CN110357919A - 一种含硅紫外吸收剂及其聚氨酯共聚物的制备 - Google Patents

一种含硅紫外吸收剂及其聚氨酯共聚物的制备 Download PDF

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CN110357919A
CN110357919A CN201910599474.5A CN201910599474A CN110357919A CN 110357919 A CN110357919 A CN 110357919A CN 201910599474 A CN201910599474 A CN 201910599474A CN 110357919 A CN110357919 A CN 110357919A
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ultraviolet absorber
siliceous
preparation
phenyl
methyl
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刘洪珠
翁舒婷
展雪
胡俊平
王瑞东
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DALIAN ZHENBANG FLUOROCOATING Co Ltd
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Abstract

本发明公开了一种含硅紫外吸收剂制备方法及其聚氨酯共聚物的制备，含硅紫外吸收剂如图所示，其中R1为C1‑C3的烷基，R2、R3、R4为C1‑C3的烷基或芳香基团。含硅紫外吸收剂是由4‑取代苯基(2,4,6‑三羟基‑3(3‑羟基‑3‑甲基丁基)苯基)甲酮及其衍生物与三异丙基硅氧基氯甲烷及其衍生物为原料合成的。其聚氨酯共聚物是由聚多元醇、二异氰酸酯和上述合成的含硅紫外吸收剂通过内乳化法制得。本发明所制备含硅紫外吸收剂不仅具有紫外吸收功能，其含有活性基团羟基可以键接到聚氨酯分子链中，并且含有的硅元素还可以有效增加聚合物的功能性。

