氨基甲酸酯丙烯酸酯的合成及其光固化性能
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摘要
利用碳酸亚乙酯与1,6-己二胺、异佛尔酮二胺反应,合成了含氨基甲酸酯二元醇,并由氨基甲酸酯二元醇与丙二酸二甲酯的酯交换反应合成了丙二酸酯封端的氨基甲酸酯。再利用其与1,6-己二醇二丙烯酸酯(HDDA)、1,3-新戊二醇二丙烯酸酯(NPGDA)及聚乙二醇二丙烯酸酯(PEG200DA)的Michael加成反应合成了含多官能度氨基甲酸酯丙烯酸酯(NIPUs)。用1HNMR及HRMS表征了合成中间体及NIPUs的结构,用FTIR考察了NIPUs光固化过程,初步评价了合成的多官能度丙烯酸酯复配物的光固化膜性能。结果表明:含占总质量分数3%的光引发剂1173及占总质量分数10%HDDA的多官能度丙烯酸酯溶液均能在60 s内光固化形成表面平整、具有较好柔韧性(0.5～2.0 mm)的膜,固化膜的凝胶率大于96%,固化膜对玻璃的附着力为0～2级,HDDA及NPGDA基的氨基甲酸酯丙烯酸酯光固化膜的铅笔硬度均达到6H。
Ethylene carbonate respectively reacted with 1,6-hexanediamine and isophoronediamine to produce carbamate diols. Subsequently, transesterification reactions between the resulting carbamate diols and dimethyl malonate led to malonate terminated carbamates. Finally, a series of multifunctional acrylates containing carbamate groups(NIPUs) were obtained by Michael addition reactions between malonate terminated carbamates and 1,6-hexanediol diacrylate, 1,3-neopentyl glycol diacrylate and polyethylene glycol diacrylate, respectively. The synthesized intermediates and NIPUs were characterized by 1 HNMR and high resolution mass spectroscopy. The UV curing process of NIPUs was studied by FTIR and the UV cured film properties of the synthesized multifunctional acrylates gel were preliminary evaluated. The results showed that the multifunctional acrylate solution with 3% photoinitiator 1173(mass fraction, based on the total mass of the mixture, the same below) and 10% HDDA could be cured within 60 s and form films with smooth surface and good flexibility(0.5～2.0 mm). The gel rate of the cured films was greater than 96%. The adhesion of the cured films to glass was level 0～2. The pencil hardness of the UV cured films based carbamate acrylates derived from HDDA and NPGDA reached 6 H.
Ethylene carbonate respectively reacted with 1,6-hexanediamine and isophoronediamine to produce carbamate diols. Subsequently, transesterification reactions between the resulting carbamate diols and dimethyl malonate led to malonate terminated carbamates. Finally, a series of multifunctional acrylates containing carbamate groups(NIPUs) were obtained by Michael addition reactions between malonate terminated carbamates and 1,6-hexanediol diacrylate, 1,3-neopentyl glycol diacrylate and polyethylene glycol diacrylate, respectively. The synthesized intermediates and NIPUs were characterized by 1 HNMR and high resolution mass spectroscopy. The UV curing process of NIPUs was studied by FTIR and the UV cured film properties of the synthesized multifunctional acrylates gel were preliminary evaluated. The results showed that the multifunctional acrylate solution with 3% photoinitiator 1173(mass fraction, based on the total mass of the mixture, the same below) and 10% HDDA could be cured within 60 s and form films with smooth surface and good flexibility(0.5～2.0 mm). The gel rate of the cured films was greater than 96%. The adhesion of the cured films to glass was level 0～2. The pencil hardness of the UV cured films based carbamate acrylates derived from HDDA and NPGDA reached 6 H.
引文
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[4]Bao F,Shi W.Synthesis and properties of hyperbranched polyurethane acrylate used for UV curing coatings[J].Progress in Organic Coatings,2010,68(4):334-339.
[5]Shen Wentong(沈文通),Zhang Huijuan(张慧娟),Zhou Hongyong(周宏勇),et al.Synthesis and properties of polyfunctional dumb bell shaped UV-curable resin[J].Fine Chemicals(精细化工),2017,34(12):1434-1440.
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[9]Cornille A,Auvergne R,Figovsky O,et al.A perspective approach to sustainable routes for non-isocyanate polyurethanes[J].European Polymer Journal,2017,87:535-552.
[10]Rix E,Grau E,Chollet G,et al.Synthesis of fatty acid-based non-isocyanate polyurethanes,NIPUs,in bulk andmini-emulsion[J].European Polymer Journal,2016,84:863-872.
[11]Agrawal A,Kaur R,Walia R S,et al.PU foam derived from renewable sources:Perspective on properties enhancement:An overview[J].European Polymer Journal,2017,95:255-274.
[12]Poussard L,Mariage J,Grignard B,et al.Non-isocyanate polyurethanes from carbonated soybean oil using monomeric or oligomeric diamines to achieve thermosets orthermoplastics[J].Macromolecules,2016,49(6):2162-2171.
[13]Liu G F,Wu G M,Chen J,et al.Synthesis,modification and properties of rosin-based non-isocyanate polyurethanes coatings[J].Progress in Organic Coatings,2016,101:461-467.
[14]Rokicki G,Piotrowska A.A new route to polyurethanes from ethylene carbonate,diamines and diols[J].Polymer,2002,43(10):2927-2935.
[15]Li C,Li S,Zhao J,et al.Synthesis and characterization of aliphatic poly(amide urethane)shaving different nylon 6 segments through non-isocyanate route[J].Journal of Polymer Research,2014,21(7):1-10.
[16]Huang Y,Pang L,Wang H,et al.Synthesis and properties of UV-curable tung oil based resins via modification of Diels-Alder reaction,nonisocyanate polyurethane and acrylates[J].Progress in Organic Coatings,2013,76(4):654-661.
[17]Li S,Zhao J,Zhang Z,et al.Synthesis and characterization of aliphatic thermoplasticpoly(ether urethane)elastomers through a non-isocyanate route[J].Polymer,2014,4(45):23720-23729.
[18]National Committee on the Standardization of Paint and Pigment(全国涂料和颜料标准化技术委员会).Determination of lexibility of films:GB/T 1731-1993[S].Beijing:China Standard Publishing House(中国标准出版社),1993:1-3.
[19]National Committee on the Standardization of Paint and Pigment(全国涂料和颜料标准化技术委员会).Paints and varnishescrosscut test for films:GB/T 9286-1988[S].Beijing:China Standard Publishing House(中国标准出版社),1998:547-555.
[20]National Committee on the Standardization of Paint and Pigment(全国涂料和颜料标准化技术委员会).Paints and varnishesdeterminationof films hardness by pencil test:GB/T 6739-2006[S].Beijing:China Standard Publishing House(中国标准出版社),2006:12-29.