CN104991418B - 一种用于uv-led光固化的增感剂及其制备方法和应用 - Google Patents
一种用于uv-led光固化的增感剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开一种用于UV‑LED光固化的增感剂,具有如式(I)所示的化学结构。该增感剂与现有光引发剂有很好的适配性,应用于光固化组合物时能够显著提升UV‑LED光源照射下的固化效率,具有优异的应用性能。
Description
技术领域
本发明属于有机化学领域,具体涉及一种适用于紫外发光二极管(UV-LED)光固化体系的增感剂及其制备方法,以及它在光固化领域中的应用。
背景技术
紫外光固化技术应用非常广泛,其所用光源主要是长波段的紫外光源(如汞灯),但这类光源在光固化技术发展进程中存在诸多不足,如易产生紫外光损害、电力消耗较高、生产效率不高等。有鉴于此,UV-LED被认为是一种前景良好的替代光源,其具有单峰波长分布的特点,可减少短波长紫外光引起的损害,节省电力消耗,同时也有助于提高生产效率。然而应用中发现,传统紫外光固化体系在使用UV-LED光源后很多都无法顺利固化或固化效果不佳,造成该现象的原因是能量无法很好地实现传递,而这也成为限制UV-LED光固化技术发展和推广的关键因素。
研究认为,在光固化体系中加入合适的增感剂是解决上述问题的有效途径。在基本不改变光固化组合物体系的前提下,通过添加少量增感剂可以达到不断吸收和传递能量的目的。这对于光固化技术来说是成本很低的改进方式,且能够确保上述UV-LED光固化技术的优点。因此,开发能够与现有光引发剂相匹配且适用于UV-LED光源的增感剂也就成为了当前光固化领域的一个研究热点。
发明内容
本发明首先提供一种用于UV-LED光固化的增感剂。该增感剂与现有光引发剂(如1173、184、BDK、907等)有很好的适配性,应用于光固化组合物时能够显著提升UV-LED光源照射下的固化效率,从而有助于UV-LED光固化技术的推广和发展。
本发明用于UV-LED光固化的增感剂,其具有如式(I)所示的结构:
其中,
R1代表C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基;
R2代表C1-C40的n价烃基,其中的-CH2-可任选地被-O-或1,4-亚苯基取代,前提是两个-O-不直接彼此相连;
n代表大于0的整数。
优选地,上述式(I)所示增感剂中,R1代表C1-C4的直链或支链烷基、C3-C8的环烷基、C4-C8的烷基环烷基或环烷基烷基。特别优选地,R1选自甲基、乙基、丙基、异丙基、丁基、环戊基、环己基、环戊基甲基、环戊基乙基。
优选地,上述式(I)所示增感剂中,R2代表C1-C10的直链或支链的n价烷基,其中的-CH2-可任选地被-O-或1,4-亚苯基取代,前提是两个-O-不直接彼此相连。特别优选地,R2选自CH3-、CH3CH2-、CH3CH2CH2-、CH3CH2CH2CH2-、CH3-(CH2)4-、CH3-(CH2)5-、CH3-(CH2)6-、CH3-(CH2)7-、C(CH2-)4、CH(CH2CH2-)3、CH(CH2CH2CH2-)3、CH(CH2-O-CH2-)3、-(CH2)9-、-(CH2)2-O-(CH2)3-O-(CH2)2-、-C6H4-C(CH3)2-C6H4-。
优选地,式(I)中n为1、2、3或4。
本发明还提供上述式(I)所示增感剂的制备方法,包括以下步骤:
(1)原料1经还原反应生成中间体a;
(2)中间体a与酰氯R1-CO-Cl在催化剂存在下发生傅克反应,得到中间体b;
(3)中间体b与醇R2-(OH)n发生酯化反应,得到目标产物;
反应过程式如下所示:
步骤(1)的还原反应优选在含有还原剂的溶剂中进行。所述溶剂优选是醋酸或盐酸,所述还原剂优选是锌粉或铁粉。反应温度通常在20-80℃之间。
