含全氟己基甲基丙烯酰类单体、聚合物的合成及性能表征
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摘要
含氟丙烯酸树脂是指传统丙烯酸树脂的主链或者侧链上的氢原子被氟原子取代后的聚合物。含氟丙烯酸树脂具有良好的成膜性、强憎水性、化学稳定性、热稳定性、抗氧化性、生物相容性以及良好的气体渗透性,这些性质使其在许多领域都得到了很好的应用,有效地改善了传统丙烯酸树脂所存在的耐水性差、低温变脆、高温易发黏等弱点。
目前开发的含氟丙烯酸树脂主要是以全氟辛烷磺酸基化合物(PFOS)和全氟辛酸(PFOA)为原料制备的,但在降解过程中会生成难降解的全氟烷基羧酸和磺酸类化合物,对环境和人体具有较大的危害。欧洲议会于2006年12月2日发布了关于限制PFOS的2006/122/ECOF法令,严格限制PFOS及其相关产品的销售和使用。另外,这类树脂的难降解性与氟碳链长度成正比,因此含短氟碳链的高性能树脂的研究成为一个重要的课题。
本课题从3-(全氟正己基)环氧丙烷(PFOP)出发合成了多种含全氟己基侧链的甲基丙烯酸酯单体；通过1HNMR、13CNMR、19FNMR及元素分析法对其进行了表征。选取其中两种含氟单体(FMA)与甲基丙烯酸丁酯(BMA)、丙烯酸丁酯(EA)聚合得到了三元共聚物,通过IR、DSC、SEM等对其涂膜性能进行了初步研究。结果表明,全氟己基侧链的引入能有效提高涂膜的拒水能力和耐高温性能；芳香环的引入提高了涂膜的硬度；利用热场发射扫描电镜对聚合物薄膜截面的氟元素含量进行了分析,结果表明,退火工艺有助于含氟基团更好的向表面迁移,氟元素沿截面呈梯度分布。
本课题采用了PFOP开环制备含氟醇,合成方法简单,为今后实验室单体制备提供了一种较为简便的方法。
本课题合成的聚合物在具有已知含氟丙烯酸酯聚合物特点的基础上,同时具有易降解、对环境污染小、对颜料、填料的附着力好的优点,综合性能良好,预期可作为防水涂料,具有较好的应用前景。
Fluorine-containing acrylic resins are the acrylic resins whose hydrogen atoms on the main or chain are replaced by the fluorine atoms. They have been widely used for their excellent properties of film forming, hydrophobic property, chemical stability, thermal stability, oxidation resistance, biocompatibility and gas permeability. Thus effectively improve the weakness such as poor water resistance, low temperature brittle and prone to high temperature of the traditional acrylic resins.
The degradation process of the current fluorine-containing acrylic resins would produce persistent organic pollutants:perfluoroalkyl carboxylic acids and sulfonic acids, which result environmental pollution and illness. European Parliament issued a decree (2006/122/ECOF) on the restriction of PFOS on December 2,2006:PFOS and the related products must be strictly limited both in business and application. In addition, the recalcitrance of the resins is directly proportional to the length of the fluorocarbon chains.
Starting from 3-perfluorohexyl-1,2-epoxypropane (FHOP), several fluorinated acrylate monomers containing tridecafluorohexane were obtained in this paper; The monomers were characterized by 1H NMR,13C NMR and 19F NMR. Fluoroacrylate copolymers P(FA-BMA-EA) were successfully synthesized by solution polymerization. IR, DSC, GPC, and SEM were used in investigating the copolymer films. The results show:The addition of tridecafluorohexane can increase the water and heat resistance; while the aromatic ring increase the heat resistance and the rigidity of the films. The Thermal Field Emission SEM was used in analyzing the distribution of fluorine on the cross-section of the films. The results show that the annealing process helps the fluoride groups migrate to the surface better, and fluorine distributes graded along the cross-section.
