含氟有机硅整理剂的合成与性能研究
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摘要
本文对一种具有拒水、拒油性能的含氟的有机硅整理剂的合成工艺、结构与性能以及中间体、产物的物化性能等作了较为深入的研究，并初步探讨了产品的应用性能。
首先，优选出一条针对国内原材料供应情况，较为合理、简单的合成工艺路线，并对氟烃基改性硅油的两步合成反应的工艺条件进行了优化，即：第一步，先利用不饱和醇与全氟辛酸在酸催化剂的作用下进行酯化反应，通过萃取、过滤，制得含碳碳不饱和键的碳氟化合物，第二步，含不饱和双键的碳氟化合物再与不同含氢量含氢硅油在铂催化剂的作用下进行硅氢化反应，制得一系列含氟量不同的含氟的有机硅材料。并且，通过正交实验设计，工艺流程得到优化。
本研究综合利用了现代先进的测试仪器，较为全面的分析了原料、中间产物、以及产物的分子结构等各方面的性能参数。利用IR谱图和~1HNMR测定了含氢硅油的分子结构和分子量，确定了中间产品的分子结构。通过对反应不同阶段的转化率分析，明确反应进程及反应物、产物的浓度的关系，对含不饱和键的碳氟化合物与含氢硅油的反应过程进行了初步的探索。
本文还对产物的应用性能进行了系列测试，通过电镜对产物在纤维表面的形貌进行了研究，并对产品的含氟量对纤维表面形貌影响进行了研究。初步探索了含氟的有机硅的拒水拒油机理和拒水拒油性能的影响因素。
The detailed research was focused on the synthesis process structure and properties of pseudo-perfluoroalkyl polysilicones and on the physical and chemical properties of intermediates and product. And preliminary research was done on the production appliance performance .
Firstly, a two-step synthesis process that point to the material providing inland was selected, this synthesis process was reasonable and easy relatively. Besides the conditions of synthesis reaction were adjusted. Namely, the first step reaction were prepared by esterifing allyl alcohol with perfluoro caprylic acid . allyl-octonary-carbon fluoric ester was attained by extraction and filtration . the second step were prepared by hydrosilylation between hydrogen-silicone and perfluoro caprylic acid a-allyl ester, in this reaction, we can attain a series of presudo- perfluoroalkyl polysilicones that have different fluoric content. At above synthesis, the optimum methodology were probed by orthogonal experiment design. Moreover, in this article through comprehensive utilization modern analytical and testing instrument . the performance parameter and molecular structure of the raws , middlings and outcome were analyzed. The molecular structure and molecular weigh of HS were analyzed by IR and 1HNMR, the molecula
r structure of intermediates was confirmed ; comparing to the concentration change of reactant and resultant, reaction course of hydrosilylation was confirmed .
Finally ,the applied properties of Fs were tested. By electron microscope we observe surface shape and visage of fibrin , and research the character that the quantity of fluoric infected to surface shape and visage of fibrin. The mechanism and the infection factor of property of resistance to water and oil on the fiber.
首先，优选出一条针对国内原材料供应情况，较为合理、简单的合成工艺路线，并对氟烃基改性硅油的两步合成反应的工艺条件进行了优化，即：第一步，先利用不饱和醇与全氟辛酸在酸催化剂的作用下进行酯化反应，通过萃取、过滤，制得含碳碳不饱和键的碳氟化合物，第二步，含不饱和双键的碳氟化合物再与不同含氢量含氢硅油在铂催化剂的作用下进行硅氢化反应，制得一系列含氟量不同的含氟的有机硅材料。并且，通过正交实验设计，工艺流程得到优化。
本研究综合利用了现代先进的测试仪器，较为全面的分析了原料、中间产物、以及产物的分子结构等各方面的性能参数。利用IR谱图和~1HNMR测定了含氢硅油的分子结构和分子量，确定了中间产品的分子结构。通过对反应不同阶段的转化率分析，明确反应进程及反应物、产物的浓度的关系，对含不饱和键的碳氟化合物与含氢硅油的反应过程进行了初步的探索。
本文还对产物的应用性能进行了系列测试，通过电镜对产物在纤维表面的形貌进行了研究，并对产品的含氟量对纤维表面形貌影响进行了研究。初步探索了含氟的有机硅的拒水拒油机理和拒水拒油性能的影响因素。
The detailed research was focused on the synthesis process structure and properties of pseudo-perfluoroalkyl polysilicones and on the physical and chemical properties of intermediates and product. And preliminary research was done on the production appliance performance .
