结构可控含氟共聚物的合成及其应用研究新进展

doi:10.16085/j.issn.1000-6613.2016.12.030

化工进展 ›› 2016, Vol. 35 ›› Issue (12): 3942-3953.DOI: 10.16085/j.issn.1000-6613.2016.12.030

结构可控含氟共聚物的合成及其应用研究新进展

吕弛^1,2, 崔崑¹, 岳春波³, 李树材², 马志¹

1 中国科学院有机功能分子合成与组装化学重点实验室, 中国科学院上海有机化学研究所, 上海 200032;
2 天津科技大学化工与材料学院, 天津 300457;
3 中国科学院有机氟化学重点实验室, 中国科学院上海有机化学研究所, 上海 200032

收稿日期:2016-03-29 修回日期:2016-06-22 出版日期:2016-12-05 发布日期:2016-12-05
通讯作者: 崔崑,助理研究员,主要从事功能高分子材料、纳米复合材料研究。E-mail:cuikun@sioc.ac.cn。
作者简介:吕弛(1991-),男,硕士研究生,主要从事RAFT聚合研究。
基金资助:
上海市自然科学基金项目（14ZR1448700）。

New progress in the synthesis and application of well-defined fluorinated copolymers

LÜ Chi^1,2, CUI Kun¹, YUE Chunbo³, LI Shucai², MA Zhi¹

1 Key Laboratory of Self-Assembly and Chemistry of Organic Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China;
2 College of Material Science and Chemical Engineering, Tianjin University of Science & Technology, Tianjin 300457, China;
3 Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Received:2016-03-29 Revised:2016-06-22 Online:2016-12-05 Published:2016-12-05

摘要/Abstract

摘要： 近年来，含氟聚合物以其优异的耐热性、耐氧化性、耐候性、耐腐蚀性以及低介电常数、低表面能等特点，在疏水材料、抗污材料、表面活性剂、造影剂等领域具有广泛的应用前景，受到研究者的密切关注，各种拓扑结构的含氟共聚物被设计合成出来并在相关领域得到应用。本文首先简要介绍了含氟聚合物的性质和研究现状，然后详细叙述了可逆加成-断裂链转移聚合（RAFT）、原子转移自由基聚合（ATRP）、碘转移自由基聚合（ITP）、单电子转移活性聚合（SET-LRP）、氮氧稳定自由基聚合（NMP）以及活性阴离子聚合（LAP）等聚合方法在结构可控含氟共聚物合成中的研究新进展，并对其聚合机理、优缺点以及所得共聚物的性质和应用进行了总结，最后对结构可控含氟共聚物的设计、合成及实际应用前景进行了展望，提出发展绿色环保功能性含氟聚合物将是未来的主要研究热点。

关键词: 聚合, 聚合物, 合成, 可控/"活性"自由基聚合, 含氟(甲基)丙烯酸酯, 氟烯烃

Abstract: In recent years,fluorinated polymers have attracted much attention because of their excellent properties of high resistance to heat and oxygen,superior weatherability,good chemical inertness,low dielectric constants,and low surface energy,and broad application prospect in fields of hydrophobic materials,antifouling materials,surfactant,and contrast agent. Fluorinated copolymers of various topologies have been synthesized and applied in related fields. In this paper,firstly,the properties and current research status of fluorinated polymers are briefly introduced. Secondly,the new research progress of well-defined fluorinated copolymers synthesized by reversible addition-fragmentation chain transfer polymerization(RAFT),atom transfer radical polymerization(ATRP),iodine transfer radical polymerization(ITP),reverse iodine transfer polymerization(RITP),single electron transfer living radical polymerization(SET-LRP),nitroxide-mediated radical polymerization(NMP),and living anionic polymerization(LAP)are reviewed in detail respectively. In addition,the mechanism,advantage and disadvantage of polymerization,and the properties and applications of the fluorinated copolymer obtained are also summarized. Finally,the research foreground and practical application of the design and synthesis of well-defined fluorinated copolymers based on controlled/"living" polymerization are prospected. We put forward that environmentally friendly functional fluorinated polymers will be the research focuses in the future.

