CN117327422B - 一种uv固化聚氨酯油墨的合成工艺 - Google Patents
一种uv固化聚氨酯油墨的合成工艺 Download PDFInfo
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Abstract
本发明涉及聚氨酯技术领域,且公开了一种UV固化聚氨酯油墨的合成工艺,将亲水性和抗菌性的咪唑盐官能团,以及烯基官能团接枝到聚氨酯的侧链,得到咪唑盐基聚氨酯具有优良的UV光固化特性,固化速率快,以水作为溶剂,绿色环保,并且扩链后的聚氨酯漆膜耐水性好,吸水率低,硬度高,附着力大,同时具有良好的抗菌性能,拓展了聚氨酯在水性油墨等领域的发展和应用。
Description
技术领域
本发明涉及聚氨酯技术领域,具体为一种UV固化聚氨酯油墨。
背景技术
油墨通常由连结料树脂、颜料、填料和溶剂等组成。广泛应用在书刊、包装装潢、建筑装饰等各种印刷领域。随着人们环保意识的日益增强,水性油墨受到广泛的研究的关注,UV固化水性聚氨酯具有绿色环保、固化速度快、涂膜性能优良,在油墨、涂料、胶黏剂等领域有着重要的应用,文献《基于TMPME与BTEA的可紫外光固化水性聚氨酯的光固化动力学及涂膜性能》,报道了以含双键二元醇三羟甲基丙烷单烯丙基醚(TMPME)与2-(3-(((2,2-二(羟甲基)丁氧基)酰胺基)甲基)-3,5,5-三甲基环己基氨基甲酰氧)丙烯酸乙酯(BTEA)作为扩链剂,在聚氨酯分子侧链上引入可UV固化的双键,得到的光固化聚氨酯具有较高的交联密度、耐水性和耐溶剂性等性能。开发新型的扩链剂提高聚氨酯的综合性能,拓展聚氨酯在油墨、涂料等领域的应用是研究热点,专利CN101891876B《咪唑盐类阳离子型聚氨酯及其制备方法》,公开了将咪唑盐二醇、长链二醇和二异氰酸酯作为反应物,合成了阳离子型聚氨酯,具有带电性,且其带电性不受酸碱破坏的特点。
发明内容
解决的技术问题:针对现有技术的不足,本发明合成了亲水性好、耐水性优良和抗菌优异的UV固化聚氨酯油墨。
技术方案:一种UV固化聚氨酯油墨的合成工艺,包括以下步骤:
(1)将多元醇和二异氰酸酯溶解到丙酮中,然后滴加二月桂酸二丁基锡,在60-75℃中回流反应2-3h,然后加入双(羟乙基咪唑)丙烯酰胺,继续反应1-2h,再加入Br(CH2)nCH3,其中n=2~6中的任一种,继续反应12-36h,反应后冷却,减压浓缩除去丙酮,得到咪唑盐基聚氨酯。
(2)将重量占比为20-35%的咪唑盐基聚氨酯、60-75%去离子水、2-5%颜料、0.2-0.6%光引发剂、0.1-0.3%分散剂、1-2%的成膜助剂混合均匀加入到分散砂磨机中,高速研磨均匀,得到UV固化聚氨酯油墨。
优选的,多元醇选自聚乙二醇、聚丙二醇、聚碳酸酯二元醇、聚酯多元醇、聚四氢呋喃醚二醇中的任一种。
优选的,二异氰酸酯选自六亚甲基二异氰酸酯、甲苯-2,4-二异氰酸酯、对苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯甲烷二异氰酸酯中的任一种。
优选的,双(羟乙基咪唑)丙烯酰胺是多元醇和二异氰酸酯总重量的6-12%。
优选的,Br(CH2)nCH3是双(羟乙基咪唑)丙烯酰胺总重量的60-95%。
优选的,光引发剂选自光引发剂184、光引发剂1173、光引发剂4265、光引发剂2,4,6-三甲基苯甲酰二苯氧磷(TPO)中的任一种。
