CN105669591A - 一类双给电子芳胺类光敏剂及其在可见led光固化的应用 - Google Patents
一类双给电子芳胺类光敏剂及其在可见led光固化的应用 Download PDFInfo
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Abstract
本发明公开一类双给电子芳胺类光敏剂,该类光敏剂的结构特点是具有芳胺类双给电子共轭基团,结构通式如Ⅰ。该类光敏剂与一般所报道的可见光引发体系相比,该类光敏剂在可见光区具有强吸收且合成方法简单,可应用在可见LED光源的自由基和阳离子固化体系中,具有应用潜力。
Description
技术领域
本发明属于光功能有机分子技术领域,具体涉及一类双给电子芳胺类光敏剂及在可见LED光源光固化的应用。
背景技术
紫外光固化技术已经被广泛应用于许多工业领域如:印刷、油墨、涂层、粘合剂、光学器件、电子电路等。近年来,在新兴的数字存储、三维精密加工等领域也有涉及。与热聚合或热固化相比,它具有固化速率快、设备简单占地面积小、可室温操作、少污染、固化产物性能优异等特点,是一种环境友好的绿色技术。但紫外光固化存在许多弱点:①紫外辐射对人体有害、环保安全性差,设备要求高;②紫外光穿透力弱,光固化配方中一些具有共轭结构的组分或色素物质对紫外光有较强吸收,导致光强衰减严重、固化不彻底、光固化膜性能差;③易产生臭氧污染环境等。为此,发展了可见光固化技术,近些年来,摈弃了紫外光固化技术缺点的可见光固化正以其广泛的适应性越来越多地得到大家的研究和关注。
可见光固化技术的关键在于寻求能够高效引发固化的可见光引发剂或引发体系。目前获取可见光引发剂有以下几种途径:①改造现有的紫外光引发剂,增加分子的共轭结构使其光吸收红移至可见光区;②利用可见光区有吸收的光敏染料作为光敏剂,配合共引发剂和增效剂组成可见光引发体系;③开发和发现新结构的可见光光敏剂;④现有可见光光敏剂的功能化改性,以提高应用性能。国外JacquesLalev′ee课题组、Yagci课题组、Previtali课题组、Fouassier课题组和国内的聂俊课题组、肖朴课题组,分别基于这四种途径开发了许多结构新颖的可见光引发体系,许多其他的研究者们也在致力于此项工作的研究。
但是现有的光敏剂剂使用时存在着溶解性不好、感光度提升效果不佳,光固化时间较长,光固化效率较低,匹配的光源波长较短,更加偏向紫外灯光源,因此,合成出具有长波长的吸收,具有更好的光敏性能的光敏剂成为该领域的研发热点。
发明内容
本发明目的在于提供一类双给电子芳胺类光敏剂,合成的新型光敏剂能够显著提高提升可见LED(455nm-532nm)光源照射下的光固化效率,应用性能优异,从而有助于可见LED光固化技术的推广。
本发明上述的光敏剂的合成结构通式如下:
其中,R1为含氮或硫的芳香杂环,其中为三苯胺、咔唑、卟啉、噻吩、苯并噻吩、苯并咪唑、N-苯基咔唑、吩噻嗪。R2为C1到C10的直链或支链烷基;作为优选方案,在本发明结构式(Ⅰ)所示的光敏剂中:R1选自:三苯胺、咔唑、卟啉、噻吩、苯并噻吩、苯并咪唑、N-苯基咔唑、吩噻嗪;作为优选方案,在本发明结构式(Ⅰ)所示的光敏剂中:R2选自:CH3-、CH3CH2-、CH3CH2CH2-、(CH3)2CH2-、CH3(CH2)3-、CH3(CH2)4-、CH3(CH2)5-、CH3(CH2)6-、CH3(CH2)7-。