Description

一种含硅紫外吸收剂及其聚氨酯共聚物的制备
技术领域
本发明属于紫外吸收剂和高分子材料领域，尤其涉及一种含硅紫外吸收剂及其聚氨酯的共聚物制备。
背景技术
紫外线经云层后到达地面的波段主要为280-400nm的UVA和UVB。它们具有极高的能量，约为300-400kJ/mol，是引起高分子材料老化的最主要外因。紫外线诱发高分子材料老化降解的机理是其能量能使高分子的分子链产生自由基从而发生断裂，造成物理机械性能下降，颜色变黄。这种现象随着紫外线照射时间的增加而更加严重。因此紫外线吸收剂的开发和应用是高分子材料抗老化防褪色最通用、最方便的方法。
目前，紫外吸收剂已广泛应用于化妆品行业、食品包装材料与涂料等方面，紫外吸收剂中含有的发色基团通过将高能量的紫外线转化为无害的热能、化学能或长波光能等能量形式，从而缓解涂料、塑料等材料的光老化。但是目前市面上和文献报道的紫外吸收剂主要功能性非常单一，基本上都只有紫外吸收这一项功能。在现代人们对于材料和原料越来越强调多功能应用上，单一的功能性很明显无法满足需求。
紫外吸收剂与共聚物材料大部分是通过物理共混来实现结合的，虽然物理共混操作简单，但通过该方法制备的紫外吸收剂容易与共聚物材料产生相分离，故存在一定的局限性。
发明内容
本发明要解决的技术问题是提供一种含硅紫外吸收剂及其聚氨酯共聚物的制备，以4-取代苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮及其衍生物与三异丙基硅氧基氯甲烷及其衍生物为原料合成一种含硅紫外吸收剂，然后再依托含硅紫外吸收剂的羟基将其引入到聚氨酯高分子主链中制备一种多功能性的水性聚氨酯乳液，成功制得具有良好抗紫外线性能、高热稳定性和防水性能的高分子材料。由于有机硅具有优良的热稳定性、抗老化性以及疏水性，可增强紫外吸收剂的相关性能，延长它的使用寿命以及增强使用效果，且硅原子的引入让含紫外吸收剂的涂料具有了其它潜在的应用价值，如为人工晶状体的涂层开发提供了有效思路。
为解决上述技术问题，本发明提供了以下技术方案：
本发明的一种含硅紫外吸收剂，其特征在于具有以下结构式：
其中R1为C1-C3的烷基，R2、R3、R4为C1-C3的烷基或芳香基团。
(1)含硅紫外吸收剂的制备方法，包括以下步骤：
将0.5-20mmol4-取代苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮及其衍生物和2-60mmol二异丙基乙基胺混合后加入3-25mL无水卤代烃和0.2-10mmol二叔丁基二氯化锡。搅拌均匀后，在50-70℃下反应15-60min后冷却到室温，然后缓慢滴加0.5-3.5mmol三异丙基硅氧基氯甲烷及其衍生物，继续搅拌1-12h。接着依次用1-10mL甲醇粹灭，0.5-8.5mL卤代烃稀释，10-200mL浓度为0.03-0.12mol/L的碳酸氢钠溶液和水萃取2-3次。合并有机层，用Na2SO4干燥12-24h，过滤后浓缩除去反应溶剂即得到含硅紫外吸收剂。反应式如下：
优选的，所述4-取代苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮及其衍生物的R1包括甲基、乙基、丙基中的任意一种。
优选的，所述三异丙基硅氧基氯甲烷及其衍生物的R2、R3、R4包括甲基、乙基、丙基、苯环中的任意一种。
优选的，所述卤代烃包括1,2-二氯乙烷、二氯甲烷、1,3-二氯丙烷、1-氯丁烷中的任意一种或多种以任意比例的混合。
(2)聚氨酯共聚物的制备方法，包括以下步骤：
在反应器中加入0.5-15mmol聚多元醇后，依次滴加0.1-25mmol二异氰酸酯和催化剂(催化剂是二异氰酸酯和聚多元醇总质量的0.01-1.2％)，将混合溶液在45-80℃下反应1-6h，再加入0.7-20mL1,4-丁二醇，在该温度下继续反应1-6h。缓慢滴加1-10mL二羟甲基丙酸的N-甲基-2-吡咯烷酮溶液(二羟甲基丙酸:N-甲基-2-吡咯烷酮的质量比＝1:1-1:20)和含硅紫外吸收剂，在该温度下继续反应3-12h。最后加入2-25mL三乙胺，在高速剪切乳化下得到最终产物。
优选的，所述聚多元醇包括聚丙二醇、聚乙二醇、聚四氢呋喃二醇、聚己二酸丁二醇酯中的任意一种或多种以任意比例的混合。
优选的，所述二异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、1,6-己二异氰酸酯中的任意一种或多种以任意比例的混合。
优选的，所述催化剂包括二月桂酸二丁基锡、辛酸亚锡、二丁基二氯化锡中的任意一种或多种以任意比例的混合。
与已有技术相比，本发明提供的一种含硅紫外吸收剂及其聚氨酯共聚物的制备具有以下有益效果：
本发明在紫外吸收剂中加入了有机硅，提高了紫外吸收剂的热稳定性、抗老化性以及疏水性，含硅紫外吸收剂相较于其他复合型紫外吸收剂在抗蛋白黏附方面有潜在的应用性，其涂层材料有助于人工晶状体在抗紫外线、抗老化的同时让附着的蛋白脱落，从而不影响人工晶状体的透光度和延长使用寿命。
在市场上，通过物理共混将紫外吸收剂与高分子材料结合是最常用的方法，然而用该方法制得的产品稳定性较差，不利于长时间储存。本发明采用化学共混的方法，使紫外吸收剂与高分子材料以化学键键合，增强了其稳定性，不易发生相分离，延长了存储时间。
附图说明
图1为本发明实施例1中聚氨酯共聚物涂层的UV-Vis谱图；
图2为本发明实施例2中聚氨酯共聚物涂层的UV-Vis谱图；