Firstly, a two-step synthesis process that point to the material providing inland was selected, this synthesis process was reasonable and easy relatively. Besides the conditions of synthesis reaction were adjusted. Namely, the first step reaction were prepared by esterifing allyl alcohol with perfluoro caprylic acid . allyl-octonary-carbon fluoric ester was attained by extraction and filtration . the second step were prepared by hydrosilylation between hydrogen-silicone and perfluoro caprylic acid a-allyl ester, in this reaction, we can attain a series of presudo- perfluoroalkyl polysilicones that have different fluoric content. At above synthesis, the optimum methodology were probed by orthogonal experiment design. Moreover, in this article through comprehensive utilization modern analytical and testing instrument . the performance parameter and molecular structure of the raws , middlings and outcome were analyzed. The molecular structure and molecular weigh of HS were analyzed by IR and 1HNMR, the molecula
r structure of intermediates was confirmed ; comparing to the concentration change of reactant and resultant, reaction course of hydrosilylation was confirmed .
Finally ,the applied properties of Fs were tested. By electron microscope we observe surface shape and visage of fibrin , and research the character that the quantity of fluoric infected to surface shape and visage of fibrin. The mechanism and the infection factor of property of resistance to water and oil on the fiber.
引文
[1]. 袁利斌 刘海梁，浅谈氟硅系列材料的性能和应用 有机氟工业 2002年第二期
[2]. 曾敏华 氟碳表面活性剂 化学工业出版社 2001年6月第一版213-314
[3]. 周宏湘 拒水、拒油、防污功能兼备的氟树脂 丝绸 1998年第七期
[4] Benerito R R, Berni R J, Fagley T F.Tex. Res.J. 1977,47:551
[5] Shiina Q, JP-KoKai 昭 54-119418 1979
[6]. Arai M. et al .JP-KoKia 2 平 289623 1990
[7]. 阿托费纳化学股份有限公司，R·阿明—萨纳伊 C·C·格雷恩，包含有机硅烷的含氟聚合物及其制备方法 US patent US60/165，123
[8]. 博士伦有限公司，J·F·孔斯勒 R·M·奥扎克，氟硅氧烷水凝胶 US patent US08/017056
[9] 德国希尔股份有限公司，P·詹克纳、A·J·弗林斯、M·霍恩、J·蒙凯维奇、B·斯坦奇，带有氟烷基团的有机硅化合物的制备及其用途German patent DE19644561．2
[10] 陶氏康宁东丽硅氧烷株式会社，小林秀树、正富亨，含氟的有机聚硅氧烷、用于碳氟树脂粉末的分散改进剂、和有机树脂组合物Japanese patent JP363069/1999
[11] 三井化学株式会社，福村考记、岛冈隆、及川英明、园田宽、后藤谦一、成濑纯子、林秀俊、安武刚，制备氟化硅化合物的方法，Japanese patent JP262847/99
[12] 中国科学院化学研究所 一种超双疏(疏水、疏油)表面处理剂和用途 中国专利 CN00103573
[13] 东华大学 卿凤翎 韦昌青 含氟有机硅的制备和应用 中国专利CN02145013
[14] Pierce O R .Appl Polym Symp. 1970,14:7
[15] Owen M J .Groh J L.J Appl Polym Sci,1990.40:789
[16] 梁治齐 陈溥 氟表面活性剂 中国轻工业出版社 313
[17] TEXT. RES. J. 1962,32,320
[18] Shafrin E G, Zisman WA. J. Phys. Chem.1962, 66; 740
[19] Skinner Philip; Dennis J;David Robert; Preparation of perfluoroic-polysilicone intermediates and compositions US 3012006. 1958; GB1188212. 1967
[20] 幸松明，王一璐．有机硅合成工艺及产品应用，化学工业出版社，2000(9)：217 445
[21] Pierce O R, et al JAme Chem. soc,1953,75:5618
[22] Pierce O R,et al. J Ame Chem Soc. 1954 76:476
[23] Trrant P,et al. J Ame Chem Soc. 1957 79:6536