Fluorinated alcohols were obtained by the ring opening reaction of PFOP in this paper. The synthesis process is simple for preparing fluorinated acrylate monomers.
Besides the features of the traditional acrylic resins, the copolymers prepared in this paper also had good performance as easy-degradation, low-pollution, excellent-adhesion, and is expected to be used as waterproof coating.
目前开发的含氟丙烯酸树脂主要是以全氟辛烷磺酸基化合物(PFOS)和全氟辛酸(PFOA)为原料制备的,但在降解过程中会生成难降解的全氟烷基羧酸和磺酸类化合物,对环境和人体具有较大的危害。欧洲议会于2006年12月2日发布了关于限制PFOS的2006/122/ECOF法令,严格限制PFOS及其相关产品的销售和使用。另外,这类树脂的难降解性与氟碳链长度成正比,因此含短氟碳链的高性能树脂的研究成为一个重要的课题。
本课题从3-(全氟正己基)环氧丙烷(PFOP)出发合成了多种含全氟己基侧链的甲基丙烯酸酯单体；通过1HNMR、13CNMR、19FNMR及元素分析法对其进行了表征。选取其中两种含氟单体(FMA)与甲基丙烯酸丁酯(BMA)、丙烯酸丁酯(EA)聚合得到了三元共聚物,通过IR、DSC、SEM等对其涂膜性能进行了初步研究。结果表明,全氟己基侧链的引入能有效提高涂膜的拒水能力和耐高温性能；芳香环的引入提高了涂膜的硬度；利用热场发射扫描电镜对聚合物薄膜截面的氟元素含量进行了分析,结果表明,退火工艺有助于含氟基团更好的向表面迁移,氟元素沿截面呈梯度分布。
本课题采用了PFOP开环制备含氟醇,合成方法简单,为今后实验室单体制备提供了一种较为简便的方法。
本课题合成的聚合物在具有已知含氟丙烯酸酯聚合物特点的基础上,同时具有易降解、对环境污染小、对颜料、填料的附着力好的优点,综合性能良好,预期可作为防水涂料,具有较好的应用前景。
Fluorine-containing acrylic resins are the acrylic resins whose hydrogen atoms on the main or chain are replaced by the fluorine atoms. They have been widely used for their excellent properties of film forming, hydrophobic property, chemical stability, thermal stability, oxidation resistance, biocompatibility and gas permeability. Thus effectively improve the weakness such as poor water resistance, low temperature brittle and prone to high temperature of the traditional acrylic resins.
The degradation process of the current fluorine-containing acrylic resins would produce persistent organic pollutants:perfluoroalkyl carboxylic acids and sulfonic acids, which result environmental pollution and illness. European Parliament issued a decree (2006/122/ECOF) on the restriction of PFOS on December 2,2006:PFOS and the related products must be strictly limited both in business and application. In addition, the recalcitrance of the resins is directly proportional to the length of the fluorocarbon chains.
Starting from 3-perfluorohexyl-1,2-epoxypropane (FHOP), several fluorinated acrylate monomers containing tridecafluorohexane were obtained in this paper; The monomers were characterized by 1H NMR,13C NMR and 19F NMR. Fluoroacrylate copolymers P(FA-BMA-EA) were successfully synthesized by solution polymerization. IR, DSC, GPC, and SEM were used in investigating the copolymer films. The results show:The addition of tridecafluorohexane can increase the water and heat resistance; while the aromatic ring increase the heat resistance and the rigidity of the films. The Thermal Field Emission SEM was used in analyzing the distribution of fluorine on the cross-section of the films. The results show that the annealing process helps the fluoride groups migrate to the surface better, and fluorine distributes graded along the cross-section.
Fluorinated alcohols were obtained by the ring opening reaction of PFOP in this paper. The synthesis process is simple for preparing fluorinated acrylate monomers.
Besides the features of the traditional acrylic resins, the copolymers prepared in this paper also had good performance as easy-degradation, low-pollution, excellent-adhesion, and is expected to be used as waterproof coating.
