CN113929795B - 一种酰基氧化膦类光引发剂 - Google Patents
一种酰基氧化膦类光引发剂 Download PDFInfo
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- XVKKIGYVKWTOKG-UHFFFAOYSA-N diphenylphosphoryl(phenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 XVKKIGYVKWTOKG-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域
本发明涉及一种酰基氧化膦类化合物,这类化合物可作为UV-LED光引发剂,在UV-LED光照下引发自由基聚合反应,用于光固化油墨、光固化胶粘剂以及光固化涂料中。本发明还涉及该类化合物的制备方法。
背景技术
光固化技术是一种新型的材料表面处理技术,因其具有节能、环保、经济、高效和适用性广等优点,在涂料、油墨、黏合剂、生物医学材料、3D打印等领域得到广泛应用。光引发剂是光固化产品配方中的重要且不可或缺的组成部分,是光固化产品的核心之一。光引发剂的选择直接关系到光固化产品的质量。通常情况下,引发活性、引发效率、合适的光的波长范围是选择光引发剂的主要指标。随着人类对于环保和健康的要求,特别是对食品、卫生领域产品的安全要求的不断提高,光引发剂的安全性,主要是指其毒性以及本身和分解产物的迁移性也逐渐被纳入考量范围。
按照引发机理的不同,光引发剂可分为自由基光引发剂与阳离子光引发剂,按自由基引发剂产生活性自由基的作用机理不同,自由基光引发剂又可以分为夺氢型光引发剂与裂解型光引发剂。在日常工业生产中,以自由基光引发剂应用最为广泛。在最常用的光引发剂中,酰基膦氧化物是一类光引发活性很高、综合性能较好的光引发剂,其中TPO、819、TPO-L等被广泛应用于UV固化油墨及涂料中。目前用量最大的酰基氧化膦引发剂为TPO(2,4,6-三甲基苯甲酰基二苯基氧化膦),在近可见光区380~400nm波长有较强的吸收,其吸收曲线甚至能延伸到480nm的可见光区,引发效率高,不易黄变。但是在研究和实际应用中发现其仍存在一定的不足,如引发效率仍需提高,主要表现为在有氧体系固化中会由于氧阻聚而降低固化效率;主要吸收波长范围仍不在可见光区,需要设计开发吸收波长比TPO更长的引发剂等。另外,TPO本身及其分解物质的毒性、气味等也限制了它在食品和卫生领域的应用。
综上所述,研究开发低迁移、低挥发、高活性、易合成的光引发剂产品依然是光固化产业的长期现实需求。
发明内容
鉴于此,本发明的设计是基于找到一类低迁移性、高反应性同时具有气味小、刺激性小等特性的化合物,并以此作为光引发剂应用于自由基聚合的光固化涂料、粘合剂及油墨中。
本发明的思路是通过在TPO结构上引入另一个苯甲酰基以增加分子的共轭性,期望共轭性的增加有利于其光吸收曲线的红移和引发效率的提高。苯甲酰基的引入事实上形成了一个二苯甲酮的结构,而二苯甲酮也是一类常用的高效光引发剂,考虑到这类引发剂属于夺氢型光引发剂,通常需要另外添加活性胺组份,于是我们又引入一个三级胺基团。这样便产生了一类新的酰基氧化膦化合物,该化合物同时具有裂解型和夺氢型自由基光引发剂的特点。其结构式如下:
式中,R1、R2为C1~6的脂肪族直链或支链烷烃,C3~6的环烷烃,C5~6的芳香烃或杂芳烃,m=0~5。推荐R1、R2为C1~6的脂肪族直链或支链烷烃。N,N-二烷基-ω-氨基烷基位置相对于羧基是对位、邻位或间位。
因此,本发明的目的是提供一种酰基膦氧化物光引发剂。
本发明的另一目的是提供一种高效便捷和实用的制备该酰基膦氧化物的方法。
反应式如下:
反应式中,halogenation为卤化反应,TPO为2,4,6-三甲基苯甲酰基二苯基氧化膦,Cat.为路易斯酸催化剂,R1、R2为C1~6的脂肪族直链或支链烷烃,C3~6的环烷烃,C5~6的芳香烃或杂芳烃,m=0~5。优选R1、R2为C1~6的脂肪族直链或支链烷烃。
所述制备方法包括以下步骤:
以3-(对二甲氨基苯甲酰基-2,4,6-三甲基)苯甲酰基二苯基氧膦的合成为例:
在有机溶剂中和室温-回流温度下,N,N-二烷基-ω-氨基烷基苯甲酰卤、路易斯酸催化剂、2,4,6-三甲基苯甲酰基二苯基氧膦进行傅克反应,反应时间1-12小时获得本发明的产物。其中N,N-二烷基-ω-氨基烷基苯甲酰卤、路易斯酸催化剂和2,4,6-三甲基苯甲酰基二苯基氧膦的摩尔比为1:0.50-2.80:0.5-1.0,优先考虑1:1-2.6:0.6-0.8。
反应完成后,产品可以采用常规方法进行水解、分相、干燥、脱溶和/或过硅胶柱进行纯化。
所述的有机溶剂可以是卤代烷烃、卤代苯类、硝基烷烃、硝基苯类和二硫化碳等,可以单独使用,也可以混合使用。
所述路易斯酸催化剂一般是指无水三氯化铝、无水氯化锌、无水三氯化铁、三氟化硼乙醚或其两种以上的混合物。