本发明结构式(Ⅰ)所示光敏剂在可见-LED光固化体系的应用,使用的光固化的激光光源波长的范围为455-532nm。其光固化体系分为阳离子光固化体系和自由基光固化体系。
阳离子光固化体系的预聚单体为E51,光引发剂为二芳基碘鎓盐、三芳基硫鎓盐,茂铁盐。该体系的按质量百分数计组成如下:
双给电子芳胺类光敏剂:0.05wt%~0.8wt%;
阳离子型光引发剂:0wt%~5wt%;
预聚单体:50wt%~95wt%;
助剂:1wt%~25wt%;
自由基光固化体系的预聚单体为TPGDA,光引发剂为二芳基碘鎓盐、三芳基硫鎓盐,助剂为N-甲基吡咯烷酮。自由基光固化体系其特征在于该体系的按质量百分数计组成如下:
双给电子芳胺类光敏剂:0.05wt%~0.8wt%;
自由基型光引发剂:0wt%~5wt%;
预聚单体:50wt%~95wt%;
助剂:1wt%~25wt%。
本发明相比具有以下优点和效果:
(1)本发明所述的光引发体系可用于引发自由基固化、阳离子固化的可见光固化。本发明的光引发体系经可见光绿色波段辐照,可有效引发自由基单体/低聚体,阳离子单体/低聚体的有效光固化。
(2)本发明的光引发体系与一般所报道的可见光引发体系相比,感光波段更长,吸光能力更强,分子结构简单,易于制备,成本低廉,能够有效引发自由基和阳离子固化体系,具有工业化应用潜力。所采用的光引发剂二芳基碘鎓盐和三芳基硫鎓盐,均是常规的光引发体系组分,因此具备工业化应用潜力。
附图说明
图1两种双给电子芳胺类光敏剂的结构图
图2为TPN的1HNMR.
图3为CPN的1HNMR.
图4自由基光固化体系中TPGDA的双键转换率图。
图5阳离子光固化体系中E51的双键转换率图。
具体实施方式
下面通过具体实施例,对本发明的技术方案作进一步的具体说明。应当理解,本发明的实施并不局限于下面的实施例,对本发明所做的任何形式上的变通或改变都将落入本发明保护范围。
在本发明中,若非特指,所有的份、百分比均为重量单位,所采用的设备和原料等均可从市场购得或是本领域常用的。
对实施例中的测试方法进行以下说明:
本发明中,所公开的光固化体系的固化转化率是通过傅立叶变换近红外光谱技术进行监测:
(1)将配制好的样品均匀涂在在两片玻璃之间的橡胶圈(直径固定)中,通过可见LED光源在室温下辐射,每个样品通过近红外扫描重复实验三次。需要说明的是,同一样品点在可见光源下每隔一段时间辐照一次立即进行一次红外扫描。此外,光源在使用前要先调节照度至适宜值。
(2)阳离子型光固化体系是通过傅立叶变换近红外光谱技术监测在6072cm-1附近处其环氧基团特征吸收峰随光照时间的变化,通过计算得到体系环氧转化率随光照时间的变化曲线。环氧转化率计算公式如下:
环氧转化率%=[1-(St/Rt)/(S0/R0)]×100%
其中,St是光照时间t时所对应的环氧基团特征峰面积;Rt是光照时间t时所对应的参比峰面积;S0是t=0时所对应的环氧基团特征峰面积;R0是t=0所对应的参比峰面积。
(3)自由基型光固化体系是通过傅立叶变换近红外光谱技术监测其在6167cm-1附近处双键基团特征吸收峰面积随着光照时间的变化,通过计算得到体系的双键转化率随光照时间的变化曲线。双键转化率计算公式如下:
双键转化率%=[1-(St/S0)]×100%
其中,St是光照时间t时所对应的环氧基团特征峰面积;S0是t=0所对应的环氧基团特征峰面积。
实施例1
增感剂TPN的合成
合成过程见下式:
