CN115215899A - 一种蓖麻油基可聚合光引发剂、其制备方法及应用 - Google Patents
一种蓖麻油基可聚合光引发剂、其制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种基于蓖麻油基可聚合光引发剂、其制备方法及应用。通过酯化反应在蓖麻油支链引入酰基膦氧化物或苯甲酰甲酸酯活性结构，制备出一种新型的光引发剂，制备方法简单，原料易得，而且蓖麻油是可再生资源。蓖麻油基光引发剂的长链结构使得其与活性单体和稀释剂具有很好的相容性，分子结构中的双键可以直接参与聚合形成大分子结构，迁移性低、毒性小、环境兼容性好；分子中多个活性官能团也有效的保障了其引发活性不低于对应的小分子引发剂，在烟包印刷、油墨、涂料、齿科材料等方面都有广阔的应用前景。
Description
技术领域
本发明涉及一种蓖麻油基可聚合光引发剂及其制备方法。
技术背景
紫外光固化技术由于具有固化速度快、节能环保等优点，因而在光固化涂料、光固化油墨、光刻胶、电子封装材料、粘合剂、纸张上光、光盘复制等工业领域有广泛的应用和良好的发展前景。在紫外光固化体系中，光引发剂至关重要，其中，酰基膦氧化物和苯甲酰甲酸酯是两类高效的裂解性光引发剂，但近几年随着科学技术的发展，不仅要求光引发剂有良好的光引发性能，而且要求与光固化体系相容性好，迁移率低、毒性小，环境兼容性好，存储稳定性高。传统的小分子由于与固化体系的相容性差，固化后容易挥发和迁移，一方面导致引发效率减低，另一方面会产生气味和毒性。因此，开发稳定、低毒、高效环保且与固化体系具有良好相容性的光引发体系受到越来越多的关注。
基于此，本发明提供了一种蓖麻油基可聚合光引发剂，其生态兼容性好，能参与活性单体交联聚合，迁移率低，毒性小，能有效的解决传统小分子光引发剂的弊端。
发明内容
本发明的目的在于针对传统小分子光引发剂的不足，提供一种蓖麻油基光引发剂，其制备方法及应用，所得光引发剂具有较高的引发效率，与很多溶剂和单体有良好的相容性，毒性低，应用范围广泛，同时制备方法简单，引发效果好。
为实现这一目的，本发明通过酯化的方法把小分子光引发剂接枝到含有不饱和双键的天然产物蓖麻油上，制备出一种新型的光引发剂并实施其应用。
一种蓖麻油基可聚合光引发剂，其特征在于，结构式如下式所示：
其中：R为
中的一种或两种，
R1、R2、R3、R4独立选自氢、卤素或者C1-C12的烷基或烷氧基。
上述的一种蓖麻油基光引发剂的制备方法，其特征在于,包括如下步骤：
(Ⅰ)氮气保护下，有机酸与卤化试剂在有机溶剂中一定温度下反应得到相应酰卤化合物；
其中X为Cl或Br
(Ⅱ)常温条件下，把一定量的蓖麻油和催化剂溶解于有机溶剂中，逐渐滴加与蓖麻油中羟基等摩尔量的酰卤化合物(预先测定蓖麻油中的羟基值)，反应完全后分离得到蓖麻油基可聚合光引发剂。
所述制备方法中有机溶剂包括：苯、甲苯、二甲苯、酮类、二氯甲烷、二氯乙烷、氯仿、四氯化碳、四氢呋喃。
所述制备方法中卤化试剂包括：三氯(溴)化磷、五氯(溴)化磷、二氯亚砜、三氯氧磷、草酰氯、光气。
所述制备方法催化剂包括：三乙胺、吡啶、碳酸钠、碳酸氢钠，氢氧化钠。
所述光引发剂用于UV固化配方时，配方包含：
(A)至少一种可以进行光聚合的烯属不饱和化合物和
(B)至少一种权利要求1所述光引发剂。
所述光引发剂UV固化配方，其除组分(A)(B)外，还可以包含其他紫外引发剂、胺促进剂、增敏剂和/或其他添加剂。
所述应用配方适用于光固化体系，主要适用于紫外光固化体系，尤其适用于紫外光固化油墨及涂料体系。
所述应用配方在物体表面涂膜后经紫外光源辐射固化成型，其中所述紫外光源可以是高压汞灯光源，也可以是UV-LED光源；所述紫外光源波长范围可以是200nm-500nm。
本发明具有的积极效果在于：