Key words: polymerization, polymers, synthesis, controlled/"living"radical polymerization, fluoroalkyl(meth)acrylates, fluoroolefin

中图分类号:

O631.5

吕弛, 崔崑, 岳春波, 李树材, 马志. 结构可控含氟共聚物的合成及其应用研究新进展[J]. 化工进展, 2016, 35(12): 3942-3953.

LÜ Chi, CUI Kun, YUE Chunbo, LI Shucai, MA Zhi. New progress in the synthesis and application of well-defined fluorinated copolymers[J]. Chemical Industry and Engineering Progree, 2016, 35(12): 3942-3953.

参考文献

[1] 徐运欢,郑成,林璟,等.含氟季铵盐表面活性剂的合成与应用研究进展[J].化工进展,2013,32(7):1641-1648.
[2] 徐涛,刘鹤,宋湛谦,等.含氟聚硅氧烷应用进展[J].化工进展,2014,33(1):140-143.
[3] 陈龙,陈文亮,赵景平,等.全氟辛烷磺酸/全氟辛酸替代物-新型含氟表面活性剂的研究进展[J].化工进展,2015,34(5):1412-1421.
[4] CHIEFARI J,CHONG Y K,ERCOLE F,et al.Living free-radical polymerization by reversible addition-fragmentation chain transfer:the RAFT process[J].Macromolecular,1998,31:5559-5562.
[5] LV C,CUI K,LI S C,et al.Polystyrene-b-poly (2,2,2-trifluoroethyl acrylate)-b-polystyrene copolymers:synthesis and fabrication of their hydrophobic porous films,spheres,and fibers[J].J.Polym.Sci.Part A:Polym.Chem.,2016,54:678-685.
[6] 毛国梁,王欣,宁英男,等.基于RAFT聚合策略合成功能化聚烯烃嵌段聚合物的研究进展[J].化工进展,2012,31(10):2282-2287.
[7] BABINOT J,RENARD E,DROUMAGUET B L,et al.Facile synthesis of multicompartment micelles based on biocompatible poly (3-hydroxyalkanoate)[J].Macromol.Rapid Commun.,2013,34:362-368.
[8] AMADO E,KRESSLER J.Triphilic block copolymers with perfluorocarbon moieties in aqueous systems and their biochemical perspectives[J].Soft Matter,2011,7:7144-7149.
[9] LI X X,YANG Y H,LI G J,et al.Synthesis and self-assembly of a novel fluorinated triphilic block copolymer[J].Polym.Chem.,2014,5:4553-4560.
[10] SEMSARILAR M,LADMIRAL V,BLANAZS A,et al.Poly(methacrylic acid)-based AB and ABC block copolymer nano-objects prepared via RAFT alcoholic dispersion polymerization[J].Polym.Chem.,2014,5:3466-3475.
[11] KOIRY B P,CHAKRABARTY A,SINGHA N K.Fluorinated amphiphilic block copolymers via RAFT polymerization and their application as surf-RAFT agent in miniemulsion polymerization[J].RSC Adv.,2015,5:15461-15468.
[12] LI G H,XU A H,GENG B,et al.Synthesis and characterization of fluorinated diblock copolymer of 2,2,2-trifluoroethyl methacrylate and methyl methacrylate based on RAFT polymerzation[J].Journal of Fluorine Chemistry,2014,165:132-137.
[13] ZHANG S X,ZHAO J Q,CHU G H,et al.Synthesis,characterization and properties of a novel fluorinated methacrylate polymer[J].Fluorine Chem.,2011,132:915-919.
[14] ZHOU D Y,TENG H X,KOIKE K,et al.Copolymers of methyl methacrylate and fluoroalkyl methacrylates:effects of fluoroalkyl groups on the thermal and optical properties of the copolymers[J].J.Polym.Sci.Part A:Polym.Chem.,2008,46:4748-4755.
[15] WANG L,ZHANG C Y,CONG H L,et al.Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies[J].J.Phys.Chem.B,2013,117:8256-8268.
[16] OGAWA M,KATAOKA H,NITAHARA S,et al.Water-soluble fluorinated polymer nanoparticle as ¹⁹F MRI contrast agent prepared by living random copolymerization from dendrimer initiator[J].Bull.Chem.Soc.Jpn.,2012,85:79-86.
[17] ROSSI S,BENAGLIA M,ORTENZI M,et al.Poly(ethylene-glycol)-based fluorinated esters:a readily available entry for novel ¹⁹F-MRI agents[J].Tetrahedron Lett.,2011,52:6581-6583.