引文
1.王金.含氟丙烯酸酯乳液的制备、结构与性能研究.华南理工大学博士论文,2009.
2.周命,张玉兴,周树军.丙烯酸树脂的制备及其在涂料中的应用与研究现状[J].上海涂料,2007,45(7)：25-29.
3.缭京媛.氟塑料加工和应用[M].北京：化学工业出版社,1987,126.
4. Murray K P, Bartoszek Jr E J. Fluorine in Coating Conference [R]. Orlando, Florida,1999,19.
5.山边正显,松尾仁.含氟材料的研究开发.华东理工大学出版社.2003,143.
6.曾昭伦.元素有机化学[M].北京：科学出版社,1965,147.
7.邹盛欧.氟树脂近况[J].化工新型材料,1997,25(9)：3-7.
8. Morita M, Ogisu H. Surface properties of perfluoroalkylethy acrylate/n-alkyl acrylate copolymers [J]. J. APPl. Poly. Sci,1999,73:1741-1749.
9. Patrice C, Hartmanna, Colleta A. Acrylic monomers and polymers with perfluoroalkylatedbiphenyl side groups:synthesis and phase transitions [J]. J. Fluorine Chem.,2004,125(12):1909-1918.
10.周钰明,黄静艳等.N-羟乙基全氟辛酰胺甲基丙烯酸酯聚合物的合成及性能研究[J].精细化工,2002,8(19)：78-79.
11. Reinhard F, Linemann, Thomas E. Latex blends of fluorinated and fluorine-fere acrylaets:emulsion polymerization and tapping mode aotmic force micorscopy of film formation [J]. Macormolecules,1999,32(6):1715-1722.
12. Hayakawa Y, Terasawa N. Synthesis of novel Polymethcrylates bearing cyclic perfluoroalkyl groups [J]. Polymer,1998,39(17):4151-4154.
13. Desimone J M, Guan Z, et al. Homogeneous free radical polymerzations of fluorinated monomers in supercritical carbon dioxide [J]. Polymer Preprints(USA), 1992,33(2):329-330.
14.魏海洋,李欣欣,王康等.含氟丙烯酸酯共聚物制备超疏水表面及其形成机理的研究.化学学报,2008,66(12)：1470-1476.
15.戴荣继,张明南,李惠黎.聚(丙烯酸全氟辛酸乙二醇酯)类防水防油剂的性能研究[J].精细石油化工,1991,(5)：35-38.
16. Hashimoto, Yataka [P]. JP 97-132606,1997.
17. Kim D K, Lee S B. Latex blends of fluorinated and fluorine-free aerylate emulsion polymerization and tapping mode atomic force microscopy of film formation [J]. J. Appl. Polym. Sci.,1999,74:1917-1924.
18. Thomas R R, Anton D R. Fluorinated acrylates emulsion polymerization and blends of fluorinated acrylate [J]. Macromolecules,1998,31:4595-4603.
19.郭小丽,熊圣东,易昌凤等.含氟丙烯酸酯三元共聚细乳液的微波辐射合成与表征[J].应用化学,2009,26(1)：86-89.
20.时米超,王明刚.有机氟硅改性丙烯酸树脂的合成及性能研究.山东大学硕士论文,2009.
21.王世敏,方章建,许祖勋等.一种含氟单体的合成及其乳液制备与性能的研究[J].化学与黏合,2006,27(2)：63-66.
22.黄月文,刘伟.含氟丙烯酸酯改性苯丙共聚物表面处理剂的研究[J].新型建筑材料,2005,11：10-12.
23. Park I J, Lee S B, Choi C K. Surface properties of the fluorine-containing graft copolymer of poly(perfluoroalkylethyl methacrylate)-g-poly(methyl methacrylate) [J]. Macromolecules,1998,31:7555-7558.