其中,原料N,N-二烷基-ω-氨基烷基苯甲酰卤是以N,N-二烷基-ω-氨基烷基苯甲酸为原料,以常规方法进行酰卤化反应获得。如3-(N,N-二烷基-ω-氨基烷基苯甲酰基)-2,4,6-三甲基苯甲酰基二苯基氧膦,所谓酰卤主要指酰氯或酰溴。
本发明提供的酰基氧化膦类化合物,通过在常规酰基氧化膦型光引发剂结构中引入含叔胺基团的苯甲酰基,增加了分子量,提高了产品的沸点,降低了产品的挥发性能。同时,由于酰基的共轭性能,使得苯甲酰基膦氧化物的最大吸收波长延长,且形成的自由基也更加稳定,比较适合UV-LED光引发。
本发明提供的此类酰基氧化膦类光引发剂的制备方法,反应操作简便,反应过程温和,适合工业化生产。
本发明提供的此类酰基膦氧化物光引发剂在相关光固化油墨、涂料及胶粘剂中使用方便,所得产品挥发性极小且气味小、刺激性小,光固化反应快速,可以满足最终产品性能要求。
具体实施例
下面结合一些实施例对本发明做进一步的阐述,但这些实施例旨在便于人们理解本发明,但是不能限制本发明范围。
实施例一
(1)对二甲氨基苯甲酰氯的合成
干燥的三口烧瓶中,安装磁力搅拌、温度计、回流冷凝管,加入对二甲氨基苯甲酸4.2克(0.025摩尔)、二氯乙烷20毫升,冰浴冷却下滴加氯化亚砜6克(0.05摩尔),然后加入2滴DMF。撤去冰水浴,缓慢升至室温,然后再慢慢加热到50℃,继续反应2小时。改蒸馏装置,蒸去未反应的氯化亚砜和溶剂,得到N,N-二甲基对氨基苯甲酰氯4.6克,不做进一步纯化,直接用于下一步反应。
(2)(3-对二甲氨基苯甲酰基-2,4,6-三甲基)苯甲酰基二苯基氧膦(DMB-TPO)的合成
向上述反应瓶中加入二氯乙烷30毫升,搅拌使溶解,分批加入无水三氯化铝8.6克(0.065摩尔),有升温。滴加TPO(6克,0.0175摩尔)的二氯乙烷(15毫升)溶液,温度变化不大。加毕,升温至70℃反应过夜,点板判断反应终点。冷却,搅拌下滴加50克水,反应放热。加毕,升温到70℃搅拌1小时。冷却,转移到分液漏斗中分相,分出有机相,水相用10毫升二氯甲烷萃取两次,合并有机相,10毫升清水洗涤三次,分出有机相,无水硫酸镁干燥,过滤,旋蒸浓缩至干,得到类白色产品9克,过硅胶柱,得到6.5克白色固体,熔点68-70℃,HPLC含量为97.3%。1H NMR(400MHz,CDCl3):δ8.02-7.97(m,4H,-C6H5),7.69-7.48(m,8H,-C6H5,-C6H4-),6.91(s,1H,-C6H),6.65-6.63(d,2H,-C6H4-),3.07(s,6H,-N(CH3)2),2.11-2.09(m,6H,-CH3),1.78(s,3H,-CH3)。13C NMR(400MHz,CDCl3):δ219.60、197.03(羰基碳),153.83、139.03、136.95、134.76、132.66、132.44、131.94、131.85、131.23、129.92、128.83、128.71、125.06、125.01、110.93(苯环碳),40.05(氮上甲基),19.71、19.45、17.18(苯环上3个甲基碳)。紫外吸收光谱如图1所示,图1-1为DMB-TPO,图1-2为TPO。
实施例二
参照如下具体配方,配制感光性树脂组合物:
按混合或研磨等常规方法将上述组分制成油墨,在氮气气氛中以395nm、385nm紫外灯照射固化,10秒即可固化。本油墨自身无气味,经光固化后亦没有气味,达到凹印软包装油墨的要求。
实施例三
与实施例二条件相同,采用TPO为光引发剂。制备的油墨在光固化后有一定的刺激性气味。通过气相色谱法顶空分析,以TPO为光引发剂的油墨,检测到3,4,5-三甲基苯醛,而实施例二中没检测到含醛基物质。
Claims (9)
2.如权利要求1所述的酰基氧化膦类光引发剂,其特征是所述的R1、R2为C1~6的脂肪族直链或支链烷烃。
4.如权利要求3所述的酰基氧化膦类光引发剂的制备方法,其特征是所述的N,N-二烷基-ω-氨基烷基苯甲酰卤、路易斯酸催化剂和2,4,6-三甲基苯甲酰基二苯基氧膦的摩尔比为1:1-2.6:0.6-0.8。
5.如权利要求3所述的制备方法,其特征在于所述的N,N-二烷基-ω-氨基烷基苯甲酸中的N,N-二烷基-ω-氨基烷基位置相对于羧基是对位、邻位或间位。
6.如权利要求3所述的制备方法,其特征在于所述的N,N-二烷基-ω-氨基烷基苯甲酰卤中的酰卤是酰氯或酰溴。
7.如权利要求3、4、5或6所述的制备方法,其特征在于所述的有机溶剂是卤代烷烃、卤代苯类、硝基烷烃、硝基苯类或二硫化碳。
8.如权利要求3、4、5或6所述的制备方法,其特征在于所述的路易斯酸催化剂指无水三氯化铝、无水氯化锌、无水三氯化铁、三氟化硼乙醚、或上述路易斯酸的混合物。
9.一种如权利要求1所述的酰基氧化膦类光引发剂用于光固化油墨、光固化胶粘剂或光固化涂料的用途。
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