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

doi:10.16085/j.issn.1000-6613.2015.05.038

摘要/Abstract

摘要： 全氟辛烷磺酸/全氟辛酸(PFOA/PFOS)由于存在有争议的环境污染和生物蓄积等问题,已经成为全世界关注的焦点之一,寻找能够替代PFOA/PFOS的新型含氟表面活性剂具有重要的意义.本文综述了可能替代PFOA/PFOS新型含氟表面活性剂的合成路线和方法,并按照分子结构进行了分类,着重介绍了以下4类:①端基为CF₃O或(CF₃)₂N系列表面活性剂;②短氟链系列表面活性剂;③基于VDF或TFP系列表面活性剂;④全氟聚醚系列表面活性剂;同时对4类新型替代物的表面活性、生物降解性及在乳液聚合中的应用进行了归纳总结.目前PFOA/PFOS替代物的研究趋势,主要朝着降低含氟表面活性剂中氟元素比例、含减少氟链“有效长度”及插入N、O等杂原子等方向发展,使得新型含氟表活性剂更易降解、更环保、更安全.

关键词: 全氟辛烷磺酸/全氟辛酸, 含氟表面活性剂, 替代物

Abstract: There are increasing debates about the problem of PFOA/PFOS in environmental pollution and bioaccumulation,which has become the focus of attention of the world. It has vital significance to look for novel fluorinated surfactants to replace PFOA/PFOS.The synthesis methods of new possible fluorinated surfactants alternatives of PFOS/PFOA are reviewed and categorized according to the characteristics of molecular structures. Four categories of alternatives:(1) surfactants including either a CF₃O or (CF₃)₂N end-group; (2) surfactants containing short fluorined chain; (3) surfactants based on VDF or TFP; (4) surfactants from fluorinated polyethers,are presented. Meanwhile,surface activity,biodegradability and application in emulision polymerization of four categories of alternatives are discussed. Preliminary analysis indicates that the current research trends of PFOA/PFOS alternatives mainly reduce the ratio of fluorine,shorten fluorine-containing chain "effective length",and insert N or O heteroatom in the fluorinated surfactants,so that the novel fluorinated surfactants are more degradable,more environmentally friendly,and safer.

Key words: PFOA/PFOS, surfactants , fluorinated surfactants, alternatives

中图分类号:

TQ423.4

陈龙, 陈文亮, 赵景平, 刘锐, 陈爱民. 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(05): 1412-1421,1439.

CHEN Long, CHEN Wenliang, ZHAO Jingping, LIU Rui, CHEN Aimin. Progress of new fluorinated surfactants alternatives for PFOA/PFOS[J]. Chemical Industry and Engineering Progree, 2015, 34(05): 1412-1421,1439.

参考文献

[1] 曾毓华. 氟碳表面活性剂[M]. 北京:化学工业出版社,2001:1-7.

[2] Pabon M,Corpart J M. Fluorinated surfactants:Synthesis,properties,effluent treatment[J]. Journal of Fluorine Chemistry, 2002,114(2):149-156.

[3] Huang P Y,Chao Y C,Liao Y T. Preparation of fluoroacrylate nanocopolymer by miniemulsion polymerization used in textile finishing[J]. Journal of Applied Polymer Science,2004,94 (4):1466-1472.

[4] Wang S W,Marchant R E. Fluorocarbon surfactant polymers:Effect of perfluorocarbon branch density on surface active properties[J]. Macromolecules,2004,37(9):3353-3359.

[5] Kovalchuk N M,Trybala A,Matar O,et al. Fluoro-vs hydrocarbon surfactants:Why do they differ in wetting performance[J]. Advances in Colloid and Interface science, 2014,210:65-71.

[6] Lim F J,Ananthanarayanan K,Luther J,et al. Influence of a novel fluorosurfactant modified PEDOT:PSS hole transport layer on the performance of inverted organic solar cells[J]. Journal of Materials Chemistry,2012,22(48):25057-25064.

[7] Dupuy N,Pasc A,Mayotet E,et al. Synthesis and self-assembling behavior of F-amphiphilic functionalized amines[J]. Journal of Fluorine Chemistry, 2012,134:115-121.

[8] Nakata H,Kannan K,Nasu T,et al. Perfluorinated contaminants in sediments and aquatic organisms collected from shallow water and tidal flat areas of the ariake sea,Japan:Environmental fate of perfluorooctane sulfonate in aquatic ecosystems[J]. Environ. Sci. Technol.,2006,40:4916-4921.