[24] Pasono H J, et al, Polymers prepared from 4,4'-bis(2-(amino(halo) phenoxyphenyl) hexafluoroisopropyl) diphenyl ether US 2686194,1954
[25] Midland Silicones Co. GB 807235, 1959
[26] Midland Silicones Co. GB 802358, 1958
[27] 唐培．精细有机合成化学及工艺学，天津大学出版社：272
[28] 邢其毅 徐瑞秋 周政 基础有机化学(上册) 人民教育出版社 1980年6月 第一版 456
[29] Marcinec B. Culinski J Urbaniak W et al, Marxiniec Bed Comprehensive handbook on hydroscilation Orford: Pergamon 1992
[30] Pukhrarevich E. Lukevics V B,Voronkov M G In: Institute of organic synthesis ed. Perspectives Hydrosilation Latvia :Riga 1992
[31] Chalk A J, Homogeneous catalysis Ⅱ.The mechanism of the hydrosilation of
[32] Lewis L N, Uriarte R J. Organometallies. 1990;9:624
[33] Lewis L N, Uriarte R J. In: Moser W R,Slocun W eds,Homogeneous transition metal catalyzed reations,Adv.Chem Ser. 230,Washongton D C; American Chemical Society, 1992:541
[34] Lewis L N, Lewis N .J.Am.Chem. Soc. 1986;108;7 228
[35] Lewis L N. J.Am.Chem. Soc. 1990;112;7 998
[36] Lewis L N, Uriarte R J. Lewis N .J. Catal.,1991;127:105
[37] Micro-miniature mercury tilt-type inertia switch USP 3 993 882
[38] 谭必思 潘慧铭 宇航材料工艺 1999年 第3期
[39]JISK-1557
[40]Analysis of silicones New York N.K.,1974: 150-151
[41]刘燕军 氨纶纺丝油剂的研制．天津纺织工学院研究生毕业论文，1995(12)
[42]王桂莲．聚醚改型硅氧烷磷酸酯的合成及性能测试研究
[43]吕彤，张纪梅．精细化工实验，天津纺织工学院材料系，1996(11)：96-98
[44]解如阜 高世伟 纺织助剂实用分析，纺织工业出版社 1987(12)
[45]Burleigh; Malcolm B. (St. Paul, MN); Jariwala; Chetan R (Woodbury, MN); Lockridge; James E. (Maplewood, MN); Hauser; Edward R. (St. Croix, WI) Process of drawing fibers through the use of a spin finish composition having a hydrocarbon sufactant, a repellent fluorochemical, and a fluorochemical compatibilizer US patent 6207088
[46]中华人民共和国专业标准 涂层织物拒油性测试方法 FZ/T 01067-1999
[47]Analysis of silicones New York N.K.,1974: 257-259
[48]Patrick cancou t .etc., Functional Polysiloxanes. Ⅰ Microstructure of Poly(hydrogenmethylisiloxane-co-dimethylsiloxane)s Obtained by Cationic Copolymerization, J. Poly. Sci. part A: Polymer Chemistry 2000.38(5):827-836
[49]姚新生 陈英杰 有机化合物波谱分析 人民卫生出版社 1983年7月
[50]项宗筠等 硅酮表面活性剂的制备和性能 表面活性剂工业 1985(3)32-35
[51]W.A.Zisman et al.. The Kirk-Othmer Encyclopedia of Chemical Technology, 2nd edn 1966,9,707
[2]. 曾敏华 氟碳表面活性剂 化学工业出版社 2001年6月第一版213-314
[3]. 周宏湘 拒水、拒油、防污功能兼备的氟树脂 丝绸 1998年第七期
[4] Benerito R R, Berni R J, Fagley T F.Tex. Res.J. 1977,47:551
[5] Shiina Q, JP-KoKai 昭 54-119418 1979
[6]. Arai M. et al .JP-KoKia 2 平 289623 1990
[7]. 阿托费纳化学股份有限公司，R·阿明—萨纳伊 C·C·格雷恩，包含有机硅烷的含氟聚合物及其制备方法 US patent US60/165，123
[8]. 博士伦有限公司，J·F·孔斯勒 R·M·奥扎克，氟硅氧烷水凝胶 US patent US08/017056
[9] 德国希尔股份有限公司，P·詹克纳、A·J·弗林斯、M·霍恩、J·蒙凯维奇、B·斯坦奇，带有氟烷基团的有机硅化合物的制备及其用途German patent DE19644561．2
[10] 陶氏康宁东丽硅氧烷株式会社，小林秀树、正富亨，含氟的有机聚硅氧烷、用于碳氟树脂粉末的分散改进剂、和有机树脂组合物Japanese patent JP363069/1999
[11] 三井化学株式会社，福村考记、岛冈隆、及川英明、园田宽、后藤谦一、成濑纯子、林秀俊、安武刚，制备氟化硅化合物的方法，Japanese patent JP262847/99
