巯基-烯光点击反应辅助合成多官能度蓖麻油基聚氨酯丙烯酸酯
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摘要
研究巯基-烯光点击反应辅助合成多官能度蓖麻油基聚氨酯丙烯酸酯。首先通过光引发的巯基-烯点击反应,于蓖麻油分子上引入巯基乙醇,形成多羟基化合物,然后加入丙烯酸羟丙酯与异佛尔酮二异氰酸酯,以物质的量为1∶1反应得到端异氰酸酯丙烯酸酯,最终得到蓖麻油基聚氨酯丙烯酸酯。通过调节羟基含量可以得到不同官能度的丙烯酸酯。采用红外光谱、核磁氢谱、热重分析等手段表征其结构和性能,并测试了合成的聚氨酯丙烯酸脂的吸水率、附着力等性能,同时考察了它的热稳定性。结果表明,在紫外光照射下,巯基和不饱和双键之间发生了加成反应;该聚合物的固化膜性能得到提高,尤其是硬度和热稳定性。由本文快速合成方法得到的树脂性能良好,具有较好的应用前景,扩大了巯基-烯光点击反应在高性能UV固化材料方面的应用范围。
To study the synthesis of polyfunctional castor oil-based polyurethane acrylate by the auxiliary of thiol-ene photo click reaction,first,the mercaptoethanol was introduced into castor oil viathiol-ene photo-click reaction with UV irradiation,forming polyhydroxy compounds.Then we added the isocyanate acrylate,which was obtained by the reaction between hydroxypropyl acrylate(HPA)and isophorone diisocyanate(IPDI),into polyhydroxy compounds,the molar ratio of HPA and IPDI is 1∶1.Finally,we got the castor oil-based polyurethane acrylate.Different functional acrylate can be obtained by adjusting the hydroxyl content.Furthermore,the structure and performance of Polyurethane acrylate were confirmed by 1 HNMR,FT-IR and TG.The water absorption and adhesion of synthetic polyurethane acrylate were tested.Meanwhile,the thermal stability was studied.The results indicated that the thiol-ene addition reaction was proceeded and the properties of cured film are improved,especially the hardness and thermal stability.In conclusion,we report a synthetic method to prepare vegetable oil-based polyurethane acrylate(PUA)resin,and the synthetic resin has good properties,which expands the application of thiol-ene click reaction in UV curing materials.
To study the synthesis of polyfunctional castor oil-based polyurethane acrylate by the auxiliary of thiol-ene photo click reaction,first,the mercaptoethanol was introduced into castor oil viathiol-ene photo-click reaction with UV irradiation,forming polyhydroxy compounds.Then we added the isocyanate acrylate,which was obtained by the reaction between hydroxypropyl acrylate(HPA)and isophorone diisocyanate(IPDI),into polyhydroxy compounds,the molar ratio of HPA and IPDI is 1∶1.Finally,we got the castor oil-based polyurethane acrylate.Different functional acrylate can be obtained by adjusting the hydroxyl content.Furthermore,the structure and performance of Polyurethane acrylate were confirmed by 1 HNMR,FT-IR and TG.The water absorption and adhesion of synthetic polyurethane acrylate were tested.Meanwhile,the thermal stability was studied.The results indicated that the thiol-ene addition reaction was proceeded and the properties of cured film are improved,especially the hardness and thermal stability.In conclusion,we report a synthetic method to prepare vegetable oil-based polyurethane acrylate(PUA)resin,and the synthetic resin has good properties,which expands the application of thiol-ene click reaction in UV curing materials.
引文
[1]付长清,杨哲,郑子童,申亮.蓖麻油基羧酸型聚氨酯亲水扩链剂的制备与应用[J].涂料工业,2013,43(11):29-34.Fu C Q,Yang Z,Zheng Z T,Shen L.Preparation and application of castor oil-based carboxyl polyurethane hydrophilic chain extender[J].Paint&Coatings Industry,2013,43(11):29-34.
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[8]Espomosa L M D,Meier M A R.Plant oils:the perfect renewable resource for polymer science[J].European Polymer Journal,2011,47(5):837-852.