24. Robert A H. Polymeric fluorocarbon siloxanes, emulsions and surface coatings thereof [P]. US 5442011.
25. Suzuki Y[P]. JP 04164990,1992.
26. Landfester K, Rothe R, Antonietti M. Convenient synthesis of fluorinated latexes and core-shell structures by miniemulsion polymerization [J]. Macromolecules, 2002,35:1658-1662.
27. Fujiwara H, Narita T, Hamana H. Novel fluorinated polymers by radical polyaddition:Inspiration and progress [J]. J. Fluorine Chem.,2004,42(6): 1279-1285.
28. Paul L, Barrlek. Reaction Products of polyfluoro-ethylenes and terminally unsaturated compounds [P]. US 2462347,1949.
29. Arthur H, Ahlbrecht W. Bear T. Fluorinated acrylates and polymers [P]. US 2642416,1953.
30.李伟华,周晓东,胡正水等.含全氟基团的丙烯酸酯单体的制备,精细化工2002,19(11)：661-663.
31.王世敏.全氟烷基丙烯酸酯单体的制备[J].化工商情,2000,3(2)：15-17.
32.李惠芳,任建刚,戴荣继等.含氟聚丙酸酯防水防油剂的合成及性能研究[J].精细化工,1995,12(5)：21-24.
33.程耀波,李文娟,王忠刚.一种含氟丙烯酸酯单体的合成与表征[J].精细化工,2009,26(4)：395-399.
34. Patrice C H, Colleta A, Viguiera M, et al. Acrylic monomers and polymers with perfluoroalkylatedbiphenyl side groups:synthesis and phase transitions[J]. J. Fluorine Chem.,2004,125 (12):1909-1918.
35. Christopher M T, Robert E A, Michael B, et al. Bis(fluoroalkyl)acrylic and methacrylic phosphate monomers, their polymers and some of their properties [J]. J. Fluorine Chem.,2003,121 (1):23-31.
36.邢其毅,徐瑞秋,周政等.基础有机化学[M].北京：高等教育出版社,1993,417-420.
37. Cirkva V, Ameduri B, Boutevin B, et al. Highly selective synthesis of [(perfluoroalkyl) methyl] oxiranes (by the addition of iodoperfluoroalkanes to allyl acetate) [J]. J. Fluorine Chem.,1997,83(2):151-158.
38. Cirkva V, Polak R, Paleta O, et al. Novel perfluoroalkylated derivatives of D-galactopyranose and xylitol for biomedical uses. Hemocompatibility and effect on perfluorocarbon emulsions [J]. Carbohydrate Research,2004,339(13): 2177.
39. Conte L, Maniero F, Zaggia A, et al. Regioselective ring opening of [(perfluoroalkyl)methyl] oxiranes with N-nucleophiles [J]. J. Fluorine Chem., 2005,126(9-10):1274.
40.周婵,许家喜.非对称环氧乙烷的区域选择性亲核开环反应[J].化学进展,2011,1(23)：165-180.
41. Charrada B, Hedhli A, Baklouti A. Aqueous ammonia:a versatile reagent for symmetrical di(F-alkylated) aminodiols synthesis [J]. Tetrahedron,2007,41(35): 7347-7349.
42. Kaplanek R, Paleta O, Michalek J, et al. Perfluoroalkylated diblock-alkyl methacrylate monomers for biomedical applications:Wettability of their copolymers with HEMA and DEGMA [J]. J. Fluorine Chem.,2005,126(4): 593-598.
43. Cirkva V, Ameduri B, Boutevin B et al. Chemistry of [(perfluoroalkyl)methyl] oxiranes:Regioselectivity of ring opening with O-nucleophiles and the preparation of amphiphilic monomers [J]. J. Fluorine Chem.,1997,84(1):53-61.
44. Das B, Krishnaiah M, Thirupathi P, et al. An efficient catalyst-free regio-and stereoselective ring-opening of epoxides with phenoxides using polyethylene glycol as the reaction medium [J]. Tetrahedron Letters.2007,48(24):4263-4265.
