CN109400529B - 适用于uv-led光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂及制备方法与应用 - Google Patents
适用于uv-led光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂及制备方法与应用 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及感光高分子领域,具体涉及一种适用于UV-LED光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂及制备方法与应用。
背景技术
UV光固化技术是20世纪中期问世的新型技术,它是利用紫外光(波长在200-400nm)为能源,引发具有化学反应活性液态物质快速转变为固体的过程。与传统的热固化技术相比,它具有速度快、高效率、污染小、性能优异和费用低的优点,是一种快速发展的“绿色”新技术。UV光固化产品由三部分材料组成,即光固化树脂,稀释剂和光引发剂。
紫外发光二极管(UV-LED)是一种半导体的电子器件,UV-LED设备能将电能转化为化学光学辐射,UV-LED作为辐射设备已在辐射固化和光聚合反应等领域得到广泛应用。与传统的UV光源相比,UV-LED光源具有以下几个特点:(1)几乎可以发出单色光,其光谱线宽度非常窄(5-20nm);(2)发光输出量几乎为100%;(3)低能耗;(4)不产生臭氧;(5)无紫外辐射;(6)产生的热量低;(7)运营成本低;(8)使用寿命长;(9)操作安全简单;(10)设计紧凑,方便携带。在工业中使用能耗低且安全性能高的UV-LED光源既能保证人员安全又能削减开支。鉴于其先进性、经济性及环境友好等特点,UV-LED有很好的发展前景,它可作为紫外线固化的一种互补,应用于一些潜在的新领域。
UV-LED光源的波长种类很多,最常用的是385nm-405nm。然而大多数已报道或商业化的光引发剂的吸收波长在365nm以上吸收光能较差,在UV-LED光源的照射下,这些光引发剂的引发性能较差,严重限制了UV-LED光固化技术的发展和推广。
发明内容
本发明所要解决的问题在于现有的光引发剂在UV-LED光源的照射下引发性能较差。
本发明是采用以下技术方案解决上述技术问题的:
本发明提供一种适用于UV-LED光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂,所述光引发剂的化学结构通式如下所示:
其中,R1选自C1-C16脂肪烃基、芳烷基或苯基,R2分别独自选自氢、烷基、烷氧基、酰基、卤原子、硝基。
优选的,所述R1选自2,6-二异丙基苯基。
本发明还提供上述光引发剂的制备方法,其通用的合成工艺如下所示:
优选的,所述光引发剂的制备方法包括以下步骤:
(1)所述步骤a中,伯胺与4-溴-1,8-萘二甲酸酐反应得到的粗产物用乙酸重结晶,得到中间产物A;
(2)所述步骤b中,将取代苄硫醇、乙酸酐(Ac2O)、无水氯化镍(NiCl2)加入到反应器中并搅拌,得到中间产物B;
(3)所述步骤c中,将步骤a中所制备的产物A和步骤b中所制备的产物B、双(二亚苄基丙酮)钯(Pd(dba)2)、1,1’-双(二苯基膦)二茂铁(dppf)、无水磷酸三钾(K3PO4)混合,并加入体积比为2:1的甲苯与丙酮混合液作溶剂。
优选的,所述伯胺选自C1-C16脂肪伯胺、芳烷基伯胺、芳香伯胺。
优选的,所述伯胺选自2,6-二异丙基苯胺。
优选的,所述步骤a中,将4-溴-1,8-萘二甲酸酐和伯胺,按1:10的摩尔比加入到反应容器中,并加入乙酸做溶剂,在氮气保护下回流搅拌;反应结束后,待反应液冷却至室温,将反应液倒入冰水中,过滤,用去离子水洗涤滤饼,真空干燥后得到粗产物后,用乙酸重结晶,得到中间产物A。
优选的,所述步骤b中取代苄硫醇为如下化合物:
优选的,所述步骤b中,将取代苄硫醇、乙酸酐(Ac2O)、无水氯化镍(NiCl2)按1:2:0.1的摩尔比加入到反应容器中,室温搅拌;反应结束后,在反应器中加入适量去离子水,用二氯甲烷萃取后,合并有机层,有机层分别用10%的碳酸氢钠水溶液和去离子水洗涤,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后,用柱色谱提纯粗产物,得到中间产物B。