[9]Desroches M,Caillol S,Lapinte V,Auvergne R,Boutevin B.Synthesis of biobased polyols by thiol-ene coupling from vegetable oils[J].Macromolecules,2011,(44):2489-2500.
[10]He M H,Jiang S,Xu R X,Yang J W,Zeng Z H,Chen G X.Facile functionalization of soybean oil by thiol-ene photo-click reaction for the synthesis of polyfunctional acrylate[J].Progress in Organic Coatings,2014,(77):868-871.
[11]Temel G,Karaca N,Arsu N.Synthesis of main chain polymeric benzophenone photoinitiator via thiol-ene click chemistry and its use in free radical polymerization[J].Journal of Polymer Science,2010,(48):5306-5312.
[12]何明辉.水性UV聚氨酯丙烯酸酯光油树脂的合成与应用[J].中国印刷与包装研究,2009,1(4):58-63.He M H.Synthesis and application of UV-cured waterborne polyurethane acrylate[J].China Printing and Packaging Study,2009,1(4):58-63.
[13]竺青,黄莉,谢晖,康小孟.UV固化丙烯海松酸聚氨酯丙烯酸酯的合成及其涂膜性能[J].涂料工业,2009,39(1):44-46.Zhu Q,Huang L,Xie H,Kang X M.Synthesis of UVcurable acrylpimaric acid polyurethane acrylate and film properties[J].Paint&Coatings Industry,2009,39(1):44-46.
[14]王青,陈广学,陈双莲,王焕美,袁雅倩.铝塑复合用聚氨酯胶粘剂的制备及性能研究[J].包装工程,2012,33(13):59-63.Wang Q,Chen G X,Chen S L,Wang H M,Yuan Y Q.Preparation and performance study of aluminum composite polyurethane adhesive[J].Packaging Engineering,2012,33(13):59-63.
[15]Wang Q,Chen G X,Tai G L,Chen Q F.Structural effect of thiol-compounds on the thiol-ene based UV curable adhesive[J].Applied Mechanics and Materials,2014,(469):162-166.
[16]王露,周爱军,陈宪宏.丙烯酸改性水性聚氨酯的制备与表征[J].包装学报,2013,5(3):16-19.Wang L,Zhou A J,Chen X H.Preparation and characterization of acrylic-modified water soluble polyurethane[J].Packaging Journal,2013,5(3):16-19.
[17]黄洪,傅和青,张心亚,陈焕钦.丙烯酸酯改性的水性聚氨酯胶粘剂的合成[J].包装工程,2006,27(5):93-95.Huang H,Fu H Q,Zhang X Y,Chen H Q.Synthesis of aqueous polyurethane adhesive modified by acrylate[J].Packaging Engineering,2006,27(5):93-95.
[18]Hoyle E,Bowman N.Thiol-ene click chemistry[J].Polymer Chemistry,2010,(49):1540-1573.
[2]王杨勇,胡剑青,郑智贤,王锋,涂伟萍.软包装用耐水丙烯酸酯胶黏剂乳液的合成研究[J].包装工程,2011,32(15):74-78.Wang Y Y,Hu J Q,Zheng Z X,Wang F,Tu W P.Synthesis of acrylic adhesive emulsion with waterproof property for soft packaging sealing[J].Packaging Engineering,2011,32(15):74-78.
[3]王齐,傅和青.蓖麻油-丙烯酸酯改性的双组分水性聚氨酯胶粘剂研究[J].包装工程,2009,29(11):91-94.Wang Q,Fu H Q.Study of modification of two-component waterborne polyurethane adhesive by castor oil and acrylate[J].Packaging Engineering,2009,29(11):91-94.
[4]Uygun M,Tasdelen M A,Yagci Y.Influence of type of initiation on thiol-ene“Click”chemistry[J].Macromolecular Chmestry and Physics,2010,(211):103-110.