45. Polshettiwar V, Kaushik M P. CsF-Celite catalyzed regio-and chemoselective Sn2 type ring opening of epoxides with thiol [J]. Catal. Commun,2004,5(9):515-518.
46. Kaplanek R, Paleta O. Amphiphilic perfluoroalkylated sulfones and sulfonate betaines [J]. J. Fluorine Chem.,2007,128 (9):789-796.
47. Directive 2006/122/ECOF of the European Parliament and of the Council of 12 December 2006 [L], Official Journal of the European Union,2006,372:32-34.
48.刘建国,李平,李萍等.甲基丙烯酰氯制备方法的改进[J].化学试剂,2007,29(11),699-700.
49. Cirkva V, Amiduri B, Boutevin B, et al. Radical-induced reaction of monoiodo-and diiodo-perfluoroalkanes with allyl acetate:telomer and rearranged products, mass-spectral distinguishing of regioisomers[J]. J. Fluorine Chem.,1995,74(1): 97-105.
50.山边正显,松尾仁.含氟材料的研究开发[M].上海：华东理工大学出版,2003,142-156.
51. GRAHAM P, STONE M, THORPE A, et al. Fluoropolymers with very low surface energy characteristics [J]. J. Fluorine Chem.,2000,104(1):29-36.
2.周命,张玉兴,周树军.丙烯酸树脂的制备及其在涂料中的应用与研究现状[J].上海涂料,2007,45(7)：25-29.
3.缭京媛.氟塑料加工和应用[M].北京：化学工业出版社,1987,126.
4. Murray K P, Bartoszek Jr E J. Fluorine in Coating Conference [R]. Orlando, Florida,1999,19.
5.山边正显,松尾仁.含氟材料的研究开发.华东理工大学出版社.2003,143.
6.曾昭伦.元素有机化学[M].北京：科学出版社,1965,147.
7.邹盛欧.氟树脂近况[J].化工新型材料,1997,25(9)：3-7.
8. Morita M, Ogisu H. Surface properties of perfluoroalkylethy acrylate/n-alkyl acrylate copolymers [J]. J. APPl. Poly. Sci,1999,73:1741-1749.
9. Patrice C, Hartmanna, Colleta A. Acrylic monomers and polymers with perfluoroalkylatedbiphenyl side groups:synthesis and phase transitions [J]. J. Fluorine Chem.,2004,125(12):1909-1918.
10.周钰明,黄静艳等.N-羟乙基全氟辛酰胺甲基丙烯酸酯聚合物的合成及性能研究[J].精细化工,2002,8(19)：78-79.
11. Reinhard F, Linemann, Thomas E. Latex blends of fluorinated and fluorine-fere acrylaets:emulsion polymerization and tapping mode aotmic force micorscopy of film formation [J]. Macormolecules,1999,32(6):1715-1722.
12. Hayakawa Y, Terasawa N. Synthesis of novel Polymethcrylates bearing cyclic perfluoroalkyl groups [J]. Polymer,1998,39(17):4151-4154.
13. Desimone J M, Guan Z, et al. Homogeneous free radical polymerzations of fluorinated monomers in supercritical carbon dioxide [J]. Polymer Preprints(USA), 1992,33(2):329-330.
14.魏海洋,李欣欣,王康等.含氟丙烯酸酯共聚物制备超疏水表面及其形成机理的研究.化学学报,2008,66(12)：1470-1476.
15.戴荣继,张明南,李惠黎.聚(丙烯酸全氟辛酸乙二醇酯)类防水防油剂的性能研究[J].精细石油化工,1991,(5)：35-38.
16. Hashimoto, Yataka [P]. JP 97-132606,1997.
17. Kim D K, Lee S B. Latex blends of fluorinated and fluorine-free aerylate emulsion polymerization and tapping mode atomic force microscopy of film formation [J]. J. Appl. Polym. Sci.,1999,74:1917-1924.
