光固化功能材料的制备及性能研究
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摘要
紫外光固化技术是一种环境友好的绿色技术,而低表面能聚合物由于其特殊的性能使其在很多领域得到了快速的发展,成为人们研究的热点。本论文对U V固化技术及低表面能材料等作了较详细的评述。
采用硅氢加成反应,将有机硅、氟引入到光固化单体中,制备出性价比较高的低表面能的有机硅、氟改性的丙烯酸酯光固化单体,用1H - N MR和F T I R跟踪反应进程并表征产物的结构,以实时红外光谱( R T -I R )研究了两种产物的光聚合动力学性质。结果表明,光聚合速率和最终转化率随Si - H键转化率的增加而增大。光固化膜的吸水率随含硅、氟单体含量的增加而下降,固化膜的吸水率可由8. 1 %降低至2 . 3 %。含氢硅油的质量分数为1 0 .8 6 %,全氟单体的质量分数为0. 9 6 %时所得光固化单体固化后的膜具有最佳性价比。有机硅接枝丙烯酸十八酯、H D D A的表面能最低为2 6 .8 8m N /m ,有机硅接枝丙烯酸十二酯、H D D A的表面能最低为4 0 . 13 mN /m ,且前者的机械性能也比后者的好。此外,对光固化膜进行热处理后,膜的凝胶率、硬度、冲击强度有所提高,但其吸水性有所增加。
以异佛尔酮二异氰酸酯、二元醇、三羟甲基丙烷、甲基丙烯酸-β-羟乙酯为原料,合成出一系列不同结构、不同官能团数的聚氨酯丙烯酸酯,并对产物进行1H N MR表征和性能测试。含有氨基的PU A热稳定性和耐黄变性较差;柔性链段的存在和稀释剂的加入,会明显降低体系的粘度; 60℃时I PD I - PE G 40 0- H E MA的粘度为74 0 0 mP a·s ,而I PD I -E PO 30 00 - H E MA的粘度为3 50 0 mP a·s ,说明柔性链段越长则产物的粘度越小;稀释剂的加入使固化过程中链段运动更加容易,从而增大固化膜的凝胶率;柔性链段的存在可以提高固化膜的柔性,但同时也降低了其硬度。
UV-curing technology is an environmentally friendly technology. The polymer with lowsurface energy has been rapidly developed and used in many areas due to its unique properties,and the researches on this material has becoming hot spots. The comments on the UV curingtechnology and low surface energy materials have been remarked.
The novel light-cured monomer organofluoro and silicone modified acrylates with thelow-surface-energy and better ratio of cost to properties were synthesized through thehydrosilylation reaction. The reaction process was traced and the products were characterized by1H-NMR and FT-IR technology. The kinetic nature of UV initiated polymerization was examinedby real-time infrared spectroscopy (RT-IR). The results indicated that the higher conversion ofSi-H bonds in the hydrosilylation is, the higher UV curing rate and the conversion of final doublebonds are. The water absorption ratio of light-cured films reduced as increase of dosage of thesilicone and organofluoro group, water absorption ratio of curing membranes reduced from 8.1%to 2.3%. The UV-gel with the methyl hydro-silicone oil (10.86%) and perfluoroalkylethylacrylates ( 0.96%) has a better ratio of cost to properties. The surface energy of silicone graftedoctadecyl acrylate、HDDA can be as low as 26.88mN / m, while the lowest surface energy ofsilicone grafted lauryl acrylate、HDDA is 40.13 mN / m. Moveover the general performance ofsilicone-graft- octadecyl acrylate、HDDA was better than that of silicone-graft-lauryl acrylate、HDDA. In addition, the further heat processes can improve the gel fraction、hardness、impactstrength of UV- curable films,but the water absorption increased.
A series of polyurethane acrylates with different structures and different number offunctional groups were made up from the reaction of isophorone diisocyanate, diols,trimethylolpropane,β-hydroxy ethyl methylacrylic ester. The products were characterized by1H-NMR technology. The PUA which contains amino has poor thermal stability and resistanceto yellowing.The presence of flexible chain segments and diluents will significantly reduce theviscosity. The viscosity of IPDI - PEG400-HEMA is 7400 mPa ? s, and the viscosity ofIPDI-EPO3000-HEMA is 3500 mPa ? s at 60℃, this shows that the product has the smallerviscosity which possesses longer flexible chain segments; Diluent makes chain segmentmovement easier during curing process, thereby increasing the rate of curing; The flexiblechains can improve flexibility of the curing membrane, but also reduces its hardness.
采用硅氢加成反应,将有机硅、氟引入到光固化单体中,制备出性价比较高的低表面能的有机硅、氟改性的丙烯酸酯光固化单体,用1H - N MR和F T I R跟踪反应进程并表征产物的结构,以实时红外光谱( R T -I R )研究了两种产物的光聚合动力学性质。结果表明,光聚合速率和最终转化率随Si - H键转化率的增加而增大。光固化膜的吸水率随含硅、氟单体含量的增加而下降,固化膜的吸水率可由8. 1 %降低至2 . 3 %。含氢硅油的质量分数为1 0 .8 6 %,全氟单体的质量分数为0. 9 6 %时所得光固化单体固化后的膜具有最佳性价比。有机硅接枝丙烯酸十八酯、H D D A的表面能最低为2 6 .8 8m N /m ,有机硅接枝丙烯酸十二酯、H D D A的表面能最低为4 0 . 13 mN /m ,且前者的机械性能也比后者的好。此外,对光固化膜进行热处理后,膜的凝胶率、硬度、冲击强度有所提高,但其吸水性有所增加。
以异佛尔酮二异氰酸酯、二元醇、三羟甲基丙烷、甲基丙烯酸-β-羟乙酯为原料,合成出一系列不同结构、不同官能团数的聚氨酯丙烯酸酯,并对产物进行1H N MR表征和性能测试。含有氨基的PU A热稳定性和耐黄变性较差;柔性链段的存在和稀释剂的加入,会明显降低体系的粘度; 60℃时I PD I - PE G 40 0- H E MA的粘度为74 0 0 mP a·s ,而I PD I -E PO 30 00 - H E MA的粘度为3 50 0 mP a·s ,说明柔性链段越长则产物的粘度越小;稀释剂的加入使固化过程中链段运动更加容易,从而增大固化膜的凝胶率;柔性链段的存在可以提高固化膜的柔性,但同时也降低了其硬度。
UV-curing technology is an environmentally friendly technology. The polymer with lowsurface energy has been rapidly developed and used in many areas due to its unique properties,and the researches on this material has becoming hot spots. The comments on the UV curingtechnology and low surface energy materials have been remarked.