(1)蓖麻油为天然可再生资源，环境相容性好，其长链的酯化结构也提供了与商业化的单体的良好的相容性；
(2)蓖麻油基光引发剂分子结构中含有不饱和双键能直接参与单体聚合，迁移性低，低VOC排放，降低了光引发剂的毒性，属环境友好型光引发剂。
附图说明
无
具体实施方式
下列实施例详细说明本发明，但以下例子又不仅限于本发明。
一、蓖麻油基光引发剂的制备
(1)蓖麻油基酰基膦氧化物P6601的制备
a、2,4,6-三甲基苯甲酰基苯基膦酰氯的制备
25g 2,4,6-三甲基苯甲酰基苯基膦酸，70ml甲苯和10.28g吡啶加入500ml三口烧瓶中，搅拌，加热至60℃，缓慢滴加约90ml二氯亚砜，控制滴加速度使反应温度不超过70℃，滴加完毕后60℃保温3h，除去溶剂甲苯及多余的二氯亚砜，得到产物用四氢呋喃溶解待用。
b、蓖麻油基光引发剂P6601合成
将20g蓖麻油溶解于50ml四氢呋喃中，常温下滴加含2,4,6-三甲基苯甲酰基苯基膦酰氯20g的四氢呋喃溶液，滴完后保温反应3h；TLC跟踪反应进程，反应完全后升温蒸除溶剂，得到31.8g浅棕色油状液体，收率84.1％。
(2)蓖麻油基苯甲酰甲酸酯P6602的制备
a、苯甲酰甲酰氯的制备
30g苯甲酰甲酸，75ml甲苯加入250ml三口烧瓶中，搅拌，加热至60℃，缓慢滴加约43.5ml二氯亚砜，控制滴加速度使反应温度不超过70℃，滴加完毕后60℃保温3h，除去溶剂甲苯及多余的二氯亚砜，得到苯甲酰甲酰氯产物用四氢呋喃溶解待用。
b、蓖麻油基光引发剂P6602合成
将20g蓖麻油溶解于60ml四氢呋喃中，常温下滴加含苯甲酰甲酰氯10.8g的四氢呋喃溶液，滴完后保温反应3h；TLC跟踪反应进程，反应完全后升温蒸除溶剂，得到24.4g浅棕色油状液体，收率86.0％。
二：光引发剂的应用
a、.将水性聚氨酯丙烯酸乳液，30～60份；蓖麻油基光引发剂，0.5～5份；颜料，8～15份；助剂，5～10份；去离子水，8～20份混合配成水溶性油墨；其中，水性聚氨酯丙烯酸乳液是由以重量份计的以下组分组成：二异氰酸酯10～20份；聚酯二元醇5～10份；二月桂酸二丁基锡0.05～0.2份；甲基丙烯酸羟丙酯10～20份；丙烯酸羟丙硅酯5～10份；阻聚剂0.05～1份；乳化剂5～10份。
b、上述油墨涂布于玻璃片上，在汞灯辐射下固化，用指压法判断固化膜的表干以表征固化速度。
c、附着力测定：利用画格法测定固化膜附着力。
d、硬度测定：利用铅笔硬度法测试固化膜硬度。
e、气味测定：将样品用线棒涂布器分别涂在PT纸上，涂布面积为1dm2 ，经紫外线固化机固化后，60℃恒温30min，评价其气味大小。数值越小表示气味越低。
f、黄变测试：按照GB/T1865-2009标准判定。
光引发剂的测试结果如下(选取光引发剂TPO-L、MBF做对比项)：
| 光引发剂 | 固化速度 | 附着力 | 硬度 | 气味 | 黄变(△E) |
| P6601 | 18s | 4 | HB | 1 | 0.22 |
| TPO-L | 15s | 3 | 2B | 3 | 0.24 |
| P6602 | 21s | 3 | HB | 1 | 0.24 |
| MBF | 18s | 3 | 2B | 4 | 0.24 |
从表中数据可知，本发明蓖麻油基光引发剂相比较光引发剂TPO-L，MBF在固化速度、附着力、黄变方面性能相当，但在成膜硬度和气味上有明显优势，这应该得益于蓖麻油基光引发剂的不饱和结构在固化结构中参与聚合所致，光引发剂本身大分子的结构也使得固化后气味更小。
Claims (9)
1.一种蓖麻油基可聚合光引发剂，其特征在于，结构式如下式所示：
其中：R为
中的一种或两种，R1、R2、R3、R4独立选自氢、卤素或者C1-C12的烷基或烷氧基。
2.权利要求1所述的一种蓖麻油基光引发剂的制备方法，其特征在于,包括如下步骤：