优选的,双(羟乙基咪唑)丙烯酰胺的合成工艺为:
(1)将丙烯酰氯溶解到二氯甲烷中,在冰水浴中滴加双(2-氯乙基)胺盐酸盐和三乙胺,搅拌反应2-4h,反应后加入0.3-0.5%的稀盐酸溶液,进行萃取,静置分层后将有机层加入硫酸钠干燥过夜,过滤后将滤液减压浓缩,得到双(2-氯乙基)丙烯酰胺。
(2)将反应物双(2-氯乙基)丙烯酰胺和4-羟乙基咪唑溶解到乙醇溶剂中,然后加入催化剂叔丁醇钾,加热至70-80℃搅拌回流反应12-24h,反应后冷却,减压浓缩,正己烷洗涤,得到双(羟乙基咪唑)丙烯酰胺。
优选的,催化剂叔丁醇钾的用量为反应物总重量的8-20%。
有益的技术效果:本发明将亲水性和抗菌性的咪唑盐官能团,以及烯基官能团接枝到聚氨酯的侧链,得到咪唑盐基聚氨酯具有优良的UV光固化特性,固化速率快,以水作为溶剂,绿色环保,并且扩链后的聚氨酯漆膜耐水性好,吸水率低,硬度高,附着力大,同时具有良好的抗菌性能,拓展了聚氨酯在水性油墨等领域的发展和应用。
附图说明
图1是双(羟乙基咪唑)丙烯酰胺的合成路线。
具体实施方式
实施例1
(1)将0.52g的丙烯酰氯溶解到二氯甲烷中,在冰水浴中滴加1g的双(2-氯乙基)胺盐酸盐和2mL的三乙胺,搅拌反应3h,反应后加入0.4%的稀盐酸溶液,进行萃取,静置分层后将有机层加入硫酸钠干燥过夜,过滤后将滤液减压浓缩,得到双(2-氯乙基)丙烯酰胺。
(2)将1.5g的双(2-氯乙基)丙烯酰胺和1.5g的4-羟乙基咪唑溶解到乙醇溶剂中,然后加入0.6g的催化剂叔丁醇钾,加热至80℃搅拌回流反应24h,反应后冷却,减压浓缩,正己烷洗涤,得到双(羟乙基咪唑)丙烯酰胺。
(3)将15g的聚酯多元醇和6.4g的甲苯-2,4-二异氰酸酯溶解到丙酮中,然后滴加二月桂酸二丁基锡,在75℃中回流反应2h,然后加入2.1g的双(羟乙基咪唑)丙烯酰胺,继续反应2h,再加入1.9g的溴丁烷Br(CH2)6CH3,继续反应24h,反应后冷却,减压浓缩除去丙酮,得到咪唑盐基聚氨酯。
(4)将重量占比为20%的咪唑盐基聚氨酯、75%去离子水、4%颜料、0.2%光引发剂184、0.2%分散剂BYK-161、1%的成膜助剂醇酯12,混合均匀加入到分散砂磨机中,高速研磨均匀,得到UV固化聚氨酯油墨。
实施例2
(1)将0.6g的丙烯酰氯溶解到二氯甲烷中,在冰水浴中滴加1g的双(2-氯乙基)胺盐酸盐和2.5mL的三乙胺,搅拌反应4h,反应后加入0.5%的稀盐酸溶液,进行萃取,静置分层后将有机层加入硫酸钠干燥过夜,过滤后将滤液减压浓缩,得到双(2-氯乙基)丙烯酰胺。
(2)将1.5g的双(2-氯乙基)丙烯酰胺和1.5g的4-羟乙基咪唑溶解到乙醇溶剂中,然后加入0.5g的催化剂叔丁醇钾,加热至80℃搅拌回流反应24h,反应后冷却,减压浓缩,正己烷洗涤,得到双(羟乙基咪唑)丙烯酰胺。
(3)将12g的聚乙二醇和7.2g的异佛尔酮二异氰酸酯溶解到丙酮中,然后滴加二月桂酸二丁基锡,在75℃中回流反应3h,然后加入1.5g的双(羟乙基咪唑)丙烯酰胺,继续反应2h,再加入0.9g的溴丙烷Br(CH2)2CH3,继续反应36h,反应后冷却,减压浓缩除去丙酮,得到咪唑盐基聚氨酯。
(4)将重量占比为30%的咪唑盐基聚氨酯、65%去离子水、3%颜料、0.6%光引发剂1173、0.2%分散剂BYK-161、1%的成膜助剂醇酯12,混合均匀加入到分散砂磨机中,高速研磨均匀,得到UV固化聚氨酯油墨。