[18] WANG K W,PENG H,THURECHT K J,et al.pH-responsive star polymer nanoparticles:potential ¹⁹F MRI contrast agents for tumour-selective imaging[J].Polym.Chem.,2013,4:4480-4489.
[19] ZHANG C,PENG H,PUTTICK S,et al.Conformation of hydrophobically modified thermoresponsive poly (OEGMA-co-TFEA) across the LCST revealed by NMR and molecular dynamics studies[J].Macromolecules,2015,48:3310-3317.
[20] WANG J S,MATYJASZEWSKI K.Controlled "living" radical polymerization.Atom transfer radical polymerization in the presence of transition-metal complexes[J].J.Am.Chem.Soc.,1995,117:5614-5615.
[21] XUE Y,LU H C,ZHAO Q L,et al.Polymethylene-b-poly(styrene-co-2,3,4,5,6-pentafluoro styrene)copolymers:synthesis and fabrication of their porous films[J].Polym.Chem.,2013,4:307-312.
[22] ZHU Y,FORD W T.Novel fluorinated block copolymer stabilizers for dispersion polymerization of cross-linked poly (2-ethylhexyl methacrylate-stat-chloromethylstyrene) in fluorinated solvents[J].Macromolecules,2008,41:6089-6093.
[23] GUO W J,TANG X D,XU J,et al.Synthesis,characterization,and property of amphiphilic fluorinated ABC-type triblock copolymers[J].J.Polym.Sci.Part A:Polym.Chem.,2011,49:1528-1534.
[24] ZHANG Y,YAN Y C,WANG Y,et al.The synthesis and solution properties of hyperbranched polyglycerolsmodified with hexafluorobutyl acrylate[J].Colloids and Surfaces A:Physicochem.Eng.Aspects,2013,436:563-569.
[25] 李时伟,邢铁玲,李战雄,等.用ATRP方法在蚕丝织物表面接枝含氟丙烯酸酯的拒水整理工艺条件优化试验[J].蚕业科学,2013,39:400-405.
[26] SUN Y,LIU W Q,MA Z Q.Synthesis of epoxy-terminated fluoropolymer via ATRP and the properties of epoxy thermosets modified with it[J].Polym.Bull.,2013,70:1531-1542.
[27] BOUTEVIN B.From telomerization to living radical polymerization[J].J.Polym.Sci.Part A:Polym.Chem.,2000,38:3235-3243.
[28] TSANG E M W,ZHANG Z,AMI C C,et al.Nanostructure,morphology,and properties of fluorous copolymers bearing ionic grafts[J].Macromolecules,2009,42:9467-9480.
[29] LI J,TAN S,DING S,et al.High-field antiferroelectric behaviour and minimized energy loss in poly (vinylidene-co-trifluoroethylene)-graft-poly (ethyl methacrylate) for energy storage application[J].J.Mater.Chem.,2012,22:23468-23476.
[30] DAVID G,BOYER C,TONNAR J,et al.Use of iodocompounds in radical polymerization[J].Chem.Rev.,2006,106:3936-3981.
[31] BOYER C,AMEDURI B,BOUTEVIN B,et al.Radical terpolymerization of 1,1,2-trifluoro-2-pentafluorosulfanylethylene and pentafluorosulfanylethylene in the presence of vinylidene fluoride and hexafluoropropylene by iodine transfer polymerization[J].Macromolecules,2008,41:1254-1263.
[32] GOHY J F,LEFEVRE N,D'HAESE C,et al.Multicompartment micelles from blends of terpolymers[J].Polym.Chem.,2011,2:328-332.
[33] LOPEZ G,THENAPPAN A,AMEDURI B.Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization[J].ACS Macro.Lett.,2015,4:16-20.
[34] LACROIX-DESMAZES P,SEVERAC R,OTAZAGHINE B,et al.Reverse iodine transfer polymerization(RITP):use of elemental iodine as a versatile control agent in living radical polymerization[J].Polym.Prepr.,2003,44:683-684.