优选的,所述步骤c中,将产物A、产物B、双(二亚苄基丙酮)钯(Pd(dba)2)、1,1’-双(二苯基膦)二茂铁(dppf)、无水磷酸三钾(K3PO4),按1:1:0.1:0.14:2.4的摩尔比加入到反应容器中,并加入适量体积比为2:1的甲苯与丙酮混合液做溶剂,在氮气保护下110℃搅拌;反应结束后,待反应液冷却至室温,将反应液倒入适量饱和氯化铵水溶液中,用二氯甲烷萃取后,合并有机层,有机层用饱和食盐水洗涤,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后,用柱色谱提纯粗产物,得到最终产物。
本发明还提供上述光引发剂在光固化体系中的应用。
本发明的有益效果在于:与传统光引发剂相比,本发明的制备的光引发剂其紫外吸收波长明显延长,在UV-LED光源作用下,具有较高的光固化效率,有助于UV-LED光固化工业的发展。
附图说明
图1为本发明实施例1-3中制备的萘二甲酰亚胺芳基苄基硫醚型光引发剂紫外吸收谱图;
图2为本发明实施例1-3中制备的萘二甲酰亚胺芳基苄基硫醚型光引发剂与光引发剂1173、184、2959引发单体聚合的实时红外谱图;
图3和图4分别为本发明实施例1中制备的光引发剂的核磁氢谱和碳谱图;
图5和图6分别为本发明实施例2中制备的光引发剂的核磁氢谱和碳谱图。
具体实施方式
以下将结合说明书附图和实施例对本发明做进一步详细说明。
下述实施例中所用的试验材料和试剂等,如无特殊说明,均可从商业途径获得。
实施例1
光引发剂NABS1具有以下结构式:
其制备方法包括以下步骤:
(a)将4-溴-1,8-萘二甲酸酐(7.20g,0.026mol)、2,6-二异丙基苯胺(46.10g,0.26mol)以及100mL乙酸加入到的250mL单口烧瓶中,在氮气保护下,升温至120℃,恒温搅拌24h;反应结束后,待反应液冷却至室温,将反应液倒入1000mL冰水中,过滤,用去离子水洗涤滤饼3次,真空干燥后得到粗产物;粗产物用乙酸重结晶,得到中间产物,命名为DPPNB;
(b)将苄硫醇(2.49g,0.02mol)、乙酸酐(4.08g,0.04mol)以及无水氯化镍(259mg,2mmol)加入到50mL单口烧瓶中,室温搅拌4h。反应结束后,在反应器中加入30mL去离子水,用二氯甲烷萃取3次,合并有机层,有机层分别用10%的碳酸氢钠水溶液和去离子水洗涤3次,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后,用柱色谱提纯粗产物,得到中间产物,命名为BET;其中减压蒸馏和柱色谱提纯步骤只要能实现对产物进行提纯即可;
(c)将DPPNB(873mg,2mmol)、BET(332mg,2mmol)、双(二亚苄基丙酮)钯(115mg,0.2mmol)、1,1’-双(二苯基膦)二茂铁(155mg,0.28mmol)、无水磷酸三钾(1.02g,4.8mmol)、4mL甲苯以及2mL丙酮加入到25mL三口烧瓶中,在氮气保护下110℃搅拌12h,反应结束后,待反应液冷却至室温,将反应液倒入10mL饱和氯化铵水溶液中,用二氯甲烷萃取3次,合并有机层,有机层用饱和食盐水洗涤3次,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后用柱色谱提纯粗产物,得到最终产物NABS1,并通过核磁共振波谱进行结构鉴定,如图3和图4所示。
光引发剂NABS1的氢谱数据为:1H NMR(400MHz,Chloroform-d)δ8.70(ddd,J=10.7,7.9,1.1Hz,2H),8.53(d,J=7.8Hz,1H),7.82(dd,J=8.5,7.3Hz,1H),7.66(d,J=7.8Hz,1H),7.52–7.46(m,2H),7.42–7.31(m,5H),4.44(s,2H),2.75(hept,J=6.9Hz,2H),1.17(d,J=6.8Hz,12H)。
光引发剂NABS1的碳谱数据为:13C NMR(100MHz,Chloroform-d)δ164.04,163.99,145.66,144.94,135.33,132.04,131.25,130.85,130.42,129.84,129.47,128.98,128.90,128.41,127.92,126.79,123.99,123.84,123.23,119.61,37.37,29.12,23.97。
实施例2
光引发剂NABS2具有以下结构式:
其制备方法包括以下步骤:
(a)将对甲基苄硫醇(2.76g,0.02mol)、乙酸酐(4.08g,0.04mol)以及无水氯化镍(259mg,2mmol)加入到50mL单口烧瓶中,室温搅拌4h。反应结束后,在反应器中加入30mL去离子水,用二氯甲烷萃取3次,合并有机层,有机层分别用10%的碳酸氢钠水溶液和去离子水洗涤3次,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后,用柱色谱提纯粗产物,得到中间产物,命名为MBET;其中减压蒸馏和柱色谱提纯步骤只要能实现对产物进行提纯即可;