实施例3
(1)将0.45g的丙烯酰氯溶解到二氯甲烷中,在冰水浴中滴加1g的双(2-氯乙基)胺盐酸盐和1.5mL的三乙胺,搅拌反应2h,反应后加入0.3%的稀盐酸溶液,进行萃取,静置分层后将有机层加入硫酸钠干燥过夜,过滤后将滤液减压浓缩,得到双(2-氯乙基)丙烯酰胺。
(2)将1.4g的双(2-氯乙基)丙烯酰胺和1.5g的4-羟乙基咪唑溶解到乙醇溶剂中,然后加入0.35g的催化剂叔丁醇钾,加热至75℃搅拌回流反应12h,反应后冷却,减压浓缩,正己烷洗涤,得到双(羟乙基咪唑)丙烯酰胺。
(3)将12g的聚酯多元醇和6.2g的异佛尔酮二异氰酸酯溶解到丙酮中,然后滴加二月桂酸二丁基锡,在75℃中回流反应2h,然后加入1.4g的双(羟乙基咪唑)丙烯酰胺,继续反应1.5h,再加入1.5g的溴戊烷Br(CH2)4CH3,继续反应24h,反应后冷却,减压浓缩除去丙酮,得到咪唑盐基聚氨酯。
(4)将重量占比为35%的咪唑盐基聚氨酯、60%去离子水、3%颜料、0.3%光引发剂184、0.1%分散剂BYK-161、2%的成膜助剂醇酯12,混合均匀加入到分散砂磨机中,高速研磨均匀,得到UV固化聚氨酯油墨。
实施例4
(1)将0.5g的丙烯酰氯溶解到二氯甲烷中,在冰水浴中滴加1g的双(2-氯乙基)胺盐酸盐和2mL的三乙胺,搅拌反应4h,反应后加入0.5%的稀盐酸溶液,进行萃取,静置分层后将有机层加入硫酸钠干燥过夜,过滤后将滤液减压浓缩,得到双(2-氯乙基)丙烯酰胺。
(2)将1.2g的双(2-氯乙基)丙烯酰胺和1.5g的4-羟乙基咪唑溶解到乙醇溶剂中,然后加入0.14g的催化剂叔丁醇钾,加热至70℃搅拌回流反应12h,反应后冷却,减压浓缩,正己烷洗涤,得到双(羟乙基咪唑)丙烯酰胺。
(3)将10g的聚四氢呋喃醚二醇和5.5g的异佛尔酮二异氰酸酯溶解到丙酮中,然后滴加二月桂酸二丁基锡,在60℃中回流反应2h,然后加入0.95g的双(羟乙基咪唑)丙烯酰胺,继续反应1h,再加入0.6g的溴乙烷Br(CH2)2CH3,继续反应12h,反应后冷却,减压浓缩除去丙酮,得到咪唑盐基聚氨酯。
(4)将重量占比为30%的咪唑盐基聚氨酯、67%去离子水、2%颜料、0.2%光引发剂1173、0.3%分散剂BYK-161、1%的成膜助剂醇酯12,混合均匀加入到分散砂磨机中,高速研磨均匀,得到UV固化聚氨酯油墨。
对比例1
(1)将0.6g的丙烯酰氯溶解到二氯甲烷中,在冰水浴中滴加1g的双(2-氯乙基)胺盐酸盐和2.5mL的三乙胺,搅拌反应2h,反应后加入0.3%的稀盐酸溶液,进行萃取,静置分层后将有机层加入硫酸钠干燥过夜,过滤后将滤液减压浓缩,得到双(2-氯乙基)丙烯酰胺。
(2)将1.2g的双(2-氯乙基)丙烯酰胺和1.5g的4-羟乙基咪唑溶解到乙醇溶剂中,然后加入0.46g的催化剂叔丁醇钾,加热至75℃搅拌回流反应24h,反应后冷却,减压浓缩,正己烷洗涤,得到双(羟乙基咪唑)丙烯酰胺。
(3)将10g的聚四氢呋喃醚二醇和5.8g的异佛尔酮二异氰酸酯、溶解到丙酮中,然后滴加二月桂酸二丁基锡,在75℃中回流反应3h,然后加入1.7g的双(羟乙基咪唑)丙烯酰胺,继续反应1h,反应后冷却,减压浓缩除去丙酮,得到咪唑基聚氨酯。
(4)将重量占比为20%的咪唑基聚氨酯、73%去离子水、5%颜料、0.2%光引发剂184、0.1%分散剂BYK-161、2%的成膜助剂醇酯12,混合均匀加入到分散砂磨机中,高速研磨均匀,得到咪唑基UV固化聚氨酯油墨。
