CN110387000A - 二苯甲酮类衍生物光引发剂及制备方法 - Google Patents
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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Abstract
本发明属于感光高分子材料领域。本发明基于4‑羟基二苯甲酮、丙烯酰氯和不同官能度的巯基化合物反应制备了二苯甲酮类衍生物光引发剂。通过在分子结构中引入不饱和双键,在将其与巯基点击化学反应,在保证其光引发活性的同时提高其分子量,来降低固化后在体系中的迁移率。本发明的合成步骤简单,制备成本低,产物迁移率较低,在紫外光固化领域有广泛的应用前景。
Description
技术领域
本发明属于感光高分子材料领域,二苯甲酮类衍生物光引发剂及制备方法。
背景技术
光固化技术作为一种反应条件温和、反应速度快、对基材损伤小、没有三废排放、不污染环境的绿色友好型技术,问世至今取得了快速的发展。并在油墨、涂料、光刻胶、微电子、生物材料和牙齿修复材料等方面均有着广泛的应用。一般而言,光固化体系包含齐聚物、单体、光引发剂和助剂,其中光引发剂虽所占含量较少但对整个体系起着至关重要的作用,因为引发剂能够在一定波长的紫外光照射下,吸收光能产生活性种、自由基或离子,从而引发单体聚合。
目前常用的一些小分子光引发剂存在着这样一些问题,它们在聚合过程中会产生小分子光解产物,并会迁移出交联的聚合网络到涂层表面,导致一些潜在的健康风险。光引发剂造成食品污染的警报出现在2005年,2-异丙基硫杂蒽酮(2-ITX)由于迁移问题,在婴儿奶粉中达到了120-300μg/L的浓度,导致超过3000万公升的牛奶退出商业市场。随着人们对食品安全的重视,相关国家己出台了光引发剂迁移限量标准,避免再次发生光引发剂污染食品的事件。随着紫外光固化技术的不断发展,为符合环保、安全的要求,研发具有反应活性高、低毒性、低气味和低迁移性等特点的新型光引发剂非常有必要。
发明内容
本发明要解决的技术问题是:为了解决一般小分子量光引发剂在体系中容易迁移的问题,本发明提供了二苯甲酮类衍生物光引发剂及制备方法,降低了光引发剂在体系中的迁移性。通过在光引发剂分子结构中引入不饱和双键,在将其与不同官能度的巯基化合物发生点击化学反应,在保证其光引发活性的同时提高分子量。相同条件下HEA/二苯甲酮类衍生物光引发剂体系浸泡后引发剂的吸光度明显低于HEA/4-羟基二苯甲酮。因分子量大的光引发剂,聚合后在聚合物大分子链中移动较难,降低了聚合物网络中小分子的迁移。在体系中迁移性的降低及引发低聚物效率与未改性前光引发剂引发效率相似,足以说明其是一种很好的光引发剂。本发明提供了这种二苯甲酮类衍生物光引发剂及制备方法,反应过程简单,反应条件温和,后处理简单并且容易纯化。
本发明解决技术问题采用的技术手段是:二苯甲酮类衍生物光引发剂及制备方法,其结构为:
二苯甲酮类衍生物光引发剂的制备反应方程式为:
所述二苯甲酮类衍生物光引发剂的制备方法,包括如下步骤:
步骤1)在溶剂中加入4-羟基二苯甲酮和三乙胺冰水浴条件下搅拌;
步骤2)将丙烯酰氯的溶于溶剂,恒压滴定到步骤1)中的混合物中,冰水浴条件下控制滴加时间,随后室温搅拌6H;
步骤3)反应完成后,过滤除去固体杂质,分别用去离子水、HCl(1mol/L)和NaHCO3(1mol/L)水溶液洗涤2次,有机层干燥过滤,旋蒸除去溶剂得到粗产物,并用乙醇重结晶,得到中间产物A;
步骤4)在溶剂中加入中间产物A、带巯基化合物,通氮气,加热条件下搅拌;
步骤5)在步骤4)的混合物中加入氢氧化钠,用TLC监测反应进度,悬蒸除去溶剂,最后得到产物;
具体地,所述4-羟基二苯甲酮与三乙胺的摩尔比为1:1-1.2;
具体地,所述三乙胺与丙烯酰氯的摩尔比为1:1;
具体地,所述带巯基化合物种类较多,且有不同官能度;
具体地,所述中间产物A与巯基化合物官能度的摩尔比为1:1-1.1;
具体地,所述加热条件为40-50℃;
具体地,所述溶剂为二氯甲烷、乙腈和四氢呋喃中的一种或几种。
