CN107163164B - 交联型大分子光稳定剂的制备方法 - Google Patents
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Abstract
本发明公开了一种UV光固化型交联型大分子光稳定剂的制备方法，包括：利用肉桂结构壳聚糖衍生物聚合物点与2，4‑二羟基二苯甲酮作为原料，通过曼尼希反应制备得到大分子紫外线吸收剂。本发明所制备得到的大分子紫外线吸收剂具有优异的紫外吸收效果；可以通过分子修饰赋予该大分子紫外线吸收剂同时具有紫外吸收、紫外光屏蔽、自由基捕捉、阻燃、耐热等多种功能，是一类性能优异的复合型光稳定剂，可以作为UV固化材料中的一种反应型大分子光稳定剂，也可以采用UV光固化交联获得不同分子量的光稳定剂。
Description
技术领域
本发明属于高分子助剂类领域，涉及一种交联型大分子光稳定剂的制备方法。
背景技术
近年来，随着地球大气中臭氧层的不断空洞化，使地面的紫外线辐射强度不断增大，给人类及其生存环境造成极为不利的影响。高分子材料长期受到紫外光的辐射会加速材料的光氧老化，从而缩短材料的使用寿命。为了减少这种紫外光引起的高分子材料老化现象，在高分子材料中添加光稳定剂是一种行之有效的方法。
低分子二苯甲酮类紫外线吸收剂因在200～400nm范围内有较好的紫外光吸收性能，被广泛应用于塑料、涂料、黏合剂、汽车部件、木塑制品等。但是，近年来人们发现，低分子光稳定剂在生物群中有较高的蓄积，对人的健康造成了威胁。所以大分子及高分子光稳定剂的研究成为一种发展趋势。但目前大部分以2,4-二羟基二苯甲酮(UV-0)为母体进行高分子化的光稳定剂均是破坏了UV-0分子中4位酚羟基，从而削弱了紫外光吸收效果，本发明以UV-0为紫外线吸收剂单体、哌啶胺为主要光稳定剂原料，在未破坏UV-0分子中4-位酚羟基的基础上制备了一种新型高效的复合型大分子光稳定剂，分子中引入了近年研究活跃的碳点纳米材料，可以进行分子修饰，合成多种功能的新型大分子光稳定剂。
发明内容
本发明的一个目的是解决至少上述问题，并提供至少后面将说明的优点。
本发明还有一个目的是提供一种交联型大分子光稳定剂的制备方法，包括以下步骤：
步骤一、以壳聚糖、肉桂醛为原料，甲醇为溶剂，硼氢化钾水溶液为还原剂，进行席夫碱反应，得N-烷基壳聚糖；
步骤二、将步骤一中得到的N-烷基壳聚糖、小分子掺杂剂以及去离子水混合，进行水热反应，得壳聚糖基聚合物点；
步骤三、将步骤二中得到的壳聚糖基聚合物点和2,4-二羟基二苯甲酮为原料，以醋酸溶液和乙醇的混合液为溶剂，进行曼尼希反应，得大分子光稳定剂；
步骤四、将步骤三中得到的大分子光稳定剂置于紫外光下照射，即得交联型大分子光稳定剂。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述步骤一，具体为：
在氮气保护氛围下，以1重量份壳聚糖、0.4-1重量份的肉桂醛为原料，甲醇为溶剂，反应时间6-18h；再向其中滴加1.5倍壳聚糖重量份的硼氢化钾水溶液，滴加完毕后继续反应12-24h，得壳聚糖衍生物。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述步骤一中，还包括：用水和甲醇进行洗涤，冷冻干燥，得所述壳聚糖衍生物。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述步骤二，具体为：
将步骤一得到的壳聚糖衍生物以及小分子掺杂剂、去离子水按比例1g:0.2-0.6g:20-40ml，混合反应，180-230℃，2-4h，得壳聚糖基聚合物点。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述小分子掺杂剂为柠檬酸、哌啶胺、N-(2-羟乙基)-乙二胺、己二胺四甲叉膦酸或氨基三亚甲基膦酸。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述步骤二中，还包括：用95％乙醇溶液沉淀并洗涤，冷冻干燥，得所述壳聚糖基聚合物点。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述步骤三，具体为：
将步骤二得到的壳聚糖基聚合物点与2,4-二羟基二苯甲酮混合，以质量分数1-2％的醋酸溶液和乙醇的混合液为溶剂，60～80℃，12-24h，得大分子光稳定剂。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述步骤三还包括：
产物用乙醇洗涤，冷冻干燥，即得大分子光稳定剂。
优选的是，所述的交联型大分子光稳定剂的制备方法，壳聚糖基聚合物点与2,4-二羟基二苯甲酮的质量比为：1:0.2-1.0；
