Synthesis of semifluorinated block copolymers by atom transfer radical polymerization

Abstract

Two sets of styrene‐based semifluorinated block copolymers, one with a perfluoroether pendant group and another with a perfluoroalkyl group, were synthesized by atom transfer radical polymerization. Microphase separation of the block copolymers was established by small‐angle X‐ray scattering and differential scanning calorimetry (DSC). DSC measurements also showed that the perfluoroether‐based polymer had a low glass‐transition temperature (−44 °C). Contact‐angle measurements indicated that the semifluorinated block copolymers had low surface energies (ca. 13 mJ/m2). These materials hold promise as low‐surface‐energy additives or surfactants for supercritical CO2 applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 853–861, 2004

Association of immunoglobulin‐like transcript 6 deficiency with Sjögren's syndrome

“…Fluorinated (meth)acrylic monomers can be combined with a range of other monomers and have previously been copolymerized with monomers of similar character such as methyl methacrylate, butyl methacrylate, and styrene 42–44. For example, Zhang et al prepared a series of semifluorinated fluorocarbon/hydrocarbon diblock and triblock copolymers by ATRP with the macroinitiators obtained from bulk ATRP of styrene, butyl acrylate, and methyl acrylate 42.…”

“…For example, Zhang et al prepared a series of semifluorinated fluorocarbon/hydrocarbon diblock and triblock copolymers by ATRP with the macroinitiators obtained from bulk ATRP of styrene, butyl acrylate, and methyl acrylate 42. Radhakrishnan et al reported the synthesis of a related PS block copolymer and a novel semifluorinated block copolymer with a perfluoroether pendant group by ATRP 43. Martinelli et al synthesized a new amphiphilic block copolymers consisting of two PS carrying an amphiphilic polyoxyethylene‐ b ‐polytetrafluoroethylene chain side‐group by ATRP 44.…”

Nanostructure, Morphology, and Properties of Fluorous Copolymers Bearing Ionic Grafts

“…65,66 These amphiphilic fluorous-ionic diblock copolymers were found to display varying degrees of nanophase separation dependent upon the ion content (IEC) of the styrene block. For 0.9-1.2 mmol/g IEC membranes, distinct perforated lamellae were observed.…”

Fluorine‐Containing Block Copolymers: Synthesis and Application as a Template for Nanocellular and Porous Structures Using Supercritical Carbon Dioxide

“…Recently, controlled-radical polymerization, such as atom-transfer radical polymerization (ATRP), nitroxide-mediated radical polymerization (NMP), and reversible additionfragmentation chain transfer (RAFT) polymerization, has been widely developed and applied to perfluoroalkylated block copolymer synthesis, as shown in Figure 23.1 (Zhang et al, 1999;Lim et al, 2002;Hussain et al, 2002;Li et al, 2002a;Andruzzi et al, 2002;Gopalan et al, 2002;Radhakrishnan et al, 2004;Hikita et al, 2004;Shemper and Mathias, 2004;Jankova and Hvilsted, 2005;Galli et al, 2005). Styrene and (meth)acrylate monomers containing perfluoroalkyl groups are used as second monomers in sequential polymerization.…”