is presented together with a critical evaluation of its potential to yield novel polymers and/or environmentally more benign synthetic procedures.

Various radical polymerizations of glycerol-based monomers

Rare-earth metal hydroxylamide complexes.

The rare-earth metal hydroxylamide compound Y[N(SiHMe2)2]2[ONBn2][THF] (1) was prepared by the silylamide elimination pathway from the reaction of N,N-dibenzylhydroxylamine, Bn2NOH (Bn = CH2C6H5), with Y[N(SiHMe2)2]3[THF]2 and was characterised by multinuclear NMR spectroscopy and elemental analysis. The compounds [Cp2Y(ONBn2)]2 (2a) [Cp2Sm(ONBn2)]2 (2b) were obtained by the reactions of MCp3 (...