[9] Schröder H F,Meesters R J W. Stability of fluorinated surfactants in advanced oxidation processes—A follow up of degradation products using flow injection-mass spectrometry,liquid chromatography-mass spectrometry and liquid chromatography-multiple stage mass spectrometry[J]. Journal of Chromatography A,2005,1082 (1):110-119.

[10] Johansson N,Fredriksson A,Eriksson P. Neonatal exposure to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) causes neurobehavioural defects in adult mice[J]. Neurotoxicology,2008,29(1):160-169.

[11] Zaggia A,Ameduri B. Recent advances on synthesis of potentially non-bioaccumulable fluorinated surfactants[J]. Current Opinion in Colloid & Interface Science,2002,17(4):188-195.

[12] Midasch O,Drexler H,Hart N,et al. Transplacental exposure of neonates to perfluorooctanesulfonate and perfluorooctanoate:A pilot study[J]. Int. Arch. Occup. Environ. Health,2007,80(7):643-648.

[13] Peschka M,Fichtner N,Hierse W,et al. Synthesis and analytical follow-up of the mineralization of a new fluorosurfactant prototype[J]. Chemosphere,2008,72(10):1534-1540.

[14] Frömel T,Peschka M,Fichtner N,et al. ω-[Bis(trifluoromethyl) amino] alkane-1-sulfonates:Synthesis and mass spectrometric study of the biotransformation products[J]. Rapid Communications in Mass Spectrometry, 2008,22(23):3957-3967.

[15] Peschka M,Frömel T,Fichtner N,et al. Mechanistic studies in biodegradation of the new synthesized fluorosurfactant 9-[4-(trifluoromethyl)phenoxy]nonane-1-sulfonate[J]. Journal of Chromatography A, 2008,1187(1-2):79-86.

[16] Hori H,Saito H,Sakai H,et al. Efficient decomposition of a new fluorochemical surfactant:Perfluoroalkane disulfonate to fluoride ions in subcritical and supercritical water[J]. Chemosphere, 2014.

[17] Olsen G W,Chang S C,Noker P E,et al. A comparison of the pharmacokinetics of perfluorobutanesulfonate (PFBS) in rats,monkeys,and humans[J]. Toxicology, 2009,256(1-2):65-74.

[18] Liu J X,Wang N,Szostek B,et al. 6-2 Fluorotelomer alcohol aerobic biodegradation in soil and mixed bacterial culture[J]. Chemosphere,2010,78(4):437–444.

[19] 陈荣圻. PFOS和PFOA替代品取向新进展(二)[J]. 印染,2012 (16):49-53.

[20] 杨百勤,陈凯,邢航,等. 以全氟丁基为基础的具有高表面活性的氟表面活性剂[J]. 物理化学学报,2009,25(12):2409-2412.

[21] 龙光斗,肖舒,付冬梅,等. 全氟丁基阳离子表面活性剂的合成与表面性能[J]. 有机氟工业,2012(3):1-4.

[22] 史鸿鑫,邱小丽,武宏科,等. 全氟己基季铵盐型表面活性剂的制备及其表面活性[J]. 精细化工,2012,29(5):438-442.

[23] 徐于娇,赵萌,李慧,等. 新型含氟表面活性剂的制备及其在含氟丙烯酸酯乳液聚合中的应用[J]. 涂料工业,2011,41(8):17-21.

[24] 徐运欢,郑成,林璟,等. 新型含氟季铵盐表面活性剂的合成及表面性能[J],化工进展,2014,33(2):439-445.

[25] Moe M K,Huber S,Svenson J,et al. The structure of the fire fighting foam surfactant Forafac^®1157 and its biological and photolytic transformation products[J]. Chemosphere,2012,89(7):869-875.

[26] Hagenaars A,Meyer I J,Herzke D,et al. The search for alternative aqueous film forming foams (AFFF) with a low environmental impact:Physiological and transcriptomic effects of two Forafac^® fluorosurfactants in turbot[J]. Aquat Toxicol,2011,104(3-4):168-176.

[27] Rahman M D,Houlihan F M,Padmanaban M,et al. Photoactive compoudns:US,20070015084A1[P]. 2007-06-18.