The novel light-cured monomer organofluoro and silicone modified acrylates with thelow-surface-energy and better ratio of cost to properties were synthesized through thehydrosilylation reaction. The reaction process was traced and the products were characterized by1H-NMR and FT-IR technology. The kinetic nature of UV initiated polymerization was examinedby real-time infrared spectroscopy (RT-IR). The results indicated that the higher conversion ofSi-H bonds in the hydrosilylation is, the higher UV curing rate and the conversion of final doublebonds are. The water absorption ratio of light-cured films reduced as increase of dosage of thesilicone and organofluoro group, water absorption ratio of curing membranes reduced from 8.1%to 2.3%. The UV-gel with the methyl hydro-silicone oil (10.86%) and perfluoroalkylethylacrylates ( 0.96%) has a better ratio of cost to properties. The surface energy of silicone graftedoctadecyl acrylate、HDDA can be as low as 26.88mN / m, while the lowest surface energy ofsilicone grafted lauryl acrylate、HDDA is 40.13 mN / m. Moveover the general performance ofsilicone-graft- octadecyl acrylate、HDDA was better than that of silicone-graft-lauryl acrylate、HDDA. In addition, the further heat processes can improve the gel fraction、hardness、impactstrength of UV- curable films,but the water absorption increased.
A series of polyurethane acrylates with different structures and different number offunctional groups were made up from the reaction of isophorone diisocyanate, diols,trimethylolpropane,β-hydroxy ethyl methylacrylic ester. The products were characterized by1H-NMR technology. The PUA which contains amino has poor thermal stability and resistanceto yellowing.The presence of flexible chain segments and diluents will significantly reduce theviscosity. The viscosity of IPDI - PEG400-HEMA is 7400 mPa ? s, and the viscosity ofIPDI-EPO3000-HEMA is 3500 mPa ? s at 60℃, this shows that the product has the smallerviscosity which possesses longer flexible chain segments; Diluent makes chain segmentmovement easier during curing process, thereby increasing the rate of curing; The flexiblechains can improve flexibility of the curing membrane, but also reduces its hardness.
引文
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[3]李振风,聂俊.吡咯烷酮-N-甲酸,丙烯酸乙二醇酯的合成及其光聚合动力学的研究[J].信息记录材料,2007,8(6):4-7.
[4]秦长喜,郑军.辐射固化技术的现状和发展趋势[J].信息记录材料,2005,6(2):21-26.
[5]李晓勇,游长江,张小燕,方旻.紫外光固化涂料及其发展状况[J].广州化学,2007,32(2):66-72.
[6]陈用烈,曾兆华,杨建华.辐射固化材料及其应用[M].化学工业出版社,2003.9.
[7]魏杰,金养智.光固化涂料[M].北京:化学工业出版社,2005:69.
[8]颜肖慈,罗明道.界面化学[M].北京:化学工业出版社,2005 ,112-172.
[9]李永清,郑淑贞.低表面能聚合物的聚合进展[J].化工新型材料,2003,31(7):1-4.
[10]谷国团,张治军,党鸿辛.一种可溶性低表面自由能聚合物的制备及其表面性质[J].高分子学报,2002(12):770-774.
[11]沈春林.有机硅防水涂料的研制与施工[J].涂料工业, 1998, 28 (7):29-31.
[12]刘秀生,高万振,郑之国.低表面能涂层技术发展现状[J].表面工程资讯,2005,5(3):3.
[13] Coulson S.R., Woodward I., Badyal J.P.S., Brewer S.A., Willis C.. Super-Repellent compositefluoropolymer surfaces [J]. Journal of physical chemistry B, 2000, 104 (37):8836-8840.
[14] Andreas F , Thnemann Antje Lieske , Bernd-Reiner Paulke.Low surface energy coatings fromwaterborne nano-dispersions of polymer complexes[J]. Advanced Materials, 1999 ,11(4) :321-324.
[15] James E, Mark A. Some Interesting things about polysiloxanes[J]. Chemical Research, 2004 ,37(12) :946-953.
[16] Peter E. , Francis F. E. , Richard J. E., Thomas G.N., James R.S., John T. .Combined nanoindentationand adhesion force mapping using the atomic force microscope: investigations of a filled polysiloxanecoating[J]. Langmuir , 2002 , 18 (25) : 10011-10015.
[17]王贤明,王华进,王力,刘登良.无毒低表面能防污涂料[J].涂料工业,2004,34(1) :40-43.
[18] Ameduri B.,Boutevin B.Use of telechelic fluorinated diiodides to obtain well-defined fluoropolymers[J].Journal of Fluorine Chemistry.1999, 100 (1):97-116.
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