Cinétique de polymérisation radicalaire de (méth)acrylates à chaîne latérale fluorée

Abstract

The radical polymerization of acrylates and methacrylates bearing a perfluorinated chain with an a ,x-bistrichloromethyled or an a ,x-dibenzylic azo initiator is presented. These initiators were synthesized in two or three steps in 40 -50% overall yields. Molecular weights of the fluorinated polymers were determined from various methods by taking into account the behavior of these monomers in the termination step (recombination or disproportionation). These methods consisted in the titration of the chlorine content by elemental analysis or from 1 H NMR by the determination of the aromatic end-groups. Although the determination of the chlorine content led to a lack of accuracy, the aromatic initiator enabled one to assess the molecular weights of the fluoropolymers produced. From the characteristic kinetic constants, the kinetics of homopolymerization of these methacrylates contributed to a simulation of these reactions which allowed one to compare the theoretical molecular weights to the experimental ones. Macromol. Chem. Phys. 200,No. 9 i

Vinyl ethers and epoxides photoinduced copolymerization with perfluoropolyalkylether monomers

“…3 and 4 , it seems that the length of the hydrogenated spacer between the PFPAE chains and the reactive end-groups of the fluorinated comonomers has an influence on reactivity. Similar behaviors were observed and studied for both living cationic [ 23 , 40 , 48 ] and radical [ 49 , 50 ] photopolymerization. This effect was observed in the photoinduced polymerization of the macromonomers studied in [ 24 ]: the long-fluorinated chain decreased the monomer reactivity by an electron withdrawing effect, lowering the nucleophilicity of the functional group.…”