[28] Bodduri V D V,Chirumarry S,Lim J M,et al. Synthesis and properties of hemifluorinated disodium alkanesulfonates[J]. Journal of Fluorine Chemistry,2014,163:42-45.

[29] Vijaykumar B V D,Premkumar B,Jang K,et al. Environmentally benign perfluorooctanesulfonate alternatives using a Zn/CuI mediated Michael-type addition in imidazolium ionic liquids[J]. Green Chemistry, 2014,16(5):2406-2410.

[30] Dramé A,Taffin de Givenchy E,Dieng S Y,et al. One F-octyl versus two F-butyl chains in surfactant aggregation behavior[J]. Langmuir,2013,29(48):14815-14822.

[31] Peng S,Hung M H. Fluorinated sulfonate surfactants[J]. Journal of Fluorine Chemistry, 2012,133:77-85.

[32] Coope T,Moloy K,Yake A,et al. Fluorinated sulfamido amphoteric surfactants[J]. Journal of Fluorine Chemistry,2014,161:41-50.

[33] Ohno A,Kushiyama A,Kondo Y,et al. Synthesis and properties of gemini-type hydrocarbon–fluorocarbon hybrid surfactants[J]. Journal of Fluorine Chemistry, 2008,129(7):577-582.

[34] Debbabi K,Guittard F,Geribaldi S. Novel highly fluorinated sulfamates:Synthesis and evaluation of their surfactant properties[J]. Journal of Colloid and Interface Science,2008,326(1):235-239.

[35] Schuster T,Schellenberger S,Friedrich R,et al. Branched fluorinated amphiphiles based on carbohydrates[J]. Journal of Fluorine Chemistry,2013,154:30-36.

[36] Guo J,Resnick P,Efimenko K,et al. Alternative fluoropolymers to avoid the challenges associated with perfluorooctanoic acid[J]. Ind. Eng. Chem. Res.,2008,47(3):502-508.

[37] Boutevin G,Tiffes D,Loubat C,et al. New fluorinated surfactants based on vinylidene fluoride telomers[J]. Journal of Fluorine Chemistry,2012,134:77-84.

[38] Boschet F,Kostov G,Ameduri B,et al. Synthesis of 3,3,3-trifluoropropene telomers and their modification into fluorosurfactants[J]. Polymer Chemistry, 2012,3(1):217-223.

[39] Kostov G,Boschet F,Buller J,et al. First Amphiphilic Poly(vinylidene fluoride-co-3,3,3-trifluoropropene)-b-oligo(vinyl alcohol) block copolymers as potential nonpersistent fluorosurfactants from radical polymerization controlled by xanthate[J]. Macromolecules,2011,44(7):1841-1855.

[40] 赵明强,李辉,张炉青,等. 全氟聚醚的研究进展[J]. 山东化工,2009,38(4):25-27.

[41] Han L,Zhang Y M,Li H,et al. The synthesis and surface activity of perfluoro-2,5-dimethyl-3,6-dioxanonanoic acid ester fluorocarbon surfactants[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,334(1-3):176-180.

[42] 方超. 全氟聚醚的合成及改性研究[D]. 长沙:湖南大学,2012.

[43] 周杰华. 新型全氟聚醚衍生氟碳表面活性剂的合成及性能[D]. 上海:东华大学,2013.

[44] Kausch C M,Leising J E,Medsker R E,et al. Synthesis,characterization,and unusual surface activity of a series of novel architecture,water-dispersible poly(fluorooxetane)s[J]. Langmuir,2002,18(15):5933-5938.

[45] EFSA,EFSA Panel on food contact materials. Scientific opinion on the safety evaluation of the substance,perfluoro[(2-ethyloxy-ethoxy)acetic acid],ammonium salt,CAS No. 908020-52-0,for use in food contact materials[J]. EFSA Journal,2011,9(6):2183-2193.

[46] 3M Innovative Properties Company. Fluorinated elastomer latex,its production method,fluorinated elastomer and fluororubber molded product:US,20060199898A1[P]. 2006-9-7.

[47] Asahi Glass Company. Aqueous polytetrafluoroethylene dispersion and product made from same:EP,1939252A1[P]. 2008-07-02.

[48] Daikin industries. Aqueous tetrafluoroethylene polymer dispersion,process for producing the same,tetrafluoroethylene polymer powder,and molded tetrafluoroethylene polymer: EP,1681308A1[P]. 2006-07-19.