UV/热双重固化聚氨酯丙烯酸酯的制备及其涂膜性能
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摘要
以蓖麻油、PEG(聚乙二醇)、PBA(聚己二酸丁二醇酯)、PEA(聚苯二酸酐丁二醇)、IPDI(异佛尔酮二异氰酸酯)、MDI(二苯基甲烷二异氰酸酯)和HEA(丙烯酸羟乙酯)为原料,以有机铋类MB20为催化剂,合成了一系列UV/热双重固化生物基PUA(聚氨酯丙烯酸酯)预聚物,探讨了催化剂用量、反应时间、反应温度、阻聚剂种类及用量等因素对合成UV/热双重固化PUA低聚物过程的影响,获得了PUA低聚物合成的最佳条件。研究结果表明:第一步反应催化剂用量为4 g/kg、反应温度为70℃、反应时间为2 h,第二步反应催化剂用量为5 g/kg、反应温度为45℃、反应时间为3 h、w(阻聚剂ST-1)=0.30%的反应工艺较优。对固化膜的性能进行研究发现:当w(NCO)=3.0%,采用TPO和184作为复合光引发剂,且用量比为1∶3,w(热引发剂BPO)=1.00%,先UV固化后热固化工艺,此时得到的涂膜综合性能较好,双重固化可以较大程度地提高涂膜的硬度和耐磨性。
Using castor oil,PEG(polyethylene glycol),PBA(polybutylene adipate),PEA(polyphenylenedianhydride butylene glycol),IPDI(isophorone diisocyanate),MDI(diphenylmethane diisocyanate)and HEA(hydroxyethyl acrylate)as raw materials,a series of UV/thermal dual curing bio-based PUA(polyurethane acrylate)prepolymers were synthesized with organic bismuth MB20 as catalyst. The effects of catalyst amount,reaction time,reaction temperature,types and dosages of inhibitors on the synthesis of UV/thermal dual curing PUA oligomers were investigated. The optimum conditions for the synthesis of PUA oligomers were obtained. The research results showed that the optimum reaction conditions were as follows:the amount of catalyst used in the first step was 4 g/kg,the reaction temperature was 70 ℃,the reaction time was 2 h,the amount of catalyst used in the second step was 5 g/kg,the reaction temperature was 45 ℃,the reaction time was 3 h,and w(inhibitor ST-1)=0.30%. It was found that when w(NCO)=3.0%,TPO and 184 were used as composite photoinitiators,and the dosage ratio was 1∶3,w(thermal initiator BPO)=1.00%,the comprehensive properties of the cured film were excellent. Dual curing could greatly improve the hardness and wear resistance of the film.
Using castor oil,PEG(polyethylene glycol),PBA(polybutylene adipate),PEA(polyphenylenedianhydride butylene glycol),IPDI(isophorone diisocyanate),MDI(diphenylmethane diisocyanate)and HEA(hydroxyethyl acrylate)as raw materials,a series of UV/thermal dual curing bio-based PUA(polyurethane acrylate)prepolymers were synthesized with organic bismuth MB20 as catalyst. The effects of catalyst amount,reaction time,reaction temperature,types and dosages of inhibitors on the synthesis of UV/thermal dual curing PUA oligomers were investigated. The optimum conditions for the synthesis of PUA oligomers were obtained. The research results showed that the optimum reaction conditions were as follows:the amount of catalyst used in the first step was 4 g/kg,the reaction temperature was 70 ℃,the reaction time was 2 h,the amount of catalyst used in the second step was 5 g/kg,the reaction temperature was 45 ℃,the reaction time was 3 h,and w(inhibitor ST-1)=0.30%. It was found that when w(NCO)=3.0%,TPO and 184 were used as composite photoinitiators,and the dosage ratio was 1∶3,w(thermal initiator BPO)=1.00%,the comprehensive properties of the cured film were excellent. Dual curing could greatly improve the hardness and wear resistance of the film.
引文
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[16]邓岚,孙金媛,袁腾.可生物降解性UV固化聚氨酯丙烯酸酯预聚物的合成[J].中国胶粘剂,2018,27(7):374-378.
[17]杨柱,夏萍,邓康清,等.热/UV双重固化制备耐划伤光学扩散膜[J].涂料工业,2013,43(8):8-12.
[18]刘红波,张武英,林峰,等.高折光紫外光-热双重固化树脂的合成及其性能[J].高分子材料科学与工程,2017,33(1):23-27.