(b)将实施例1中合成的DPPNB(873mg,2mmol)、MBET(361mg,2mmol)、双(二亚苄基丙酮)钯(115mg,0.2mmol)、1,1’-双(二苯基膦)二茂铁(155mg,0.28mmol)、无水磷酸三钾(1.02g,4.8mmol)、4mL甲苯以及2mL丙酮加入到25mL三口烧瓶中,在氮气保护下110℃搅拌12h;反应结束后,待反应液冷却至室温,将反应液倒入10mL饱和氯化铵水溶液中,用二氯甲烷萃取3次,合并有机层,有机层用饱和食盐水洗涤3次,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后用柱色谱提纯粗产物,得到最终产物,命名为NABS2,并通过核磁共振波谱进行结构鉴定,如图5和图6所示。
光引发剂NABS2的氢谱数据为:1H NMR(400MHz,Chloroform-d)δ8.69(dd,J=11.6,7.9Hz,2H),8.53(d,J=7.8Hz,1H),7.82(t,J=7.9Hz,1H),7.66(d,J=7.8Hz,1H),7.49(t,J=7.7Hz,1H),7.36(dd,J=12.2,7.8Hz,4H),7.20(d,J=7.7Hz,2H),4.41(s,2H),2.75(hept,J=6.9Hz,2H),2.38(s,3H),1.17(d,J=6.8Hz,13H)。
光引发剂NABS2的碳谱数据为:13C NMR(100MHz,Chloroform-d)δ164.06,164.02,145.67,145.23,137.76,132.15,132.02,131.27,130.42,129.78,129.58,129.47,128.98,128.81,126.74,123.99,123.64,123.21,123.19,119.48,37.07,29.12,23.97,21.15。
实施例3
光引发剂NABS3具有以下结构式:
其制备方法包括以下步骤:
(a)将对甲氧基苄硫醇(3.09g,0.02mol)、乙酸酐(4.08g,0.04mol)以及无水氯化镍(259mg,2mmol)加入到50mL单口烧瓶中,室温搅拌4h。反应结束后,在反应器中加入30mL去离子水,用二氯甲烷萃取3次,合并有机层,有机层分别用10%的碳酸氢钠水溶液和去离子水洗涤3次,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后,用柱色谱提纯粗产物,得到中间产物,命名为MOBET;其中减压蒸馏和柱色谱提纯步骤只要能实现对产物进行提纯即可;
(b)将实施例1中合成的DPPNB(873mg,2mmol)、MOBET(393mg,2mmol)、双(二亚苄基丙酮)钯(115mg,0.2mmol)、1,1’-双(二苯基膦)二茂铁(155mg,0.28mmol)、无水磷酸三钾(1.02g,4.8mmol)、4mL甲苯以及2mL丙酮加入到25mL三口烧瓶中,在氮气保护下110℃搅拌12h,反应结束后,待反应液冷却至室温,将反应液倒入10mL饱和氯化铵水溶液中,用二氯甲烷萃取3次,合并有机层,有机层用饱和食盐水洗涤3次,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后用柱色谱提纯粗产物,得到最终产物NABS3,并通过核磁共振波谱进行结构鉴定。
光引发剂NABS3的氢谱数据为:1H NMR(400MHz,Chloroform-d)δ8.69(dd,J=12.5,7.9Hz,2H),8.53(d,J=7.8Hz,1H),7.85–7.77(m,1H),7.66(d,J=7.9Hz,1H),7.48(m,1H),7.40(d,J=8.3Hz,2H),7.34(d,J=7.8Hz,2H),6.95–6.88(m,2H),4.40(s,2H),3.84(s,3H),2.75(hept,J=6.9Hz,2H),1.17(d,J=6.9Hz,12H)。
光引发剂NABS3的碳谱数据为:13C NMR(100MHz,Chloroform-d)δ164.06,164.03,159.32,145.67,145.23,132.02,131.26,130.86,130.44,129.82,129.47,128.98,128.41,127.07,126.75,125.45,123.99,123.75,123.21,114.30,55.34,36.89,29.12,23.97。
实施例4-9
测定现有光引发剂与实施例1-3中制备的萘二甲酰亚胺芳基苄基硫醚型光引发剂在UV-LED光源照射下引发单体聚合效果:
(1)配制感光性树脂组合物:其配比为:
A:1,6-己二醇二丙烯酸酯(100质量份);
B:光引发剂(0.5质量份)。
表1为各实施例中组合物配比:
实施例4 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 | |
A | 100 | 100 | 100 | 100 | 100 | 100 |
B1(NABS1) | 0.5 | |||||
B2(NABS2) | 0.5 | |||||
B3(NABS3) | 0.5 | |||||
B4(光引发剂1173) | 0.5 | |||||
B5(光引发剂184) | 0.5 | |||||
B6(光引发剂2959) | 0.5 |
(2)聚合性能测试
测试方法:将上述组合物避光搅拌均匀后,用毛细管均匀涂抹到溴化钾盐片上,形成约30μm的涂膜,然后盖上另一片溴化钾盐片,放置于实时红外仪器中(美国赛默飞世尔科技公司,型号Nicolet 5700),然后用UV-LED光源(深圳市兰谱里克科技有限公司,型号UVEC-4II,光强100mW/cm2)在405nm波长下,对涂膜进行曝光,曝光时间200s。
测试结果:如图2所示,含有三种常用商业化光引发剂的感光树脂组合物在405nm的UV-LED光源照射下,不能引发聚合(实施例7-9),而含有本发明所制备的光引发剂的感光树脂组合物在405nm的UV-LED光源照射下,可以顺利引发光聚合(实施例4-6),表明本发明制备的光引发剂在UV-LED光固化体系下具有较好的适用性。
以上仅是本发明的优选实施方式,本发明的保护范围并不仅局限于上述实施例,与本发明构思无实质性差异的各种工艺方案均在本发明的保护范围内。
Claims (8)
3.根据权利要求2所述的适用于UV-LED光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂的制备方法,其特征在于:所述光引发剂的制备方法包括以下步骤:
(1)所述步骤(a)中,伯胺与4-溴-1,8-萘二甲酸酐反应得到的粗产物用乙酸重结晶,得到中间产物(A);
(2)所述步骤(b)中,将取代苄硫醇、乙酸酐、无水氯化镍加入到反应器中并搅拌,得到中间产物( B) ;
(3)所述步骤(c)中,将步骤(a)中所制备的产物(A)和步骤(b)中所制备的产物(B)、双(二亚苄基丙酮)钯、1,1’-双(二苯基膦)二茂铁、无水磷酸三钾混合,并加入体积比为2:1的甲苯与丙酮混合液作溶剂。
4.根据权利要求3所述的适用于UV-LED光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂的制备方法,其特征在于:所述步骤(a)中,将4-溴-1,8-萘二甲酸酐和伯胺,按1:10的摩尔比加入到反应容器中,并加入乙酸做溶剂,在氮气保护下回流搅拌;反应结束后,待反应液冷却至室温,将反应液倒入冰水中,过滤,用去离子水洗涤滤饼,真空干燥后得到粗产物后,用乙酸重结晶,得到中间产物(A)。
6.根据权利要求3所述的适用于UV-LED光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂的制备方法,其特征在于:所述步骤(b)中,将取代苄硫醇、乙酸酐、无水氯化镍按1:2:0.1的摩尔比加入到反应容器中,室温搅拌;反应结束后,在反应器中加入适量去离子水,用二氯甲烷萃取后,合并有机层,有机层分别用10%的碳酸氢钠水溶液和去离子水洗涤,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后,用柱色谱提纯粗产物,得到中间产物(B)。
7.根据权利要求3所述的适用于UV-LED光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂的制备方法,其特征在于:所述步骤(c)中,将产物(A)、产物(B)、双(二亚苄基丙酮)钯、1,1’-双(二苯基膦)二茂铁、无水磷酸三钾,按1:1:0.1:0.14:2.4的摩尔比加入到反应容器中,并加入适量体积比为2:1的甲苯与丙酮混合液做溶剂,在氮气保护下110℃搅拌;反应结束后,待反应液冷却至室温,将反应液倒入适量饱和氯化铵水溶液中,用二氯甲烷萃取后,合并有机层,有机层用饱和食盐水洗涤,有机层经无水Na2SO4干燥后,过滤,减压蒸馏除去溶剂得到粗产物,然后,用柱色谱提纯粗产物,得到最终产物。
8.权利要求1所述的适用于UV-LED光固化的萘二甲酰亚胺芳基苄基硫醚型光引发剂在光固化体系中的应用。
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