具有“树枝状”结构的短氟碳链含氟单体的合成与表征
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摘要
首先以乙二醇单乙烯基醚为成核分子引发缩水甘油开环聚合,优化反应条件,合成中心含乙烯氧基的超支化聚缩水甘油醚;后将其磺酸酯化,在40℃,氟醇与磺酸酯基团的摩尔比为1.5:1时,用全氟己基乙醇亲核取代合成出具有"树枝状"结构的含氟单体,探讨了各步反应影响因素,并用傅里叶变换红外光谱进行了结构表征。利用该"树枝状"新型结构,大量氟链段可稳定聚集于表面,为进一步制备获得具有优异拒水拒油性能的含氟聚合物提供了有利的基本条件。
Firstly,the hyperbranched polyglycidol(HPG)with ethyleneoxy groups was synthesized by using ethylene glycol vinyl ether(EGVE)as core-forming molecule to initiate the ring-opening polymerization of glycidyl.Subsequently,the hydroxyl groups on the terminal of the HPG were transformed into sulfonate groups,and nucleophilic substituting sulfonate with RFOH under the RFOH is 1.5equivalent of hydroxyl group at 40℃,thus fluoromonomer with dendritic structure was synthesized.The factors of each step reaction were discussed and the structure was characterized by FT-IR.Based on the new structure of "dendritic",a large number of fluorine segments can be stably gathered on the surface,which provides favorable basic conditions for further preparation of fluoropolymers with excellent water repellency and oil repellency properties.
Firstly,the hyperbranched polyglycidol(HPG)with ethyleneoxy groups was synthesized by using ethylene glycol vinyl ether(EGVE)as core-forming molecule to initiate the ring-opening polymerization of glycidyl.Subsequently,the hydroxyl groups on the terminal of the HPG were transformed into sulfonate groups,and nucleophilic substituting sulfonate with RFOH under the RFOH is 1.5equivalent of hydroxyl group at 40℃,thus fluoromonomer with dendritic structure was synthesized.The factors of each step reaction were discussed and the structure was characterized by FT-IR.Based on the new structure of "dendritic",a large number of fluorine segments can be stably gathered on the surface,which provides favorable basic conditions for further preparation of fluoropolymers with excellent water repellency and oil repellency properties.
引文
[1]王文贵,杨勇,陈秉倪.高分子含氟聚合物材料的发展及应用现状[J].有机硅氟资讯,2008(2):20-24.Wang W G,Yang Y,Chen B N.Development and application of polymer fluoropolymer materials[J].Silicone and Fluorine Information,2008(2):20-24.
[2] Ellis D A,Martin J W,Desilva A O,et al.Degradation of fluorotelomer alcohols:alikely atmospheric source of perfluorinated carboxylic acids[J].Environ.Sci.Technol.,2004,38:3316-3321.
[3] Lehmler H J,Rama Rao V V V N S,Nauduri D,et al.Synthesis and structure of environmentally relevant perfluorinated sulfonamides[J].J.Fluorine Chem.,2007,128:595-607.
[4] Stock N L,Furdui V I,Muir D C G,et al.Perfluoroalkyl contaminants in the Canadian arctic:evidence of atmospheric transport and local contamination[J].Environ.Sci.Technol.,2007,41:3529-3536.
[5]郭睿,蔡亚岐,江桂斌.全氟辛烷磺酰基化合物(PFOS)的污染现状与研究趋势[J].化学进展,2006,18(6):808-813.Guo R,Cai Y J,Jiang G B.Current research of perfluorooctane sulfonate[J].Progress in Chemistry.2006,18(6):808-813.
[6]成丽.短氟链含氟聚丙烯酸酯的合成及其织物整理应用[D].苏州:苏州大学,2011.Cheng L.Synthesis of fluorinated short-chain alkyl acrylate copolymer emulsion and application an texitle finishing[D].Suzhou:Soochow University,2011.
[7] Honda K,Morita M,Otsuka H,et al.Molecular aggregation structure and surface properties of poly(fluoroalkyl acrylate)thin films[J].Macromolecules,2005,38:5699-5705.
[8] Ji G,Paul R,Kirill E,et al.Alternative fluoropolymers to avoid thechallenges associated with perfluorooctanoic acid[J].Ind.Eng.Chem.Res.,2008,47:502-508.
[9] Qiongyan W,Qinghua Z,Xiaoli Z,et al.Structure and surface properties of polyacrylates with short fluorocarbon side chain:role of the main chain and spacer groud[J].J.Polym.Sci.Part A:Polym.Chem.,2010,48:2584-2593.
[10] Sa6di S,Guittard F,Guimon C,et al.Fluorinated acrylic polymers:surface properties and XPS investigations[J].J.Appl.Polym.Sci.,2006,99:821-827.
[11] Sa6di S,Guittard F,Guimon C,et al.Synthesis and characterization of copolymers based on styrene and partially fluorinated acrylates[J].Eur.Polym.J.,2006,42:702-710.