在100ml单口瓶内加入N-乙基-6-溴吩噻嗪-3-醛(0.2409g,0.8mmol)、Pd(PPh3)2Cl2(8.5mg,0.012mmol)、CuI(7.6mg,0.04mmol)、三苯基膦(10.5mg,0.04mmol)、TEA10ml和DMF40ml,氮气保护下,将溶解三苯胺乙炔(0.2574g,0.96mmol)的DMF20ml滴加入体系中,85C。油浴加热至N-乙基-6-溴吩噻嗪-3-醛反应完全,反应体系待冷却后倾倒入水中,过滤,晾干。柱层析提纯(PE:DCM=4:1),得到橙黄色固体。在氮气保护,依次加入橙黄色固体(0.2611g,0.5mmol)、氰基乙酸(0.2102g,2.5mmol)、哌啶0.5ml以及三氯甲烷20ml溶液至100ml单口瓶内。回流至原料反应完全,配置浓度2M的盐酸,将母液加入搅拌,分液加入三氯甲烷萃取,加入四氢呋喃稀释,用水洗涤干燥旋转蒸发蒸除溶剂,柱色谱提纯(CH2Cl2:MeOH=10:1)得深红色固体,产率76%。增感剂TPN经1HNMR得到确认:表征结果如下:
1HNMR(400MHz,DMSO-d6)δ8.79(s,1H),8.46(s,1H),8.39(s,1H),8.34(s,1H),8.26(d,J=8.2Hz,2H),7.80(d,J=8.8Hz,1H),7.73(d,J=2.4Hz,3H),7.65(d,J=14.1Hz,3H),7.50(s,1H),7.26(d,J=7.4Hz,1H),4.48(dt,J=14.2,7.3Hz,6H),1.34(q,J=6.9Hz,6H).
实施例2
增感剂CPN的合成
合成过程见下式:
在100ml单口瓶内加入N-乙基-6-溴吩噻嗪-3-醛(0.2409g,0.8mmol)、Pd(PPh3)2Cl2(8.5mg,0.012mmol)、CuI(7.6mg,0.04mmol)、三苯基膦(10.5mg,0.04mmol)、TEA10ml和DMF40ml,氮气保护下,将溶解N-乙基咔唑炔(0.2103g,0.96mmol)的DMF20ml滴加入体系中,85C。油浴加热至N-乙基-6-溴吩噻嗪-3-醛反应完全,反应体系待冷却后倾倒入水中,过滤,晾干。柱层析提纯(PE:DCM=4:1),得到橙黄色固体。氮气保护下,依次加入橙黄色固体(0.2361g,0.5mmol)、氰基乙酸(0.2102g,2.5mmol)、哌啶0.5ml以及三氯甲烷20ml溶液至100ml单口瓶内。回流至原料反应完全,配置浓度2M的盐酸,将母液加入搅拌,分液加入三氯甲烷萃取,加入四氢呋喃稀释,用水洗涤干燥旋转蒸发蒸除溶剂,柱色谱提纯(CH2Cl2:MeOH=10:1)得深红色固体,产率75%。增感剂TPN经1HNMR得到确认:表征结果如下:
1HNMR(400MHz,DMSO-d6)δ8.39(d,J=1.5Hz,1H),8.23(d,J=7.7Hz,1H),7.94(s,1H),7.78(dd,J=8.7,2.1Hz,1H),7.69(d,J=2.1Hz,1H),7.67–7.58(m,3H),7.50(t,J=7.7Hz,1H),7.40(dd,J=8.5,2.0Hz,1H),7.32(d,J=1.9Hz,1H),7.24(t,J=7.5Hz,1H),7.13(d,J=8.7Hz,1H),7.08(d,J=8.6Hz,1H),4.47(q,J=7.1Hz,2H),3.99(q,J=6.9Hz,2H),1.34(dt,J=7.0,3.4Hz,6H).