步骤(2)的傅克反应在含有催化剂的溶液体系中进行。反应中使用的溶剂并没有特殊限定,只要能够溶解反应试剂且对反应无不良影响即可,例如二氯甲烷、二氯乙烷、甲苯、苯、二甲苯等烃类溶剂。所述催化剂优选是三氯化铝。反应温度根据反应试剂的种类而有所差异,通常在-10-40℃之间,这对于本领域技术人员来说是容易确定的。
步骤(3)的酯化反应是在催化剂存在条件下进行。所述催化剂优选是浓硫酸。根据反应体系的实际情况(如反应试剂种类),体系中可选择性地添加或不添加溶剂和/或阻聚剂。其中,对溶剂种类没有特别限定,只要其能够溶解反应试剂且对反应无不良影响即可,例如可以是甲苯、苯、二甲苯等常规烃类溶剂。阻聚剂优选是对羟基苯甲醚。酯化反应温度根据反应试剂的种类而有所差异,通常在50-180℃之间,这对于本领域技术人员来说是容易确定的。
在制备上述式(I)所示增感剂的过程中,使用的反应试剂都是现有技术中的已知化合物,可通过商购获得或由现有的合成方法方便地制得。
本发明的式(I)所示增感剂可用于UV-LED光固化体系。在UV-LED光源作用下,该增感剂与现有光引发剂特别是1173、184、BDK、907等有极佳的协同功效,能够显著提升UV-LED光源照射下的固化效率,具有优异的应用性能。
附图说明
图1是不同情况下甲基丙烯酸羟乙酯双键转化率图。
具体实施方式
以下将结合具体实施例对本发明作进一步详细说明,但不应将其理解为对本发明保护范围的限制。
制备实施例
实施例1
(1)中间体1a的制备
向500mL的四口烧瓶中加入原料1a 126g、锌粉50g、醋酸100mL,室温(约25℃)搅拌3h,关闭反应,将反应溶液硅藻土过滤,然后将滤液倒入500mL冰水中,搅拌,析出白色固体,水洗,烘干,得中间体1a 122g。
中间体1a的结构经1H-NMR得到确认,表征结果如下。
1H-NMR(CDCl3,500MHz):5.0481-5.3002(2H,s),7.3351-8.6179(7H,m),10.7352-11.0352(1H,s)。
(2)中间体1b的制备
向500mL的四口烧瓶中加入76g中间体1a、100mL二氯甲烷、60g三氯化铝,控温0℃搅拌,然后滴加50mL含48g乙酰氯的二氯甲烷溶液,约2h滴加完,滴加完毕后继续搅拌2h,液相跟踪反应至完全。将反应液倒入500mL降温的碳酸氢钠水溶液(5质量%)中,搅拌并分离出有机层,水洗至中性,旋蒸二氯甲烷产物溶液,得淡黄色固体93g,即中间体1b。
中间体1b的结构经1H-NMR得到确认,表征结果如下。
1H-NMR(CDCl3,500MHz):2.0012(6H,s),7.3481-8.4064(7H,m),10.8621-11.1237(1H,s)。
(3)化合物1的制备
向250mL四口烧瓶中加入中间体1b 68g、甲醇50mL、70%浓硫酸5g,并连接蒸馏装置及分水器,在分水器中加入5mL甲苯,70℃加热回流,边反应边蒸出反应中产生的水份,液相跟踪反应至不再发生变化,即得产物粗品,乙腈重结晶得白色固体,烘干得产物67g,纯度99%,即为化合物1。
产物结构经1H-NMR得到确认,表征结果如下。
1H-NMR(CDCl3,500MHz):2.0804(6H,s),3.7892(3H,s),7.3593-8.2769(7H,m)。
实施例2
(1)中间体2a的制备
向500mL的四口烧瓶中加入原料2a 126g、锌粉50g、醋酸100mL,室温搅拌3h,关闭反应。将产物溶液经硅藻土过滤,然后将滤液倒入500mL冰水中搅拌,析出白色固体,水洗,烘干,得中间体2a 122g。
中间体2a的结构经1H-NMR得到确认,表征结果如下。
1H-NMR(CDCl3,500MHz):5.0031-5.4321(2H,s),7.4453-8.6401(6H,m),10.9042-11.2042(2H,s)。