[12] Sa6di S,Guittard F,Guimon C,et al.Fluorinated comblike homopolymers:the effect of spacer lengths on surface properties[J].J.Polym.Sci.Part A:Polym.Chem.,2005,43:3737-3747.
[13] Huang J Q,Meng W D,Qing F L.Synthesis and repellent properties of vinylidene fluoride-containing polyacrylates[J].J.Fluorine Chem.,2007,128:1469-1477.
[14]邓瑾妮,郝国庆,郑朝晖,等.具有“伞形”结构的短氟碳链含氟丙烯酸酯聚合物的制备及拒水性能[J].高分子材料科学与工程,2016,32(5):11-17.Deng J N,Hao G Q,Zheng Z H,et al.Preparation and water repellent properties of short-chain fluorinated acrylate polymer with“umbrella”structure[J].Polymer Materials Science&Engineering.2016,32(5):11-17.
[15] Jikei M,Kakimoto M A.Hyperbranched Polymers a promising new class of materials[J].Prog.Polym.Sci.,2001,26:1233-1285.
[16] Sunder A,Hanselmann R,Frey H,et al.Controlled synthesis of hyperbranched polyglycerols by ring-opening multibranching polymerization[J].Macromolecules.1999,32:4240-4246.
[2] Ellis D A,Martin J W,Desilva A O,et al.Degradation of fluorotelomer alcohols:alikely atmospheric source of perfluorinated carboxylic acids[J].Environ.Sci.Technol.,2004,38:3316-3321.
[3] Lehmler H J,Rama Rao V V V N S,Nauduri D,et al.Synthesis and structure of environmentally relevant perfluorinated sulfonamides[J].J.Fluorine Chem.,2007,128:595-607.
[4] Stock N L,Furdui V I,Muir D C G,et al.Perfluoroalkyl contaminants in the Canadian arctic:evidence of atmospheric transport and local contamination[J].Environ.Sci.Technol.,2007,41:3529-3536.
[5]郭睿,蔡亚岐,江桂斌.全氟辛烷磺酰基化合物(PFOS)的污染现状与研究趋势[J].化学进展,2006,18(6):808-813.Guo R,Cai Y J,Jiang G B.Current research of perfluorooctane sulfonate[J].Progress in Chemistry.2006,18(6):808-813.
[6]成丽.短氟链含氟聚丙烯酸酯的合成及其织物整理应用[D].苏州:苏州大学,2011.Cheng L.Synthesis of fluorinated short-chain alkyl acrylate copolymer emulsion and application an texitle finishing[D].Suzhou:Soochow University,2011.
[7] Honda K,Morita M,Otsuka H,et al.Molecular aggregation structure and surface properties of poly(fluoroalkyl acrylate)thin films[J].Macromolecules,2005,38:5699-5705.
[8] Ji G,Paul R,Kirill E,et al.Alternative fluoropolymers to avoid thechallenges associated with perfluorooctanoic acid[J].Ind.Eng.Chem.Res.,2008,47:502-508.
[9] Qiongyan W,Qinghua Z,Xiaoli Z,et al.Structure and surface properties of polyacrylates with short fluorocarbon side chain:role of the main chain and spacer groud[J].J.Polym.Sci.Part A:Polym.Chem.,2010,48:2584-2593.
[10] Sa6di S,Guittard F,Guimon C,et al.Fluorinated acrylic polymers:surface properties and XPS investigations[J].J.Appl.Polym.Sci.,2006,99:821-827.
[11] Sa6di S,Guittard F,Guimon C,et al.Synthesis and characterization of copolymers based on styrene and partially fluorinated acrylates[J].Eur.Polym.J.,2006,42:702-710.
[12] Sa6di S,Guittard F,Guimon C,et al.Fluorinated comblike homopolymers:the effect of spacer lengths on surface properties[J].J.Polym.Sci.Part A:Polym.Chem.,2005,43:3737-3747.
[13] Huang J Q,Meng W D,Qing F L.Synthesis and repellent properties of vinylidene fluoride-containing polyacrylates[J].J.Fluorine Chem.,2007,128:1469-1477.
[14]邓瑾妮,郝国庆,郑朝晖,等.具有“伞形”结构的短氟碳链含氟丙烯酸酯聚合物的制备及拒水性能[J].高分子材料科学与工程,2016,32(5):11-17.Deng J N,Hao G Q,Zheng Z H,et al.Preparation and water repellent properties of short-chain fluorinated acrylate polymer with“umbrella”structure[J].Polymer Materials Science&Engineering.2016,32(5):11-17.
[15] Jikei M,Kakimoto M A.Hyperbranched Polymers a promising new class of materials[J].Prog.Polym.Sci.,2001,26:1233-1285.
[16] Sunder A,Hanselmann R,Frey H,et al.Controlled synthesis of hyperbranched polyglycerols by ring-opening multibranching polymerization[J].Macromolecules.1999,32:4240-4246.