Novel Polymerization of Fluorinated 2‐Vinylcyclopropane in Aqueous Solution via Cyclodextrin Complexes

Abstract

We report on the first examples of the free radical polymerization of a fluorinated 2‐vinylcyclopropane 1 and its copolymerization with an alkyl 2‐vinylcyclopropane 2 in aqueous solution via their host‐guest complexation with a random methylated β‐cyclodextrin (RAMEB) using a water‐soluble initiator (VA50). Upon polymerization, the dethreaded cyclodextrin remained in water solution, whereas the water‐insoluble polymer precipitated out and was isolated. The polymers prepared exhibited mesophase behavior over a wide range of temperature. Both Tg and Ti of the copolymers increased linearly with the amount of fluorinated co‐units.Complexation of fluorinated vinylcyclopropane 1 with RAMEB and polymerization in water solution.magnified imageComplexation of fluorinated vinylcyclopropane 1 with RAMEB and polymerization in water solution.

Living Free Radical Polymerization of Cyclodextrin Host‐Guest Complexes of Styrene via the Reversible Addition Fragmentation Chain Transfer (RAFT) Process in Aqueous Solution

“…Our group has investigated the radical polymerization of several CD-complexed vinylmonomers. [10][11][12][13][14][15][16][17] It was shown that this new type of precipitating polymerization can be described by kinetic equations similar to those for classical polymerization in solution. [18,19] Furthermore, we have demonstrated that the polymerization of MMA-CD-complexes in aqueous medium using ATRP has a living character.…”

Cyclodextrin in polymer chemistry: Kinetic studies on the free-radical polymerization of cyclodextrin-complexed styrene from homogeneous aqueous solution

“…Furthermore, the preparation and polymerization of equimolar cyclodextrin complexes of commercial standard monomers like styrene 1 and methyl methacrylate (MMA have been described. It was also shown that the precipitation polymerization of a cyclodextrin complex of a poorly water-soluble monomer like MMA can be described by kinetic equations similar to those for the classical polymerization in solution [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20].…”

Kinetic Studies upon the Influence of Cyclodextrin on the Polymerization of Methacrylamides in Homogenous Aqueous Solution

“…The free-radical [5][6][7][8][9][10][11][12][13][14][15] and controlled 'living' [16] polymerizations of various CD-complexed vinyl derivatives and also some other types of monomers in water have recently been investigated. The synthesis of electrical conducting polymers from aqueous media via oxidative coupling have also been described, [17,18] and some kinetics of the homoand copolymerization of several kinds of CD-complexed monomers in aqueous medium have been studied.…”