(2)中间体2b的制备
向500mL的四口烧瓶中加入76g中间体2a、100mL二氯甲烷、60g三氯化铝,控温0℃搅拌,然后滴加50mL含88g环己甲酰氯的二氯甲烷溶液,约2h滴加完,滴加完毕后继续搅拌2h,液相跟踪反应至完全。接着将反应液倒入500mL降温的碳酸氢钠水溶液(5质量%)中,搅拌并分离出有机层,水洗至中性,旋蒸二氯甲烷产物溶液,得淡黄色固体134g,即中间体2b。
中间体2b的结构经1H-NMR得到确认,表征结果如下。
1H-NMR(CDCl3,500MHz):1.4023-1.4732(12H,m),1.6521-1.7034(8H,m),2.1032-2.3023(2H,m),8.4345-8.9041(6H,m),10.9862-11.2032(2H,s)。
(3)化合物2的制备
向500mL四口烧瓶中加入中间体2b 103g、季戊四醇20g、70%浓硫酸8g、甲苯100mL,并连接蒸馏装置及分水器,在分水器中加入5mL甲苯,110℃加热回流,边反应边蒸出反应产生的水份,液相跟踪反应至不再发生变化,接着蒸馏除去多余的甲苯,水洗除去季戊四醇,石油醚重结晶得白色粘稠物103g,收率94%,纯度99%,即为化合物2。
产物结构经1H-NMR得到确认,表征结果如下。
1H-NMR(CDCl3,500MHz):1.4042-1.5149(24H,m),1.6687-1.7218(16H,m),2.2546-2.3302(4H,m),4.1982(8H,s),7.5193-8.6769(28H,m)。
实施例3-10
参照实施例1和2的方法,合成化合物3-10,其结构和相应的1H-NMR数据列于表1.
表1
性能评价
通过配制示例性光固化组合物(即感光性树脂组合物),对本发明式(I)所示增感剂的应用性能进行评价。
1、配制感光性树脂组合物
参照如下比例和表2中所示的具体配方,配制感光性树脂组合物。
表2
2、成膜性能测试
(1)高压汞灯下成膜性能测试
将上述组合物在黄光灯下搅拌,取料于PET模板上滚涂成膜,在90℃下干燥5min除去溶剂,形成膜厚约2μm的涂膜。将形成有涂膜的基板冷却至室温,用高压汞灯(曝光机型号RW-UV70201,光强50mW/cm2)照射对涂膜进行曝光,曝光时间120s,观察其是否能够固化成膜。
(2)UV-LED光源下成膜性能测试
将上述组合物避光搅拌,取料于PET模板上,利用线棒涂膜,在90℃下干燥5min除去溶剂,形成膜厚约2μm的涂膜。将形成有涂膜的基板冷却至室温,用UV-LED光源照射(深圳市蓝谱里克科技有限公司,型号UVEL-ET,光强500mW/cm2)在395nm波长下对涂膜进行曝光,曝光时间120s,观察其是否能够固化成膜。
测试结果如表3中所示。
表3
从表3可以看出,含光引发剂的感光性树脂组合物在汞灯照射下能够顺利固化(比较例4和5),而在UV-LED光源照射下均不能固化(比较例1-3)。在添加了少量本发明的增感剂后,UV-LED光源照射下的光固化体系均能够顺利固化(实施例1-4),这表明本发明的增感剂在UV-LED光固化体系下具有很好的适用性。
3、增感性能评价
利用实时红外检测,在紫外全波段点光源和UV-LED点光源下对增感剂的增感性能进行评价,以比较在不同光源照射、有无添加增感剂情况下的双键转化率。
双键转化率越高、双键转化率越快,说明固化效果越好。测试组合物的配方情况及光源情况如表4所示。
表4
将上述配方组合物分别混匀并涂于KBr盐片上,然后放入Nicolet5700中用不同的点光源照射,调节样品表面的紫外光强为35mW/cm2,单体的双键转化率用近红外实时采集,设定采集时间为300s,利用甲基丙烯酸羟乙酯碳碳双键的特征吸收峰的变化来观察聚合反应的变化程度。双键转化率(DC)由OMNIC7.1红外软件和Origin7.5数据处理软件结合下式计算得到:
DC(%)=[1-(At/Ao)]*100%
