新型UV固化多官能度有机硅功能低聚物的合成及应用
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摘要
以端含氢硅油、甲基乙烯基二氯硅烷和丙烯酸-β-羟乙酯为原料,经硅氢加成和醇解两步反应,制备了一种与UV固化涂料相容性好,新型多官能度、可UV固化的有机硅功能低聚物。优化了硅氢加成反应条件,产物结构经IR进行了表征。将有机硅功能低聚物应用于UV固化涂料,制得UV固化耐污涂料。研究了涂膜的光固化时间、耐试剂性以及热稳定性,并探究了有机硅低聚物含量与涂膜表面水接触角、吸水率和耐污性等之间的关系。硅氢加成反应的最佳条件:反应温度85℃,催化剂用量为0.4%,n(端基含氢硅油)∶n(甲基乙烯基二氯硅烷)=1∶2,溶剂甲苯的用量为30%。此条件下端基含氢硅油的转化率达到98%;将多官能度有机硅低聚物应用于UV固化涂料,制备有机硅耐污功能材料。涂膜固化时间为46 s,附着力达2级,硬度为3H,具有较好的力学性质。当有机硅低聚物质量分数为1.2%时,材料涂膜表面水接触角达到110°,具有优良的疏水性;涂膜耐水、耐盐及耐碱性较好,且对酱油、碳素墨水以及水性彩笔表现出良好的耐污性能。此外,固化膜在325℃内稳定存在,具有良好的热稳定性。
A new organosilicon oligomer with multiple UV-curable and multi-functional groups was synthesized by hydrogen-containing silicone oil,dichloromethylvinylsilane and 2-hydroxyethyl acrylate via hydrosilylation and alcoholysis reaction,which had good compatibility with UV coating.The conditions of hydrosilylation were optimized,and the structure of the products was characterized by IR.The UV-curable silicone stain resistant coatings was prepared by applying this functional oligomer onto UV curing coating.The curing time,reagent resistance and thermal stability of coatings were studied,and the effects of silicone oligomer content on the water contact angle,water absorption and stain properties of UV-cured films were also discussed.The best conditions of hydrosilylation:reaction temperature was 85℃,catalyst quantity was 0.4%,the mole ratio of hydrogen-containing silicone oil and dichloromethylvinylsilane was 1∶2,the solvent quantity of toluene was30%,and the conversion rate of the hydrogen-containing silicone oil reached 98%.The multi-functionality silicone oligomer was applied on the UV curable coating so as to prepare the stain resistance silicone material.Results showed that coating curing time was 46s,adhesion was Class 2,and the hardness was 3H,the material had good machnical property.When the mass fraction of the oligomer was 1.2%,the water contact angle reached 110°,the UV-curable coating could be cured quickly to give a film with excellent water and stain resistances.The film kept stable in 325 centigrade,and had good thermal stability.
A new organosilicon oligomer with multiple UV-curable and multi-functional groups was synthesized by hydrogen-containing silicone oil,dichloromethylvinylsilane and 2-hydroxyethyl acrylate via hydrosilylation and alcoholysis reaction,which had good compatibility with UV coating.The conditions of hydrosilylation were optimized,and the structure of the products was characterized by IR.The UV-curable silicone stain resistant coatings was prepared by applying this functional oligomer onto UV curing coating.The curing time,reagent resistance and thermal stability of coatings were studied,and the effects of silicone oligomer content on the water contact angle,water absorption and stain properties of UV-cured films were also discussed.The best conditions of hydrosilylation:reaction temperature was 85℃,catalyst quantity was 0.4%,the mole ratio of hydrogen-containing silicone oil and dichloromethylvinylsilane was 1∶2,the solvent quantity of toluene was30%,and the conversion rate of the hydrogen-containing silicone oil reached 98%.The multi-functionality silicone oligomer was applied on the UV curable coating so as to prepare the stain resistance silicone material.Results showed that coating curing time was 46s,adhesion was Class 2,and the hardness was 3H,the material had good machnical property.When the mass fraction of the oligomer was 1.2%,the water contact angle reached 110°,the UV-curable coating could be cured quickly to give a film with excellent water and stain resistances.The film kept stable in 325 centigrade,and had good thermal stability.
引文
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[2]ATAPATTU S N,POOLE C F.Determination of descriptors for semivolatile organosilicon compounds by gas chromatography and non-aqueous liquid-liquid partition[J].J Chromatogr A,2009,1216(45):7882-7888.
[3]CHANG C J,TZENG H Y.Preparation and properties of waterborne dual curable monomers and cured hybrid polymers for ink-jet applications[J].Polymer,2006,47(26):8536-8547.
[4]BANERJEE I,PANGULE R C.Antifouling coatings:recent developments in the design of surfaces that prevent fouling by proteins,bacteria,and marine organisms[J].Adv Mater,2011,23(6):690-718.
[5]Vaterrodt A,Thallinger B.Antifouling and antibacterial multifunctional polyzwitterion/enzyme coating on silicone catheter material prepared by electrostatic layer-by-layer assembly[J].ACS Langmuir,2016,32(5):1347-1359.
[6]刘长利,吴文健,张学骜,等.紫外光固化有机硅预聚物的研究进展[J].有机硅材料,2005,19(5):26-32.
[7]CHANG C W,LU K T.Epoxy Acrylate UV/PU dualcured cwood coatings[J].J Appl Polym Sci,2010,115(4):2197-2202.
[8]LIU R,ZHANG X P.UV-Curable coatings from multiarmed cardanol-based acrylate oligomers[J].ACS Sustainable Chem Eng,2015,3(7):1313-1320.
[9]LIU H B,CHEN M C,HUANG Z T.The influence of silicon-containing acrylate as active diluent on the properties of uv-cured epoxydiacrylate[J].Eur Polym J,2004,40(3):609-613.
[10]杜现礼,刘长利,胡碧茹.光敏性有机硅丙烯酸酯的合成及其改性紫外光固化材料研究[J].化工新型材料,2009,3(37):66-67.
[11]张琳琳,涂姜磊.可紫外光固化有机硅丙烯酸酯的合成及性能[J].化学工业与工程,2011,2(28):1-5.
[12]TAN B E,PAN H M.Synthesis of ultraviolet-curable modified polysiloxane and its surface properties[J].JAppl Polym Sci,2002,86(9):2135-2139.
[13]张招贵,曹文丽.有机硅改性萜烯树脂及其应用[J].应用化学,2001,18(12):1017-1018.
[14]乔秀芬,周元林,杨文彬.紫外光固化有机硅的合成研究[J].化工新型材料,2008,36(10):5-6.