[5]付长清,陈樟,乔永洛,陈义旺,申亮.蓖麻油改性巯基-烯UV固化水性聚氨酯分散体的制备[J].涂料工业,2012,42(10):37-44.Fu C Q,Chen Z,Qiao Y L,Chen Y W,Shen L.Preparation of castor oil modified thiol-ene UV-curable waterborne polyurethane dispersions[J].Paint&Coatings Industry,2012,42(10):37-44.
[6]王永真,李予,刘迎沛,黄灵阁.UV喷墨墨水用聚氨酯丙烯酸酯的合成及过程控制[J].包装工程,2013,34(13):106-109.Wang Y Z,Li Y,Liu Y P,Huang L G.Synthesis and process control of PUA for UV inkjet ink[J].Packaging Engineering,2013,34(13):106-109.
[7]付长清,程传杰,申亮,陈义旺.巯基点击反应研究进展[J].高分子通报,2012,(1):29-36.Fu C Q,Cheng C J,Shen L,Chen Y W.Research and development of thiol click reaction[J].Polymer Bulletin,2011,(1):29-36.
[8]Espomosa L M D,Meier M A R.Plant oils:the perfect renewable resource for polymer science[J].European Polymer Journal,2011,47(5):837-852.
[9]Desroches M,Caillol S,Lapinte V,Auvergne R,Boutevin B.Synthesis of biobased polyols by thiol-ene coupling from vegetable oils[J].Macromolecules,2011,(44):2489-2500.
[10]He M H,Jiang S,Xu R X,Yang J W,Zeng Z H,Chen G X.Facile functionalization of soybean oil by thiol-ene photo-click reaction for the synthesis of polyfunctional acrylate[J].Progress in Organic Coatings,2014,(77):868-871.
[11]Temel G,Karaca N,Arsu N.Synthesis of main chain polymeric benzophenone photoinitiator via thiol-ene click chemistry and its use in free radical polymerization[J].Journal of Polymer Science,2010,(48):5306-5312.
[12]何明辉.水性UV聚氨酯丙烯酸酯光油树脂的合成与应用[J].中国印刷与包装研究,2009,1(4):58-63.He M H.Synthesis and application of UV-cured waterborne polyurethane acrylate[J].China Printing and Packaging Study,2009,1(4):58-63.
[13]竺青,黄莉,谢晖,康小孟.UV固化丙烯海松酸聚氨酯丙烯酸酯的合成及其涂膜性能[J].涂料工业,2009,39(1):44-46.Zhu Q,Huang L,Xie H,Kang X M.Synthesis of UVcurable acrylpimaric acid polyurethane acrylate and film properties[J].Paint&Coatings Industry,2009,39(1):44-46.
[14]王青,陈广学,陈双莲,王焕美,袁雅倩.铝塑复合用聚氨酯胶粘剂的制备及性能研究[J].包装工程,2012,33(13):59-63.Wang Q,Chen G X,Chen S L,Wang H M,Yuan Y Q.Preparation and performance study of aluminum composite polyurethane adhesive[J].Packaging Engineering,2012,33(13):59-63.
[15]Wang Q,Chen G X,Tai G L,Chen Q F.Structural effect of thiol-compounds on the thiol-ene based UV curable adhesive[J].Applied Mechanics and Materials,2014,(469):162-166.
[16]王露,周爱军,陈宪宏.丙烯酸改性水性聚氨酯的制备与表征[J].包装学报,2013,5(3):16-19.Wang L,Zhou A J,Chen X H.Preparation and characterization of acrylic-modified water soluble polyurethane[J].Packaging Journal,2013,5(3):16-19.
[17]黄洪,傅和青,张心亚,陈焕钦.丙烯酸酯改性的水性聚氨酯胶粘剂的合成[J].包装工程,2006,27(5):93-95.Huang H,Fu H Q,Zhang X Y,Chen H Q.Synthesis of aqueous polyurethane adhesive modified by acrylate[J].Packaging Engineering,2006,27(5):93-95.
[18]Hoyle E,Bowman N.Thiol-ene click chemistry[J].Polymer Chemistry,2010,(49):1540-1573.