本发明的有益效果是:本发明提供了二苯甲酮类衍生物光引发剂及制备方法,降低了光引发剂在体系中的迁移性。通过在光引发剂分子结构中引入不饱和双键,在将其与不同官能度的巯基发生点击化学反应,在保证其光引发活性的同时提高分子量。相同条件下HEA/二苯甲酮类衍生物光引发剂体系浸泡后引发剂的吸光度明显低于HEA/4-羟基二苯甲酮。因分子量大的光引发剂,聚合后在聚合物大分子链中移动较难,降低了聚合物网络中小分子的迁移。在体系中迁移性的降低及引发低聚物效率与未改性前光引发剂引发效率相似,足以说明其是一种很好的光引发剂。本发明提供了这类二苯甲酮类衍生物光引发剂及制备方法,反应过程简单,反应条件温和,后处理简单并且容易纯化。
具体实施方式
下列实施例详细说明本发明,但并不限制本发明的范围。
实施例1:
化合物1的结构式:
将4-羟基二苯甲酮(19.8g,0.1mol)、三乙胺(12.12g,0.12mol)以及100ml二氯甲烷加入到装配有机械搅拌和和恒压滴液漏斗的250ml三口烧瓶中,冰水浴条件下搅拌5min。将丙烯酰氯(10.86g,0.12mol)加入到装有50ml二氯甲烷溶剂的恒压滴液漏斗中,控制滴加速度,2H内滴加完毕,最后室温搅拌6H。反应完成后,过滤除去固体杂质,分别用去离子水、HCl(1mol/L)和NaHCO3(1mol/L)水溶液洗涤2次,有机层干燥过滤,旋蒸除去溶剂得到粗产物,并用乙醇重结晶,得到中间产物A。随后将溶于60ml乙腈中的中间产物A和3-巯基丙酸甲酯(12.0g,0.1mol)加入到装配有机械搅拌和恒压滴液漏斗的250ml四口烧瓶中,通氮气,45℃搅拌,用TLC监测反应进度,悬蒸除去溶剂,用凝胶色谱柱分离进一步提纯,最终得到纯净产物1,并通过核磁共振波谱进行结构鉴定。
1HNMR(400MHz,Acetone-d6)δ(ppm):7.43-7.81(9H,aromatics),2.58-2.83(8H,-CH2-),3.60(3H,-CH3).
实施例2
化合物2的结构式为:
将4-羟基二苯甲酮(19.8g,0.1mol)、三乙胺(12.12g,0.12mol)以及100ml二氯甲烷加入到装配有机械搅拌和和恒压滴液漏斗的250ml三口烧瓶中,冰水浴条件下搅拌5min。将丙烯酰氯(10.86g,0.12mol)加入到装有50ml二氯甲烷溶剂的恒压滴液漏斗中,控制滴加速度,2H内滴加完毕,最后室温搅拌6H。反应完成后,过滤除去固体杂质,分别用去离子水、HCl(1mol/L)和NaHCO3(1mol/L)水溶液洗涤2次,有机层干燥过滤,旋蒸除去溶剂得到粗产物,并用乙醇重结晶,得到中间产物A。随后将溶于60ml乙腈中的中间产物A和2,3-二巯基丁二酸(18.2g,0.1mol)加入到装配有机械搅拌和恒压滴液漏斗的250ml四口烧瓶中,通氮气,45℃搅拌,用TLC监测反应进度,悬蒸除去溶剂,用凝胶色谱柱分离进一步提纯,最终得到纯净产物2,并通过核磁共振波谱进行结构鉴定。
1HNMR(400MHz,Acetone-d6)δ(ppm):7.43-7.81(18H,aromatics),2.82-2.83(8H,-CH2-),14.17(2H,-OH).
实施例3
化合物3的结构式为:
将4-羟基二苯甲酮(19.8g,0.1mol)、三乙胺(12.12g,0.12mol)以及100ml二氯甲烷加入到装配有机械搅拌和和恒压滴液漏斗的250ml三口烧瓶中,冰水浴条件下搅拌5min。将丙烯酰氯(10.86g,0.12mol)加入到装有50ml二氯甲烷溶剂的恒压滴液漏斗中,控制滴加速度,2H内滴加完毕,最后室温搅拌6H。反应完成后,过滤除去固体杂质,分别用去离子水、HCl(1mol/L)和NaHCO3(1mol/L)水溶液洗涤2次,有机层干燥过滤,旋蒸除去溶剂得到粗产物,并用乙醇重结晶,得到中间产物A。随后将溶于60ml四氢呋喃中的中间产物A和三羟甲基丙烷三(3-巯基丙酸)酯(39.8g,0.1mol)加入到装配有机械搅拌和恒压滴液漏斗的250ml四口烧瓶中,通氮气,50℃搅拌,用TLC监测反应进度,悬蒸除去溶剂,用凝胶色谱柱分离进一步提纯,最终得到纯净产物3,并通过核磁共振波谱进行结构鉴定。
1HNMR(400MHz,Acetone-d6)δ(ppm):7.33-7.93(27H,aromatics),1.69-2.83(32H,-CH2-),0.83(3H,-CH3).