[12] 中国科学院化学研究所 一种超双疏(疏水、疏油)表面处理剂和用途 中国专利 CN00103573
[13] 东华大学 卿凤翎 韦昌青 含氟有机硅的制备和应用 中国专利CN02145013
[14] Pierce O R .Appl Polym Symp. 1970,14:7
[15] Owen M J .Groh J L.J Appl Polym Sci,1990.40:789
[16] 梁治齐 陈溥 氟表面活性剂 中国轻工业出版社 313
[17] TEXT. RES. J. 1962,32,320
[18] Shafrin E G, Zisman WA. J. Phys. Chem.1962, 66; 740
[19] Skinner Philip; Dennis J;David Robert; Preparation of perfluoroic-polysilicone intermediates and compositions US 3012006. 1958; GB1188212. 1967
[20] 幸松明，王一璐．有机硅合成工艺及产品应用，化学工业出版社，2000(9)：217 445
[21] Pierce O R, et al JAme Chem. soc,1953,75:5618
[22] Pierce O R,et al. J Ame Chem Soc. 1954 76:476
[23] Trrant P,et al. J Ame Chem Soc. 1957 79:6536
[24] Pasono H J, et al, Polymers prepared from 4,4'-bis(2-(amino(halo) phenoxyphenyl) hexafluoroisopropyl) diphenyl ether US 2686194,1954
[25] Midland Silicones Co. GB 807235, 1959
[26] Midland Silicones Co. GB 802358, 1958
[27] 唐培．精细有机合成化学及工艺学，天津大学出版社：272
[28] 邢其毅 徐瑞秋 周政 基础有机化学(上册) 人民教育出版社 1980年6月 第一版 456
[29] Marcinec B. Culinski J Urbaniak W et al, Marxiniec Bed Comprehensive handbook on hydroscilation Orford: Pergamon 1992
[30] Pukhrarevich E. Lukevics V B,Voronkov M G In: Institute of organic synthesis ed. Perspectives Hydrosilation Latvia :Riga 1992
[31] Chalk A J, Homogeneous catalysis Ⅱ.The mechanism of the hydrosilation of
[32] Lewis L N, Uriarte R J. Organometallies. 1990;9:624
[33] Lewis L N, Uriarte R J. In: Moser W R,Slocun W eds,Homogeneous transition metal catalyzed reations,Adv.Chem Ser. 230,Washongton D C; American Chemical Society, 1992:541
[34] Lewis L N, Lewis N .J.Am.Chem. Soc. 1986;108;7 228
[35] Lewis L N. J.Am.Chem. Soc. 1990;112;7 998
[36] Lewis L N, Uriarte R J. Lewis N .J. Catal.,1991;127:105
[37] Micro-miniature mercury tilt-type inertia switch USP 3 993 882
[38] 谭必思 潘慧铭 宇航材料工艺 1999年 第3期
[39]JISK-1557
[40]Analysis of silicones New York N.K.,1974: 150-151
[41]刘燕军 氨纶纺丝油剂的研制．天津纺织工学院研究生毕业论文，1995(12)
[42]王桂莲．聚醚改型硅氧烷磷酸酯的合成及性能测试研究
[43]吕彤，张纪梅．精细化工实验，天津纺织工学院材料系，1996(11)：96-98
[44]解如阜 高世伟 纺织助剂实用分析，纺织工业出版社 1987(12)
[45]Burleigh; Malcolm B. (St. Paul, MN); Jariwala; Chetan R (Woodbury, MN); Lockridge; James E. (Maplewood, MN); Hauser; Edward R. (St. Croix, WI) Process of drawing fibers through the use of a spin finish composition having a hydrocarbon sufactant, a repellent fluorochemical, and a fluorochemical compatibilizer US patent 6207088
[46]中华人民共和国专业标准 涂层织物拒油性测试方法 FZ/T 01067-1999
[47]Analysis of silicones New York N.K.,1974: 257-259
[48]Patrick cancou t .etc., Functional Polysiloxanes. Ⅰ Microstructure of Poly(hydrogenmethylisiloxane-co-dimethylsiloxane)s Obtained by Cationic Copolymerization, J. Poly. Sci. part A: Polymer Chemistry 2000.38(5):827-836
[49]姚新生 陈英杰 有机化合物波谱分析 人民卫生出版社 1983年7月
[50]项宗筠等 硅酮表面活性剂的制备和性能 表面活性剂工业 1985(3)32-35
[51]W.A.Zisman et al.. The Kirk-Othmer Encyclopedia of Chemical Technology, 2nd edn 1966,9,707