Synthesis of fluorinated gradient copolymers via in situ transesterification with fluoroalcohols in tandem living radical polymerization

Abstract

Fluorinated gradient copolymers were synthesized by the tandem catalysis of ruthenium-catalyzed living radical polymerization and titanium alkoxide-mediated transesterification of methyl methacrylate (MMA) with fluoroalcohols.

Facile, highly efficient and environmentally friendly transesterification mediated by platinum dioxide and nickel oxide under essentially neutral conditions

“…Although a few novel and practical transesterification reactions have been reported in the literature, [6][7][8][9][10][11][12][13][14][15][16][17] highly efficient and environmentally friendly catalysts for transesterification still need to be developed to solve the shortcomings of existing ones, such as environmental pollution, separation difficulty and poor substrate applicability.…”

One-pot synthesis for gradient copolymers via concurrent tandem living radical polymerization: mild and selective transesterification of methyl acrylate through Al(acac)3 with common alcohols

“…In addition, in molecular sieve (MS, 4 Å), the transesterification efficiency was enhanced by removing of the methanol molecule that formed during the reaction. 23 …”

Asymmetric Copolymers: Synthesis, Properties, and Applications of Gradient and Other Partially Segregated Copolymers

“…[134,135,137] This constraint is met for methacrylate (co) polymerization, however the technique is less reliable for the synthesis of acrylate-based gradients, [134,135] due to the decreased steric bulk around the polymeric ester moieties and hence increased rate of transesterification. For methacrylates the technique appears general with primary alcohols bearing a range of functionalities, with aliphatic alcohols, [134,135] poly(ethylene glycol), [135,136] fluorinated alcohols, [138,139] and alcohols bearing hydrogen-bond motifs [140] being exploited to date.…”