实施例3
一种引发自由基固化的可见光引发体系的各组分比例:
光敏剂TPN:0.2wt%;
自由基光引发剂:2wt%;
助剂:0.2wt%。
按照上述的配比配制可见光引发体系,以自由基聚合单体的重量为100%计,将可见光引发体系加入自由基聚合单体:TPGDA,充分混合得到透明澄清的光固化反应液。将配好的光固化体系加入到1.8mm厚,直径为1.5mm的橡胶圈模具中,用两片洁净的玻璃片将其固定,分别用455nm和532nm的激光二极管照射,保证样品和激发光源的距离为15cm。为了保证实验结果的可信性,对每个光固化体系样品进行三次NIR测试,以平均结果作为最后的结果。
实施例4
一种引发阳离子固化的可见光引发体系的各组分比例:
光敏剂TPN:0.2wt%;
阳离子光引发剂:2wt%;
助剂:0.2wt%。
按照上述的配比配制可见光引发体系,以阳离子聚合单体的重量为100%计,将可见光引发体系加入阳离子聚合单体:E51,充分混合得到透明澄清的光固化反应液。将配好的光固化体系加入到1.8mm厚,直径为1.5mm的橡胶圈模具中,用两片洁净的玻璃片将其固定,分别用455nm和532nm的激光二极管照射,保证样品和激发光源的距离为15cm。为了保证实验结果的可信性,对每个光固化体系样品进行三次NIR测试,以平均结果作为最后的结果。
实施例5
一种引发自由基固化的可见光引发体系的各组分比例:
光敏剂CPN:0.2wt%;
阳离子光引发剂:2wt%;
助剂:0.2wt%。
按照上述的配比配制可见光引发体系,以自由基聚合单体的重量为100%计,将可见光引发体系加入自由基聚合单体:TPGDA,充分混合得到透明澄清的光固化反应液。将配好的光固化体系加入到1.8mm厚,直径为1.5mm的橡胶圈模具中,用两片洁净的玻璃片将其固定,分别用455nm和532nm的激光二极管照射,保证样品和激发光源的距离为15cm。为了保证实验结果的可信性,对每个光固化体系样品进行三次NIR测试,以平均结果作为最后的结果。
实施例6
一种引发阳离子固化的可见光引发体系的各组分比例:
光敏剂CPN:0.2wt%;
阳离子光引发剂:2wt%;
助剂:0.2wt%。
按照上述的配比配制可见光引发体系,以阳离子聚合单体的重量为100%计,将可见光引发体系加入阳离子聚合单体:E51,充分混合得到透明澄清的光固化反应液。将配好的光固化体系加入到1.8mm厚,直径为1.5mm的橡胶圈模具中,用两片洁净的玻璃片将其固定,分别用455nm和532nm的激光二极管照射,保证样品和激发光源的距离为15cm。为了保证实验结果的可信性,对每个光固化体系样品进行三次NIR测试,以平均结果作为最后的结果。
上述实施例4-6中,可见光引发体系引发自由基和阳离子体系光固化的转化率分别列于如图4、图5所示
如图4所示,通过测试发现不加光敏剂,在同样的条件下单独的二芳基碘鎓盐引发的自由基固化体系在455和532nm都不能固化。
在455nm激光光源下,分别添加光敏剂TPN和CPN,光固化速度非常快,15s后,双键转换率都达到70%。
在532nm激光光源下,分别添加光敏剂TPN和CPN,光固化速度非常快,20s后,双键转换率都达到60%。
另外在图4中可以看出来,同样的配方下,在455nm的光源下,TPN的固化速度比CPN快,且最终双键转换率更高。在532nm的光源下,TPN的固化速度比CPN快,但是最终转换率相比更低。说明不同的光敏剂在不同的光源下对光固化速度和双键转换率影响是不一样的。同样的配方下,在不同的激发光源下,光固化速度和双键转换率也是不一样的