式中Ao和At分别为样品在固化前和光照后t时刻在1630cm-1处甲基丙烯酸羟乙酯双键特征吸收峰的面积。
测试结果如图1所示。
从图1中可以看到,在紫外全波段点光源照射下,即使不添加增感剂(比较例8),树脂组合物也能够顺利固化,但在开始阶段固化速度较慢,100s时双键转化率仅不足5%。而在添加了少量本发明的增感剂后(比较例7),固化速度明显加快,100s时双键转化率达到85%左右。
在UV-LED点光源照射下,不添加本发明增感剂(比较例6)时固化速度及双键转化率非常低,即使到了300s,双键转化率也仅为15%左右。而在添加了少量本发明的增感剂后(实施例5),无论是固化速度还是双键转化率都有显著的提高,在75s时双键转化率即可达到约95%。
另外值得一提的是,由实施例5和比较例7可以看出,对于相同组成的含增感剂组合物来说,两种光源照射条件下最终的双键转化率相当,但UV-LED点光源照射下的固化速度明显高于紫外全波段点光源下的固化速度。
综上可知,本发明公开的式(I)所示增感剂在应用于常规的紫外光固化体系后,可以很好地与UV-LED光源匹配使用,从而能够解决传统光固化体系在LED光源照射下固化效率低的缺陷。
Claims (6)
1.具有如式(I)所示结构的化合物作为增感剂在UV-LED光固化体系中的应用,
其中,
R1代表C1-C4的直链或支链烷基、C3-C8的环烷基、C4-C8的烷基环烷基或环烷基烷基;
R2代表C1-C10的直链或支链的n价烷基,其中的-CH2-可任选地被-O-或1,4-亚苯基取代,前提是两个-O-不直接彼此相连;
n为2、3或4;
所述UV-LED的波长为395nm。
2.根据权利要求1所述的应用,其特征在于:R1选自甲基、乙基、丙基、异丙基、丁基、环戊基、环己基、环戊基甲基、环戊基乙基。
3.根据权利要求1所述的应用,其特征在于:R2选自C(CH2-)4、CH(CH2CH2-)3、CH(CH2CH2CH2-)3、CH(CH2-O-CH2-)3、-(CH2)9-、-(CH2)2-O-(CH2)3-O-(CH2)2-、-C6H4-C(CH3)2-C6H4-。
4.根据权利要求1-3中任一项所述的应用,其特征在于,具有式(I)所示结构的化合物的制备方法包括以下步骤:
(1)原料1经还原反应生成中间体a;
(2)中间体a与酰氯R1-CO-Cl在催化剂存在下发生傅克反应,得到中间体b;
(3)中间体b与醇R2-(OH)n发生酯化反应,得到目标产物;
反应过程式如下所示:
5.根据权利要求4所述的应用,其特征在于:步骤(1)的还原反应是在含有还原剂的溶剂中进行,所述溶剂是醋酸或盐酸,所述还原剂是锌粉或铁粉。
6.根据权利要求4所述的应用,其特征在于:步骤(2)的反应中,所述催化剂是三氯化铝。
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KR20180012302A (ko) | 2018-02-05 |
KR102047043B1 (ko) | 2019-11-20 |
CN104991418A (zh) | 2015-10-21 |
EP3316036B1 (en) | 2020-06-17 |
US20180186723A1 (en) | 2018-07-05 |
EP3316036A4 (en) | 2019-02-27 |
JP2018527418A (ja) | 2018-09-20 |
US10421708B2 (en) | 2019-09-24 |
EP3316036A1 (en) | 2018-05-02 |
WO2016206602A1 (zh) | 2016-12-29 |
JP6483289B2 (ja) | 2019-03-13 |
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