将UV固化聚氨酯油墨在UV固化机中进行光固化,将固化后的聚氨酯胶膜参考标准ASTMD870-2002测试耐水性;将聚氨酯胶膜称重,并至于去离子水中浸没48h,取出后擦拭表面水分并称重,计算吸水率W,W=(m1-m)/m;m1聚氨酯胶膜吸水后重量;m是吸水前重量。参考标准ASTM D3359-2002测试附着力;
采用光学接触角测试仪对聚氨酯胶膜进行水接触角测试。
参考QB/T2591-2003的方法,测试UV固化聚氨酯胶膜的抗菌性能:移取100μL的大肠杆菌菌悬液中加入牛肉膏蛋白胨培养液,在37℃中进行摇床培养12h,培养后加入去离子水稀释至1×106CFU/mL;将规格为1cm×1cm的聚氨酯胶膜放入到稀释后的菌悬液中,在37℃摇床培养2h;不加聚氨酯胶膜作为空白样。
将培养后菌悬液均匀涂覆在琼脂培养基上,在37℃的恒温培养箱内培养24h,统计细菌菌落数,并计算抗菌率;抗菌率S=(A-B)/A×100%,其中:A为空白样24h后每片平均回收细菌数;B为聚氨酯胶膜样品板24h后每片平均回收细菌数。
实施例1-4以双(羟乙基咪唑)丙烯酰胺作为扩链剂,然后经过Br(CH2)nCH3季铵化,得到的UV固化聚氨酯油墨的亲水性好,耐水性高,抗菌率达到98.4-99.8%,而对比例1合成的咪唑基UV固化聚氨酯的亲水性和耐水性不高,抗菌性能很差。
Claims (7)
1.一种UV固化聚氨酯油墨的合成工艺,其特征在于:所述UV固化聚氨酯油墨的合成工艺包括以下步骤:
(1)将多元醇和二异氰酸酯溶解到丙酮中,然后滴加二月桂酸二丁基锡,在60-75℃中回流反应2-3h,然后加入双(羟乙基咪唑)丙烯酰胺,继续反应1-2h,再加入Br(CH2)nCH3,其中n=2~6中的任一种,继续反应12-36h,反应后冷却,减压浓缩除去丙酮,得到咪唑盐基聚氨酯;
(2)将重量占比为20-35%的咪唑盐基聚氨酯、60-75%去离子水、2-5%颜料、0.2-0.6%光引发剂、0.1-0.3%分散剂、1-2%的成膜助剂混合均匀加入到分散砂磨机中,高速研磨均匀,得到UV固化聚氨酯油墨;
所述双(羟乙基咪唑)丙烯酰胺的合成工艺为:
步骤(1)丙烯酰氯溶解到二氯甲烷中,在冰水浴中滴加双(2-氯乙基)胺盐酸盐和三乙胺,搅拌反应2-4h,反应后加入0.3-0.5%的稀盐酸溶液,进行萃取,静置分层后将有机层加入硫酸钠干燥过夜,过滤后将滤液减压浓缩,得到双(2-氯乙基)丙烯酰胺;
步骤(2)将反应物双(2-氯乙基)丙烯酰胺和4-羟乙基咪唑溶解到乙醇溶剂中,然后加入催化剂叔丁醇钾,加热至70-80℃搅拌回流反应12-24h,反应后冷却,减压浓缩,正己烷洗涤,得到双(羟乙基咪唑)丙烯酰胺。
2.根据权利要求1所述的UV固化聚氨酯油墨的合成工艺,其特征在于:所述多元醇选自聚乙二醇、聚丙二醇、聚碳酸酯二元醇、聚酯多元醇、聚四氢呋喃醚二醇中的任一种。
3.根据权利要求1所述的UV固化聚氨酯油墨的合成工艺,其特征在于:所述二异氰酸酯选自六亚甲基二异氰酸酯、甲苯-2,4-二异氰酸酯、对苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯甲烷二异氰酸酯中的任一种。
4.根据权利要求1所述的UV固化聚氨酯油墨的合成工艺,其特征在于:所述(1)中双(羟乙基咪唑)丙烯酰胺是多元醇和二异氰酸酯总重量的6-12%。