18. Thomas R R, Anton D R. Fluorinated acrylates emulsion polymerization and blends of fluorinated acrylate [J]. Macromolecules,1998,31:4595-4603.
19.郭小丽,熊圣东,易昌凤等.含氟丙烯酸酯三元共聚细乳液的微波辐射合成与表征[J].应用化学,2009,26(1)：86-89.
20.时米超,王明刚.有机氟硅改性丙烯酸树脂的合成及性能研究.山东大学硕士论文,2009.
21.王世敏,方章建,许祖勋等.一种含氟单体的合成及其乳液制备与性能的研究[J].化学与黏合,2006,27(2)：63-66.
22.黄月文,刘伟.含氟丙烯酸酯改性苯丙共聚物表面处理剂的研究[J].新型建筑材料,2005,11：10-12.
23. Park I J, Lee S B, Choi C K. Surface properties of the fluorine-containing graft copolymer of poly(perfluoroalkylethyl methacrylate)-g-poly(methyl methacrylate) [J]. Macromolecules,1998,31:7555-7558.
24. Robert A H. Polymeric fluorocarbon siloxanes, emulsions and surface coatings thereof [P]. US 5442011.
25. Suzuki Y[P]. JP 04164990,1992.
26. Landfester K, Rothe R, Antonietti M. Convenient synthesis of fluorinated latexes and core-shell structures by miniemulsion polymerization [J]. Macromolecules, 2002,35:1658-1662.
27. Fujiwara H, Narita T, Hamana H. Novel fluorinated polymers by radical polyaddition:Inspiration and progress [J]. J. Fluorine Chem.,2004,42(6): 1279-1285.
28. Paul L, Barrlek. Reaction Products of polyfluoro-ethylenes and terminally unsaturated compounds [P]. US 2462347,1949.
29. Arthur H, Ahlbrecht W. Bear T. Fluorinated acrylates and polymers [P]. US 2642416,1953.
30.李伟华,周晓东,胡正水等.含全氟基团的丙烯酸酯单体的制备,精细化工2002,19(11)：661-663.
31.王世敏.全氟烷基丙烯酸酯单体的制备[J].化工商情,2000,3(2)：15-17.
32.李惠芳,任建刚,戴荣继等.含氟聚丙酸酯防水防油剂的合成及性能研究[J].精细化工,1995,12(5)：21-24.
33.程耀波,李文娟,王忠刚.一种含氟丙烯酸酯单体的合成与表征[J].精细化工,2009,26(4)：395-399.
34. Patrice C H, Colleta A, Viguiera M, et al. Acrylic monomers and polymers with perfluoroalkylatedbiphenyl side groups:synthesis and phase transitions[J]. J. Fluorine Chem.,2004,125 (12):1909-1918.
35. Christopher M T, Robert E A, Michael B, et al. Bis(fluoroalkyl)acrylic and methacrylic phosphate monomers, their polymers and some of their properties [J]. J. Fluorine Chem.,2003,121 (1):23-31.
36.邢其毅,徐瑞秋,周政等.基础有机化学[M].北京：高等教育出版社,1993,417-420.
37. Cirkva V, Ameduri B, Boutevin B, et al. Highly selective synthesis of [(perfluoroalkyl) methyl] oxiranes (by the addition of iodoperfluoroalkanes to allyl acetate) [J]. J. Fluorine Chem.,1997,83(2):151-158.
38. Cirkva V, Polak R, Paleta O, et al. Novel perfluoroalkylated derivatives of D-galactopyranose and xylitol for biomedical uses. Hemocompatibility and effect on perfluorocarbon emulsions [J]. Carbohydrate Research,2004,339(13): 2177.
39. Conte L, Maniero F, Zaggia A, et al. Regioselective ring opening of [(perfluoroalkyl)methyl] oxiranes with N-nucleophiles [J]. J. Fluorine Chem., 2005,126(9-10):1274.
40.周婵,许家喜.非对称环氧乙烷的区域选择性亲核开环反应[J].化学进展,2011,1(23)：165-180.
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