Copolymerization of Fluorinated Monomers with Hydrophilic Monomers in Aqueous Solution in Presence of Cyclodextrin

Abstract

Summary: New fluorinated copolymers were synthesized by copolymerization of 1H,1H,2H,2H‐perfluorodecyl methacrylate (1) with hydrophilic comonomers methacrylic acid (3), 2‐acrylamido‐2‐methylpropane sulfonic acid (6), 3‐trimethylammonium propyl methacrylamide chloride (7) and N,N‐dimethylmethacrylamidopropyl‐N‐3‐sulfopropylammoniumbetaine (8). The reaction was carried out in water using randomly methylated β‐cyclodextrin (RAMEB) for solubilization of the fluorinated monomer by forming a host‐guest complex (1a). Polymerization kinetics were investigated and copolymerization parameters were determined. Additionally, a RAMEB complex of tert‐butyl methacrylate (2a) was copolymerized with 1a in water. For comparison, copolymerization of the uncomplexed monomers 1 and 2 were carried out in organic solvents. Evaluation of copolymerization kinetics and parameters showed significant differences in the relative reactivities of the free monomers and the monomer‐RAMEB complexes. magnified image

New, Aqueous Radical (Co)Polymerization of Olefins at Low Temperature and Pressure

“…The hydrophobic cavity of CDs binds suitable organics by hydrophobic interactions and/or H-bonds, while the hydrophilic outer shell provides the water solubility. Ritter et al successfully polymerized various hydrophobic monomers, such as styrene [33][34][35][36][37][38], (meth)acrylates [33,34,[39][40][41][42][43][44], phenol derivatives [45,46], fumarates [47,48], dienes [49,50], halo-olefins [51][52][53], and other non-commercial ones [54][55][56][57][58][59][60][61] in water, solubilized by CD, via free radical polymerization methods. During the polymerization, the CD, every time, slips off from the last monomeric unit of the polymer, and the product precipitates, resulting in a pure product, or simple purification.…”

Three different β‐cyclodextrins direct the emulsion copolymerization of a highly fluorinated methacrylate toward distinctive nanostructured particle morphologies

“…Formation of ICs with β‐CDs allows free radical22, 26–30 or even catalytic31 polymerization of hydrophobic monomers, including FMA,32 to proceed in aqueous solution according to what has been described as a dispersion or precipitation polymerization of an initially soluble IC. While the CD can be recycled, yet such procedure is impractical as it requires very high concentrations of a highly soluble functional β‐CD (e.g., methyl‐ or hydroxypropyl‐derivatives) and does not allow to obtain a stable polymer latex 33, 34…”

Semicontinuous Emulsion Polymerization of Butyl Methacrylate and 1, 3-Butadiene in the Presence of Cyclodextrins and Cytocompatibility of Dicarboxylic Acid Telechelic Oligo(butyl Methacrylate)s Derived from Ozonolysis of the Latexes

“…Several examples of polymerizations in water of hydrophobic monomers have been reported. Thus, Ritter et al formed CD‐monomer complexes and then polymerized these using radical polymerizations 10–19. These polymerizations used the unique solubilizing power of CDs so that it was possible to produce aqueous solutions of the CD‐monomer complexes formed from monomers that are otherwise water insoluble.…”