[19]齐亚龙,徐婷,张清华.光热双重固化胶粘剂的热固反应动力学研究[J].热固性树脂,2016,31(5):5-10.
[20] HUANG J J,YUAN T,YANG Z C,et al.UV/thermal dual curing of tung oil-based polymers induced by cationic photoinitiator[J].ProgressinOrganicCoatings,2019,126:8-17.
[21]肖俊芳,冯钦,贺建国,等.低温光-热双重固化材料的制备及其性能研究[J].涂料工业,2013,43(2):48-51.
[2]王邦清.聚酯型聚氨酯丙烯酸酯的合成及应用[D].广州:华南理工大学,2012.
[3]商武,袁腾,王邦清,等.UV固化聚酯型聚氨酯丙烯酸酯低聚物的制备研究[J]. 2013,28(6):14-18.
[4] CHEN C Y,HUANG C K,LIN S P,et al.Low-shrinkage visible-light-curable urethane-modified epoxy acrylate/SiO2composites as dental restorative materials[J]. Composites Science&Technology,2008,68(13):2811-2817.
[5] BLANC D,LAST A,FRANC J,et al.Hard UV-curable organo-mineral coatings for optical applications[J]. Thin Solid Films,2006,515(3):942-946.
[6] MAUGUIèRE-GUYONNET F,BURGET D,FOUASSIER J P. Photopolymerization of wood coatings under visible lights[J].ProgressinOrganicCoatings,2006,57(1):23-32.
[7] JU A J,KIM B K. Controls of solubility parameter and crosslinking density in polyurethane acrylate based holographic polymer dispersed liquid crystal[J]. Optics Communications,2005,247(1-3):125-132.
[8] STROPP J P,WOLFF U,KERNAGHAN S,et al. UV curing systems for automotive refinish applications[J].Progress in Organic Coatings,2006,55(2):201-205.
[9] KARATA?S,KAYAMAN-APOHAN N,TURUN?O,et al.Synthesis and characterization of UV-curable phosphorus containing hybrid materials prepared by sol-gel technique[J].Polymers for Advanced Technologies,2011,22(5):567-576.
[10] KUO K H,CHIU W Y,DON T M.Synthesis of UV-curable alkali soluble dispersants used for black photo resist with a high loading of carbon black[J].Journal of Applied Polymer Science,2010,115(3):1803-1813.
[11] KAHRAMAN M V,KAYAMAN-APOHAN N,ARSU N,et al. Flame retardance of epoxy acrylate resin modified with phosphorus containing compounds[J]. Progress in Organic Coatings,2004,51(3):213-219.
[12] NOBEL M L,PICKEN S J,MENDES E. Waterborne nanocomposite resins for automotive coating applications[J].Progress in Organic Coatings,2007,58(2):96-104.
[13] PARK Y J,LIM D H,KIM H J,et al.UV-and thermalcuring behaviors of dual-curable adhesives based on epoxy acrylate oligomers[J]. International Journal of Adhesion and Adhesives,2009,29(27):710-717.
[14] SCHLGL S,REISCHL M,RIBITSCH V. UV induced microcellular foaming-a new approach towards the production of 3D structures in offset printing techniques[J]. China Printing&Packaging Study,2012,73(1):54-61.
[15] SAIKI N,YAMAZAKI O,EBE K.UV/heat dual-curable adhesive tapes for fabricating stacked packages of semiconductors[J].Journal of Applied Polymer Science,2010,108(2):1178-1183.
[16]邓岚,孙金媛,袁腾.可生物降解性UV固化聚氨酯丙烯酸酯预聚物的合成[J].中国胶粘剂,2018,27(7):374-378.
[17]杨柱,夏萍,邓康清,等.热/UV双重固化制备耐划伤光学扩散膜[J].涂料工业,2013,43(8):8-12.
[18]刘红波,张武英,林峰,等.高折光紫外光-热双重固化树脂的合成及其性能[J].高分子材料科学与工程,2017,33(1):23-27.
[19]齐亚龙,徐婷,张清华.光热双重固化胶粘剂的热固反应动力学研究[J].热固性树脂,2016,31(5):5-10.
[20] HUANG J J,YUAN T,YANG Z C,et al.UV/thermal dual curing of tung oil-based polymers induced by cationic photoinitiator[J].ProgressinOrganicCoatings,2019,126:8-17.
[21]肖俊芳,冯钦,贺建国,等.低温光-热双重固化材料的制备及其性能研究[J].涂料工业,2013,43(2):48-51.