图3为本发明实施例3中聚氨酯共聚物涂层的UV-Vis谱图。
具体实施方式
下面结合技术方案详细叙述本发明的具体实施例。
实施例1
(1)含硅紫外吸收剂的制备方法：
将0.5mmol4-甲基苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮和3mmol二异丙基乙基胺混合后加入5mL无水1,2-二氯乙烷和0.2mmol二叔丁基二氯化锡。搅拌均匀后，在50℃下反应15min后冷却到室温，然后缓慢滴加0.8mmol三异丙基硅氧基氯甲烷，继续搅拌1.5h。接着依次用1mL甲醇粹灭，0.5mL二氯甲烷稀释，10mL浓度为0.03mol/L的碳酸氢钠溶液和水萃取2次。合并有机层，用Na2SO4干燥12h，过滤后浓缩除去反应溶剂即得到含硅紫外吸收剂。
(2)聚氨酯共聚物的制备方法：
在反应器中加入0.5mmol聚丙二醇后，依次滴加0.1mmol异佛尔酮二异氰酸酯和二月桂酸二丁基锡(二月桂酸二丁基锡是异佛尔酮二异氰酸酯和聚丙二醇总质量的0.03％)，将混合溶液在45℃下反应2h，再加入0.7mL1,4-丁二醇，在该温度下继续反应3h。缓慢滴加1.5mL二羟甲基丙酸的N-甲基-2-吡咯烷酮溶液(二羟甲基丙酸:N-甲基-2-吡咯烷酮的质量比＝1:1)和含硅紫外吸收剂，在该温度下继续反应3h。最后加入2mL三乙胺，在高速剪切乳化下得到最终产物。
实施例2
(1)含硅紫外吸收剂的制备方法：
将2mmol 4-乙基苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮和10mmol二异丙基乙基胺混合后加入7mL无水1,3-二氯丙烷和0.5mmol二叔丁基二氯化锡。搅拌均匀后，在60℃下反应30min后冷却到室温，然后缓慢滴加1.2mmol三异甲基硅氧基氯甲烷，继续搅拌3h。接着依次用3mL甲醇粹灭，1.3mL二氯甲烷稀释，50mL浓度为0.05mol/L的碳酸氢钠溶液和水萃取2次。合并有机层，用Na2SO4干燥15h，过滤后浓缩除去反应溶剂即得到含硅紫外吸收剂。
(2)聚氨酯共聚物的制备方法：
在反应器中加入9mmol聚乙二醇后，依次滴加2.3mmol甲苯二异氰酸酯和辛酸亚锡(辛酸亚锡是甲苯二异氰酸酯和聚乙二醇总质量的0.17％)，将混合溶液在55℃下反应2.5h，再加入2.5mL1,4-丁二醇，在该温度下继续反应4.5h。缓慢滴加4mL二羟甲基丙酸的N-甲基-2-吡咯烷酮溶液(二羟甲基丙酸:N-甲基-2-吡咯烷酮的质量比＝1:5)和含硅紫外吸收剂，在该温度下继续反应5h。最后加入6mL三乙胺，在高速剪切乳化下得到最终产物。
实施例3
(1)含硅紫外吸收剂的制备方法：
将8mmol 4-丙基苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮和26mmol二异丙基乙基胺混合后加入12mL无水1-氯丁烷和3.6mmol二叔丁基二氯化锡。搅拌均匀后，在65℃下反应45min后冷却到室温，然后缓慢滴加2.7mmol三异乙基硅氧基氯甲烷，继续搅拌5h。接着依次用6mL甲醇粹灭，4.8mL二氯甲烷稀释，120mL浓度为0.08mol/L的碳酸氢钠溶液和水萃取3次。合并有机层，用Na2SO4干燥20h，过滤后浓缩除去反应溶剂即得到含硅紫外吸收剂。
(2)聚氨酯共聚物的制备方法：
在反应器中加入13.5mmol聚四氢呋喃二醇后，依次滴加14.5mmol六亚甲基二异氰酸酯和二丁基二氯化锡(二丁基二氯化锡是六亚甲基二异氰酸酯和聚四氢呋喃二醇总质量的0.68％)，将混合溶液在65℃下反应4.5h，再加入10mL1,4-丁二醇，在该温度下继续反应5h。缓慢滴加6mL二羟甲基丙酸的N-甲基-2-吡咯烷酮溶液(二羟甲基丙酸:N-甲基-2-吡咯烷酮的质量比＝1:10)和含硅紫外吸收剂，在该温度下继续反应8h。最后加入10mL三乙胺，在高速剪切乳化下得到最终产物。
实施例4
(1)含硅紫外吸收剂的制备方法：
将16mmol4-丙基苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮和55mmol二异丙基乙基胺混合后加入25mL无水1,2-二氯乙烷和7mmol二叔丁基二氯化锡。搅拌均匀后，在70℃下反应15-60min后冷却到室温，然后缓慢滴加3.5mmol二甲基苯基硅氧基氯甲烷，继续搅拌7h。接着依次用10mL甲醇粹灭，8.5mL1,3-二氯丙烷稀释，120mL浓度为0.1mol/L的碳酸氢钠溶液和水萃取3次。合并有机层，用Na2SO4干燥24h，过滤后浓缩除去反应溶剂即得到含硅紫外吸收剂。
(2)聚氨酯共聚物的制备方法：
在反应器中加入15mmol聚己二酸丁二醇酯后，依次滴加25mmol1,6-己二异氰酸酯和二月桂酸二丁基锡(二月桂酸二丁基锡是1,6-己二异氰酸酯中和聚己二酸丁二醇总质量的1.2％)，将混合溶液在75℃下反应6h，再加入15mL1,4-丁二醇，在该温度下继续反应6h。缓慢滴加10mL二羟甲基丙酸的N-甲基-2-吡咯烷酮溶液(二羟甲基丙酸:N-甲基-2-吡咯烷酮的质量比＝1:15)和含硅紫外吸收剂，在该温度下继续反应12h。最后加入15mL三乙胺，在高速剪切乳化下得到最终产物。
以上仅为本发明的具体实施例，但本发明的技术特征并不局限于此。任何以本发明为基础，为解决基本相同的技术问题，实现基本相同的技术效果，所做出的简单变化、等同替换或者修饰等，皆涵盖于本发明的保护范围之中。

