P[CF3(CF2)5CH2MA-co-MMA] and P[CF3(CF2)5CH2MA-co-BA] copolymers: Reactivity ratios and surface properties

Abstract

This study aimed at reducing the surface energy of coatings by copolymerization of commonly used monomers with fluorine‐containing monomers. Copolymers of 1,1‐dihydroperfluoroheptyl methacrylate (FHMA) and methyl methacrylate (MMA) or butyl acrylate (BA) are prepared by low‐conversion polymerization in solution. Using 1H‐NMR data and nonlinear least‐squares data fitting, reactivity ratios of these systems at 80°C are determined to be rFHMA = 1.31, rMMA = 0.76, and rFHMA = 3.15, rBA = 0.38, respectively. We assume that the penultimate unit effect plays an important role in these systems. Introduction of the perfluoroalkyl side chain lowers the polymer surface energy significantly; copolymers of MMA and FHMA show a reduction in total surface energy of about 50 % at a content of 15 mol % FHMA as compared with pure PMMA. The attainable reduction in surface energy is much larger than with, for example, Teflon. This is due to the preferential adsorption of the —CF3 groups of the fluoroalkyl side chain, if compared to that of the —CF2— groups of Teflon. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 159–165, 2001

The Preparation and Surface Properties of Silicone-grafted Acrylic Copolymer Coatings

“…Figures 5 and 6 also show that the surface energy of the acrylic polymer less than 15.0 mN m 21 can be reached through grafting with HSO, which is close to the surface free energy of the polydimethylsiloxane (14.1 mN m 21 ) [12], polytetrafluoroethylene (21.5 mN m 21 ) [12] and poly(1,1-dihydroperfluoroheptyl methacrylate) (12.6 mN m 21 ) [13]. Thus, grafting of HSO on the acrylic main chain is an effective and simple method to reduce the surface energy of the polymer.…”

“…The 13 C-NMR spectra of the solid-state polymers were determined by AVANCE DMX300 (Bruker Biospin GmbH, German). Proton decoupled solid-state NMR spectra were acquired at 75.5 MHz for 13 C using cross-polarization combined with the magic angle spinning (CP/MAS) technique.…”

New perfluoropolyether urethane methacrylates as surface modifiers: Effect of molecular weight and end group structure

“…Therefore, fluoropolymers are high value materials in many applications from biomedical devices, optical fibres to fuel cells, advanced textiles: many well-architectured structures have been studied and industrialised, as recently reviewed by Ameduri and Boutevin [4]. Synthesis of fluoroacrylates has received great interest [5] and the corresponding polymers or copolymers [6][7][8][9] have found application in various fields, in particular as high performance coatings: when tested on different substrates such as metals, paper, stone, optical fibres and textiles they give good protection against corrosion, environmental pollution, weather aggression and graffiti.…”

Copolymerizations of butyl methacrylate and fluorinated methacrylates via RAFT miniemulsion polymerization

“…The result we got from Figure 5 is that r BMA = 0.63, r HFBMA = 0.63 in poly(BMA‐ co ‐HFBMA) and r BMA = 1.08, r TFEMA = 0.33 in poly(BMA‐ co ‐TFEMA). In poly(BMA‐ co ‐HFBMA), although the introduction of fluorinated group affects the reactivity of monomer, the similarity of chemical structures and sizes between BMA and HFBMA make them compatible well 10. As a result of these two effects, BMA and HFBMA finally have the same reactivity ratios.…”

“…It is known that the reactivity ratios are the important parameters for the prediction of the compositions for any starting feed and to understand the kinetics and mechanistic aspects of copolymers 8, 9. Despite the industrial interest, up to date, only a few investigations have been carried out on the reactivity ratios of the fluorinated monomers 10. In addition, the accurate control over molecular weight and chain structures has attracted many investigators because they can hardly be achieved with traditional free radical polymerization.…”