[35] ENRIQUEZ-MEDRANO F J,GUERRERO-SANTOS R,HERNANDEZ-VALDEZ M,et al.Synthesis of diblock and triblock copolymers from butyl acrylate and styrene by reverse iodine transfer polymerization[J].Journal of Applied Polymer Science,2011,119:2476-2484.
[36] BOUILHAC C,CHIRAT M,JOLY-DUHAMEL C,et al.Reverse iodine transfer polymerization(RITP)of 1,1,2,2-tetrahydroperfl uorodecyl acrylate in supercritical carbon dioxide[J].Macromol.Chem.Phys.,2013,214:2259-2265.
[37] PERCEC V,GULIASHVILI T,LADISLAW J S,et al.Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates,methacrylates,and vinyl chloride mediated by SET at 25℃[J].J.Am.Chem.Soc.,2006,128:14156-14165.
[38] SAMANTA S R,CAI R L,PERCEC V.SET-LRP of semifluorinated acrylates and methacrylates[J].Polym.Chem.,2014,5:5479-5491.
[39] SAMANTA S R,CAI R L,PERCEC V.A rational approach to activated polyacrylates and polymethacrylates by using a combination of model reactions and SET-LRP of hexafluoroisopropyl acrylate and methacrylate[J].Polym.Chem.,2015,6:3259-3270.
[40] GEORGE M K,VEREGIN R P N,KAZMAIER P M,et al.Narrow molecular weight resins by a free-radical polymerization process[J].Macromoleculars,1993,26:2987-2988.
[41] TSOUKATOS T,PISPAS S,HADJICHRISTIDIS N.Complex macromolecular architectures by combining TEMPO living free radical and anionic polymerization[J].Macromoleculars,2000,33:9504-9511.
[42] BOSMAN A W,VESTBERG R,HEUMANN A,et al.A modular approach toward functionalized three-dimensional macromolecules:from synthetic concepts to practical applications[J].J.Am.Chem.Soc.,2003,125:715-728.
[43] LACROIX-DESMAZES P,ANDRE P,DESIMONE J M,et al.Macromolecular surfactants for supercritical carbon dioxide applications:synthesis and characterization of fluorinated block copolymers prepared by nitroxide-mediated radical polymerization[J].J.Polym.Sci.Part A:Polym.Chem.,2004,42:3537-3552.
[44] SZWARC M."Living" polymers[J].Nature,1956,178:1168-1169.
[45] HADJICHRISTIDIS N,PITSIKALIS M,PISPAS S,et al.Polymers with complex architecture by living anionic polymerization[J].Chem.Rev.,2001,101:3747-3792.
[46] UMINO Y,NARITA T,HAMANA H.Initiation reactivity of anionic polymerization of fluorinated acrylates and methacrylates with diethyl (ethyl cyanoacetato) aluminum[J].J.Polym.Sci.Part A:Polym.Chem.,2008,46:7011-7021.
[47] YAN Z L,LIU W Q,SUN Y,et al.Controlled synthesis,characterization and application of novel functional fluorinated polymer by metal-free anionic polymerization[J].Journal of Macromolecular Science Part A:Pure and Applied Chemistry,2012,49:764-771.
[48] YAN Z L,LIU W Q,GAO N,et al.Synthesis and characterization of a novel difunctional fluorinated acrylic oligomer used for UV-cured coatings[J].Journal of Fluorine Chemistry,2013,147:49-55.
[49] XIONG D,LIU G J,HONG L Z,et al.Superamphiphobic diblock copolymer coatings[J].Chem.Mater.,2011,23:4357-4366.
[50] BOYER C,VALADE D,AMEDURI B,et al.Kinetics of the iodine transfer polymerization of vinylidene fluoride[J].J.Polym.Sci.Part A:Polym.Chem.,2006,44:5763-5777.

结构可控含氟共聚物的合成及其应用研究新进展

New progress in the synthesis and application of well-defined fluorinated copolymers

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