实施例4
化合物4的结构式为:
将4-羟基二苯甲酮(19.8g,0.1mol)、三乙胺(12.12g,0.12mol)以及100ml二氯甲烷加入到装配有机械搅拌和和恒压滴液漏斗的250ml三口烧瓶中,冰水浴条件下搅拌5min。将丙烯酰氯(10.86g,0.12mol)加入到装有50ml二氯甲烷溶剂的恒压滴液漏斗中,控制滴加速度,2H内滴加完毕,最后室温搅拌6H。反应完成后,过滤除去固体杂质,分别用去离子水、HCl(1mol/L)和NaHCO3(1mol/L)水溶液洗涤2次,有机层干燥过滤,旋蒸除去溶剂得到粗产物,并用乙醇重结晶,得到中间产物A。随后将溶于60ml四氢呋喃中的中间产物A和四(3-巯基丙酸)季戊四醇酯(48.8g,0.1mol)加入到装配有机械搅拌和恒压滴液漏斗的250ml四口烧瓶中,通氮气,50℃搅拌,用TLC监测反应进度,悬蒸除去溶剂,用凝胶色谱柱分离进一步提纯,最终得到纯净产物4,并通过核磁共振波谱进行结构鉴定。
1HNMR(400MHz,Acetone-d6)δ(ppm):7.33-7.93(36H,aromatics),2.05-2.83(40H,-CH2-).
对比实例5
将上述实施例1-4所制得的产物以及4-羟基二苯甲酮引发丙烯酸羟乙酯(HEA)聚合,对二甲氨基苯甲酸乙酯(EDAB)为助引发剂。其中,HEA为99.2%(wt),各引发剂及EDAB的浓度均为0.4%(wt),将上述配方分别注入圆形硅胶模具中,在UV固化箱中光照10min,使其固化后得到直径约为12mm,厚度为1mm的样品,所用光强为35mW/cm2。将固化膜碎片在10ml乙腈中浸泡5天后,各浸泡液中的光引发剂的紫外吸收光谱,可以看出,体系固化后仍有光引发剂残留在体系中。根据光引发剂在各自最大吸收波长处的吸光度值可以计算出他们的萃取质量占总质量的百分比,所得数据列于表1。结果表明,这类二苯甲酮类衍生物光引发剂能够有效的降低迁移率,是一种很好的光引发剂。
表1光引发剂残留量数据分析
Claims (7)
1.二苯甲酮类衍生物光引发剂及制备方法,其特征在于包括如下步骤:
步骤1)在溶剂中加入4-羟基二苯甲酮和三乙胺冰水浴条件下搅拌;
步骤2)将丙烯酰氯的溶于溶剂,恒压滴定到步骤1)中的混合物中,冰水浴条件下控制滴加时间,随后室温搅拌6H;
步骤3)反应完成后,过滤除去固体杂质,分别用去离子水、HCl(1mol/L)和NaHCO3(1mol/L)水溶液洗涤2次,有机层干燥过滤,旋蒸除去溶剂得到粗产物,并用乙醇重结晶,得到中间产物A,结构式如下;
步骤4)在溶剂中加入中间产物A、带巯基化合物,通氮气,加热条件下搅拌;
步骤5)在步骤4)的混合物中加入氢氧化钠,用TLC监测反应进度,悬蒸除去溶剂,最后得到产物。
2.如权利要求1所述的二苯甲酮类衍生物光引发剂及制备方法,其特征在于:所述4-羟基二苯甲酮与三乙胺的摩尔比为1:1-1.2。
3.如权利要求1所述的二苯甲酮类衍生物光引发剂及制备方法,其特征在于:所述三乙胺与丙烯酰氯的摩尔比为1:1。
4.如权利要求1所述的二苯甲酮类衍生物光引发剂及制备方法,其特征在于:所述带巯基化合物种类较多,且有不同官能度。
5.如权利要求1所述的二苯甲酮类衍生物光引发剂及制备方法,其特征在于:所述中间产物A与巯基化合物官能度的摩尔比为1:1-1.1。
6.如权利要求1所述的二苯甲酮类衍生物光引发剂及制备方法,其特征在于:所述步骤4)中加热条件为40-50℃。
7.如权利要求1所述的二苯甲酮类衍生物光引发剂及制备方法,其特征在于:所述溶剂为二氯甲烷、乙腈和四氢呋喃中的一种或几种。
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WO2021064530A1 (en) * | 2019-09-30 | 2021-04-08 | 3M Innovative Properties Company | Dicarboxylic acid compounds. inorganic particles treated with the dicarboxylic acid compounds, and compositions thereof |
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WO2021064530A1 (en) * | 2019-09-30 | 2021-04-08 | 3M Innovative Properties Company | Dicarboxylic acid compounds. inorganic particles treated with the dicarboxylic acid compounds, and compositions thereof |
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