通过测试发现不加光敏剂,在同样的条件下单独的二芳基碘鎓盐引发的阳离子光固化体系分别在455和532nm不能固化。测试结果如图5所示。
在455nm激光光源下,分别添加光敏剂TPN和CPN,光固化速度非常快,90s后,双键转换率都达到60%。
在532nm激光光源下,分别添加光敏剂TPN和CPN,光固化速度非常快,120s后,双键转换率都达到35%。
另外在图4中可以看出来,同样的配方下,在455nm的光源下,CPN的固化速度比TPN快,且最终双键转换率更高。在532nm的光源下,TPN的固化速度不仅比CPN快,而且最终转换率相比更高,说明不同的光敏剂在不同的光源下对光固化速度和双键转换率影响是不一样的。
综上所述,455nm-532nm光源下,在不添加本发明公开的式(Ⅰ)所示的光敏剂,自由基和阳离子光固化体系不能够发生固化,相比添加本发明公开的式(Ⅰ)所示的光敏剂后,不仅能够发生固化,而且对于自由基光固化体系和阳离子光固化体系均具有良好的固化性能。在455nm激光光源下,添加本发明公开的式(Ⅰ)所示的光敏剂后,自由激光固化体系在15s内,双键转换率达到70%以上;阳离子光固化体系在90s内达到60%以上;在532nm激光光源下,添加本发明公开的式(Ⅰ)所示的光敏剂后,自由激光固化体系在20s内,双键转换率达到60%以上;阳离子光固化体系在120s内达到35%以上。因此,本发明公开的式(Ⅰ)所示的光敏剂应用于常规的光固化体系,可以很好的与可见-LED光源匹配从而解决了传统光固化体系在LED光源下不能固化或则固化速率低的缺陷,扩大了光固化体系应用空间。
Claims (10)
1.一类双给电子芳胺类光敏剂,其特征在于所述的结构式为:
其中,R1为含氮或硫芳香杂环,其中为三苯胺、咔唑、卟啉、噻吩、苯并噻吩、苯并咪唑、N-苯基咔唑、吩噻嗪;
R2为C1到C10的直链或支链烷基。
2.根据权利保护书1所述,其结构特征在于:R1选自:三苯胺、咔唑、卟啉、噻吩、苯并噻吩、苯并咪唑、N-苯基咔唑、吩噻嗪。
3.根据权利保护书1~2所述,其结构特征在于:R2选自:CH3-、CH3CH2-、CH3CH2CH2-、(CH3)2CH2-、CH3(CH2)3-、CH3(CH2)4-、CH3(CH2)5-、CH3(CH2)6-、CH3(CH2)7-。
4.根据权利要求书1~3所述的具有结构式(Ⅰ)的一类双给电子芳胺类光敏剂在可见-LED光固化体系的应用。
5.根据权利要求书4所述,其应用特征在于,光固化的激光光源波长的范围为455-532nm。
6.根据权利要求书4~5所述,其应用特征在于,光固化体系分为阳离子光固化体系和自由基光固化体系。
7.根据权利要求书6所述,阳离子光固化体系,其特征在于,该体系的按质量百分数计组成如下:
双给电子芳胺类光敏剂:0.05wt%~0.8wt%;
阳离子型光引发剂:0wt%~5wt%;
预聚单体:50wt%~95wt%;
助剂:1wt%~25wt%。
8.根据权利要求书6和7所述,阳离子光固化体系,其特征在于,预聚单体为E51,光引发剂为二芳基碘鎓盐、三芳基硫鎓盐、茂铁盐。
9.根据权利要求书6所述,自由基光固化体系,其特征在于,该体系的按质量百分数计组成如下:
双给电子芳胺类光敏剂:0.05wt%~0.8wt%;
自由基型光引发剂:0wt%~5wt%;
预聚单体:50wt%~95wt%;
助剂:1wt%~25wt%。
10.根据权利要求书6和9所述,自由基光固化体系,其特征在于,预聚单体为TPGDA,光引发剂为二芳基碘鎓盐和三芳基硫鎓盐。
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