(Ⅰ)氮气保护下，有机酸与卤化试剂在有机溶剂中一定温度下反应得到相应酰卤化合物；
其中X为Cl或Br
(Ⅱ)常温条件下，把一定量的蓖麻油和催化剂分散于有机溶剂中，逐渐滴加与蓖麻油中羟基(测定蓖麻油中的羟基值得到)等摩尔量的酰卤化合物，反应完全后分离得到蓖麻油基可聚合光引发剂。
3.根据权利要求2所述制备方法，其特征在于所述的有机溶剂包括：苯、甲苯、二甲苯、酮类、二氯甲烷、二氯乙烷、氯仿、四氯化碳、四氢呋喃。
4.根据权利要求2所述制备方法，其特征在于步骤(Ⅰ)中所述卤化试剂包括：三氯(溴)化磷、五氯(溴)化磷、二氯亚砜、三氯氧磷、草酰氯、光气。
5.根据权利要求2所述制备方法，其特征在于步骤(Ⅱ)中催化剂包括：三乙胺、吡啶、碳酸钠、碳酸氢钠，氢氧化钠。
6.关于权利要求1所述光引发剂的应用，其特征在于所述光引发剂用于UV固化配方时，配方包含：
(A)至少一种可以进行光聚合的烯属不饱和化合物和
(B)至少一种权利要求1所述光引发剂。
7.关于权利要求6所述光引发剂UV固化配方，其除组分(A)(B)外，还可以包含其他紫外引发剂、胺促进剂、增敏剂和/或其他添加剂。
8.根据权利要求6所述光引发剂UV固化配方，其特征在于，所述应用配方适用于光固化体系，主要适用于紫外光固化体系，尤其适用于紫外光固化油墨及涂料体系。
9.根据权利要求6所述光引发剂UV固化配方，其特征在于，该应用配方在物体表面涂膜后经紫外光源辐射固化成型，其中所述紫外光源可以是高压汞灯光源，也可以是UV-LED光源；所述紫外光源波长范围可以是200nm-500nm。
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| CN101811968A (zh) * | 2010-02-09 | 2010-08-25 | 深圳市有为化学技术有限公司 | 多官能团化苯甲酰甲酸羟基酮酯类化合物及含有该类化合物的光引发剂 |
| CN102432699A (zh) * | 2011-08-31 | 2012-05-02 | 上海交通大学 | 基于植物油的光引发剂及其制备方法 |
| WO2016058958A1 (en) * | 2014-10-13 | 2016-04-21 | L'oreal | Latex nail compositions having low amounts of photo-initiator |
| CN110144020A (zh) * | 2019-06-11 | 2019-08-20 | 长沙新宇高分子科技有限公司 | 一种环糊精基光引发剂、其制备方法及应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101811968A (zh) * | 2010-02-09 | 2010-08-25 | 深圳市有为化学技术有限公司 | 多官能团化苯甲酰甲酸羟基酮酯类化合物及含有该类化合物的光引发剂 |
| CN102432699A (zh) * | 2011-08-31 | 2012-05-02 | 上海交通大学 | 基于植物油的光引发剂及其制备方法 |
| WO2016058958A1 (en) * | 2014-10-13 | 2016-04-21 | L'oreal | Latex nail compositions having low amounts of photo-initiator |
| CN110144020A (zh) * | 2019-06-11 | 2019-08-20 | 长沙新宇高分子科技有限公司 | 一种环糊精基光引发剂、其制备方法及应用 |
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