22 6 2010 6 PROGRESS IN CHEMISTRY Vol. 22 No. 6 Jun. 2010 * 510640 O631. 1 O647. 5 A 1005-281X 2010 06-1133-09 Structures and Surface Wettability of Fluorinated Meth Acrylate Polymers Yang Hao Pi Pihui Wen Xiufang Zheng Dafeng Cheng Jiang Yang Zhuoru School of Chemistry and Chemical Engineering South China University of Technology Guangzhou 510640 China Abstract Fluorinated meth acrylate polymers are a class of novel low surface energy materials in which the fluorinated chains confer them hydrophobic and oleophobic properties and the non-fluorinated chains render them fine solubility and compatibility. The surface wettability can be changed by designing and controlling the structures of fluorinated meth acrylate polymers. In this article we review the influence factors of surface wettability for fluorinated meth acrylate homopolymers random block graft core-shell copolymers and crosslinked network copolymers etc. The relationships between the structures and surface wettability including wetting stability of the polymers are discussed by means of analyzing the crystallinity surface element content surface energy and contact angle of the polymers and the related models are also given which providing theoretical basis and guidance for design and synthesis of stable surface wettability of fluorinated meth acrylate polymers. Key words fluorinated meth acrylate polymer structures surface wettability wetting stability contact angle hysteresis Contents 1 Introduction 2 Contact angle hysteresis and wetting stability 3 The influence of fluorinated meth acrylate polymers structures on surface wettability and wetting stability 3. 1 Homopolymers 3. 2 Copolymers 4 Conclusion and outlook 2009 9 2009 12 * No. 2008B0106004 Corresponding author e-mail zhryang@ scut. edu. cn
1134 22 1 / 22 PTFE PVDF PTFE PTFE CF 3 Gibbs 6. 7mN / m 1 PTFE 2 5 3 2 θ A advancing angle θ R receding angle θ A - θ R spacer group vinyl ester 6 7 8 10 3 1 11 13 14 16 23 24 2 25 3 17 21 26 1 CF 2 n - θ A / θ R 3. 1 CH 2 m / 17 n 8
6 1135 1 Fig. 1 Chemical structures of fluorinated meth acrylate homopolymers 23 2 < n 6 2 Fig. 2 Schematic illustration of structures and models for water repellency of homopolymers 23 γ p γ d n 8 n 6 27 n 2 Corpart 25 N- n = 6 n = 8 N- γ p γ d - 2 23 Caillier 26 n = 6 m m = 0 29 30 α- m Saidi 24 n = 4 6 8 m = 2 3. 2 4 6 / 1 1 2- Hartmann 28
1136 22 / 3. 2. 1 / θ R θ A AIBN BPO 4 3 4 θ R m 16 / γ d γ p Fig. 4 22 PFA-ran-PAA Models for water repellency of PFA-ran-PAA 22 CH 2 m Hartmann 17 m = 1 18 m = 0 6 11 3 b 3 Fig. 3 Chemical structures of fluorinated meth acrylate copolymers 10mol% θ A 125 30mol% m Morita 22 FA m n = 9 AA m = 1 2 4 8 12 m = 0 16 18 m = 6 PFA-ran-PAA 3 a 11 m < 8 8 m < m = 18 m = 1 16 m 16 m θ A θ R 31 m < 8 θ R 45 m 8 θ R m 16 θ R 98 m < 8 Saidi 32 33 F CF 2 8 CH 2 m OC O CH CH 2 F 8 A m 16 BA MMA m < 8 F 8 A / BA / γ d γ p / F 8 A / BA / MMA XPS
6 1137 20 25 / 66 60 m 25 5 F 8 A / BA / MMA m = 2 F 8 A / BA m = 8 Takahashi 34 MMA FOM FOSAM MPEGMA MMA / FOSAM MMA / MPEGMA / FOM MMA / FOSAM θ R N S / θ R MMA / MPEGMA / FOM θ R MMA / MPEGMA MMA PEG PEG θ R θ R Fujimori 35 5 a b 35 FF 10 EA Fig. 5 Models for layer structures a acrylate OA FF 10 EA / OA copolymers b methacrylate copolymers 35 FF 10 EMA / OMA X WAXD X 3. 2. 2 SAXS X NEXAFS sub-cell ATRP RAFT FF 10 EA / OA = 2 1 5 1 1 FF 10 EA / OA = 1 5
1138 22 PSt-b-PFA PFA 18. 7mol% 120 Wang 36 0 - PSt-b- PFMA n m 76 75 PFA n m miscible state n 6 A S A CF 3 S A 10. 8mN / m n > 6 B S B Valtola 38 CF 3 FMA EIMA 8mN / m PFMA-b-PEIMA PFMA-ran-PEIMA DSC 6 FMA Luo 39 - - PDMS-b-PMMA-b-PFMA PDMS-b-PFMA PFMA 121 PFMA 25. 3 141 XPS F / Si PMMA 36 6 end-capped Ni 40 42 ATRP Fig. 6 Schematic representation of the relationship between 2 3 the fluorinated side chain end structures and their critical surface tensions PMMA-ec- 36 FMA PMMA-ran- PFMA FMA Hikita 37 0. 38mol% ATRP - 120 84
6 1139 13. 63mol% FMA 0. 001 0. 1wt% PMMA γ d γ p - push-me / pull-you 43 / / 7 46 49 PTFE PTFE / PTFE 7 a PMMA-ec-FMA b PMMA-ran- 41 PFMA Fig. 7 a Self-assembly of the PMMA-ec-FMA. b Segregation of the fluorinated components in the PMMA-ran- PFMA 41 3. 2. 3 Ameduri 20 52 UV 44 45 < 1wt% XPS Park 45 / / PFMA-g-PMMA / MMA PMMA FMA / / - Qu 50 51 3. 2. 4
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