5.根据权利要求1所述的UV固化聚氨酯油墨的合成工艺,其特征在于:所述(1)中Br(CH2)nCH3是双(羟乙基咪唑)丙烯酰胺总重量的60-95%。
6.根据权利要求1所述的UV固化聚氨酯油墨的合成工艺,其特征在于:所述(2)中光引发剂选自光引发剂184、光引发剂1173、光引发剂4265、光引发剂2,4,6-三甲基苯甲酰二苯氧磷(TPO)中的任一种。
7.根据权利要求1所述的UV固化聚氨酯油墨的合成工艺,其特征在于:所述双(羟乙基咪唑)丙烯酰胺的合成工艺的步骤(2)中,催化剂叔丁醇钾的用量为反应物总重量的8-20%。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012036546A1 (en) * | 2010-09-13 | 2012-03-22 | Dsm Ip Assets B.V. | Curable liquid resin composition for outermost covering layers of optical fiber line |
CN107162981A (zh) * | 2017-05-23 | 2017-09-15 | 华南理工大学 | 含卤化咪唑盐结构的抗菌性可聚合单体及其制法和应用 |
CN107236103A (zh) * | 2017-06-08 | 2017-10-10 | 滁州金桥德克新材料有限公司 | 一种电子束固化高柔韧改性聚氨酯丙烯酸酯及其制备方法 |
CN107266636A (zh) * | 2017-06-08 | 2017-10-20 | 滁州金桥德克新材料有限公司 | 一种电子束固化耐划伤改性聚氨酯丙烯酸酯及其制备方法 |
JP7075533B1 (ja) * | 2021-09-29 | 2022-05-25 | 大日精化工業株式会社 | 活性エネルギー線硬化型インキ組成物及び印刷物 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012036546A1 (en) * | 2010-09-13 | 2012-03-22 | Dsm Ip Assets B.V. | Curable liquid resin composition for outermost covering layers of optical fiber line |
CN107162981A (zh) * | 2017-05-23 | 2017-09-15 | 华南理工大学 | 含卤化咪唑盐结构的抗菌性可聚合单体及其制法和应用 |
CN107236103A (zh) * | 2017-06-08 | 2017-10-10 | 滁州金桥德克新材料有限公司 | 一种电子束固化高柔韧改性聚氨酯丙烯酸酯及其制备方法 |
CN107266636A (zh) * | 2017-06-08 | 2017-10-20 | 滁州金桥德克新材料有限公司 | 一种电子束固化耐划伤改性聚氨酯丙烯酸酯及其制备方法 |
JP7075533B1 (ja) * | 2021-09-29 | 2022-05-25 | 大日精化工業株式会社 | 活性エネルギー線硬化型インキ組成物及び印刷物 |
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