Claims (9)

1.一种含硅紫外吸收剂，其特征在于具有以下结构式：
其中R1为C1-C3的烷基，R2、R3、R4为C1-C3的烷基或芳香基团。
2.权利要求1所述含硅紫外吸收剂的制备方法，其特征在于包括以下步骤：
将0.5-20mmol4-取代苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮及其衍生物和2-60mmol二异丙基乙基胺混合后加入3-25mL无水卤代烃和0.2-10mmol二叔丁基二氯化锡。搅拌均匀后，在50-70℃下反应15-60min后冷却到室温，然后缓慢滴加0.5-3.5mmol三异丙基硅氧基氯甲烷及其衍生物，继续搅拌1-12h。接着依次用1-10mL甲醇粹灭，0.5-8.5mL卤代烃稀释，10-200mL浓度为0.03-0.12mol/L的碳酸氢钠溶液和水萃取2-3次。合并有机层，用Na2SO4干燥12-24h，过滤后浓缩除去反应溶剂即得到含硅紫外吸收剂。
3.根据权利要求2所述含硅紫外吸收剂的制备方法，其特征在于：所述4-取代苯基(2,4,6-三羟基-3(3-羟基-3-甲基丁基)苯基)甲酮及其衍生物的R1包括甲基、乙基、丙基中的任意一种。
4.根据权利要求2所述含硅紫外吸收剂的制备方法，其特征在于：所述三异丙基硅氧基氯甲烷及其衍生物的R2、R3、R4包括甲基、乙基、丙基、苯环中的任意一种。
5.根据权利要求2所述含硅紫外吸收剂的制备方法，其特征在于：所述卤代烃包括1,2-二氯乙烷、二氯甲烷、1,3-二氯丙烷、1-氯丁烷中的任意一种或多种以任意比例的混合。
6.聚氨酯共聚物的制备方法，其特征在于包括以下步骤：
在反应器中加入0.5-15mmol聚多元醇后，依次滴加0.1-25mmol二异氰酸酯和催化剂(催化剂是二异氰酸酯和聚多元醇总质量的0.01-1.2％)，将混合溶液在45-80℃下反应1-6h，再加入0.7-20mL1,4-丁二醇，在该温度下继续反应1-6h。缓慢滴加1-10mL二羟甲基丙酸的N-甲基-2-吡咯烷酮溶液(二羟甲基丙酸:N-甲基-2-吡咯烷酮的质量比＝1:1-1:20)和含硅紫外吸收剂，在该温度下继续反应3-12h。最后加入2-25mL三乙胺，在高速剪切乳化下得到最终产物。
7.根据权利要求6所述的聚氨酯共聚物的制备方法，其特征在于：所述聚多元醇包括聚丙二醇、聚乙二醇、聚四氢呋喃二醇、聚己二酸丁二醇酯中的任意一种或多种以任意比例的混合。
8.根据权利要求6所述的聚氨酯共聚物的制备方法，其特征在于：所述二异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、1,6-己二异氰酸酯中的任意一种或多种以任意比例的混合。
9.根据权利要求6所述的聚氨酯共聚物的制备方法，其特征在于：所述催化剂包括二月桂酸二丁基锡、辛酸亚锡、二丁基二氯化锡中的任意一种或多种以任意比例的混合。
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