首先，先将壳聚糖基聚合物点溶解于质量分数1-2％的醋酸溶液和乙醇的混合液，然后向其中分批加入2,4-二羟基二苯甲酮的乙醇溶液；
其中，质量分数1-2％的醋酸水溶液与乙醇的体积比为100：20-40。
优选的是，所述的交联型大分子光稳定剂的制备方法，所述步骤四，具体为：
按1g/5-10ml比例将步骤三中得到的大分子光稳定剂分散于四氢呋喃溶液中，并置于紫外光下照射12-48h，即得交联型大分子光稳定剂。
本发明主要包括以下有益效果：本发明设计开发了一种可通过UV光固化大分子复合光稳定剂。本发明制备得到的大分子紫外线吸收剂具有优异的紫外吸收，主要由壳聚糖基聚合物点为核心，首先通过分子修饰，合成壳聚糖衍生物基聚合物点荧光材料，然后通过曼尼希反应与UV-0分子在未破坏4-位酚羟基的情况下合成具有支化结构的新型大分子复合光稳定剂，根据结构分析，特别适合应用于沥青以及木塑复合材料中。另外该大分子光稳定剂反应无需催化剂、反应条件温和，特别适合工业化生产。
本发明的其它优点、目标和特征将部分通过下面的说明体现，部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1为本发明的步骤二得到的壳聚糖基聚合物点的红外谱图；
图2为本发明目标产物交联型大分子光稳定剂的红外谱图；
图3为本发明目标产物交联型大分子光稳定剂的紫外吸收谱图。
具体实施方式
下面结合附图对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
应当理解，本文所使用的诸如“具有”、“包含”以及“包括”术语并不配出一个或多个其它元件或其组合的存在或添加。
(1)N-烷基壳聚糖的合成
取1g壳聚糖于三口瓶中，0.4-1g的肉桂醛，以甲醇为溶剂，在氮气保护下搅拌反应6h-18，取1.5倍壳聚糖氨基物质量的硼氢化钾水溶液分别滴加到上述反应液中，滴加完毕继续反应，结束后用水和甲醇进行洗涤，冷冻干燥即得到产物，产率76％。反应方程式如下
(2)壳聚糖基衍生物聚合物点的合成
将(1)中所合成的壳聚糖衍生物、掺杂剂小分子化合物(柠檬酸、哌啶胺、N-(2-羟乙基)-乙二胺、己二胺四甲叉膦酸、氨基三亚甲基膦酸)、去离子水混合后加入聚四氟乙烯高压反应釜于180-230℃反应2-4h，结束后用95％乙醇溶液沉淀并洗涤，冷冻干燥便得到壳聚糖基聚合物点荧光材料，产率52％。
壳聚糖基聚合物点的红外谱图如图2所示。
反应方程式如下
(3)壳聚糖基聚合物点-UV-0复合光稳定剂的合成
取壳聚糖基聚合物点(1g)加入到三口烧瓶中，以1％的醋酸水溶液为溶剂，溶解后分批次投入多聚甲醛粉末，在70℃反应1h，然后加入不同量的UV-0(0.2-1g)的DMF溶液，于60～80℃反应12-24h，产物用乙醇洗涤，真空或冷冻干燥即得到大分子复合型光稳定剂，产率78％。反应方程式如下
(4)UV光固化型大分子光稳定剂的制备
将上述合成的复合型光稳定剂1g置于三口瓶中，分散在四氢呋喃溶液5-10mL中，通入氮气，然后置于紫外光下照射，照射12-48h，即得到交联型大分子光稳定剂。
图1可以看出，在3454cm-1为壳聚糖分子中O-H、N-H伸缩振动吸收峰，2925-2958cm-1为-CH2的特征吸收峰，1645cm-1为C＝N伸缩振动峰；1588cm-1为苯环中骨架振动峰。说明聚合物点表面含有肉桂苯环骨架以及壳聚糖中的O-H、N-H官能团。
从图2中可以看出接枝UV-0后，在3419cm-1处红外峰明显变宽，为壳聚糖分子中-OH、-NH与UV-0中酚羟基-OH的缔合伸缩振动吸收峰，2927-2967cm-1与图1相比也明显变宽，为分子在亚甲基-CH2的特征吸收峰，在1620cm-1处出现了UV-0中酮羰基-C＝O的特征吸收峰，这些可以说明在聚合物点中成功引入了UV-0单体。
从图3为本发明的目标产物大分子光稳定剂的紫外吸收，该光稳定剂在260nm与345nm处有强紫外吸收，紫外吸收峰覆盖了UV-A与UV-B区域，可谓是达到了广谱紫外吸收，其中260nm归属于苯环的π-π*的跃迁，345nm为二苯甲酮中羰基的n-π*跃迁。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。
Claims (9)
1.一种交联型大分子光稳定剂的制备方法，其特征在于，包括以下步骤：
步骤一、以壳聚糖、肉桂醛为原料，甲醇为溶剂，硼氢化钾水溶液为还原剂，进行席夫碱反应，得N-烷基壳聚糖；
步骤二、将步骤一中得到的N-烷基壳聚糖、小分子掺杂剂以及去离子水混合，进行水热反应，得壳聚糖基聚合物点；
步骤三、将步骤二中得到的壳聚糖基聚合物点和2,4-二羟基二苯甲酮为原料，以醋酸溶液和乙醇的混合液为溶剂，进行曼尼希反应，得大分子光稳定剂；
步骤四、将步骤三中得到的大分子光稳定剂置于紫外光下照射，即得交联型大分子光稳定剂；
所述小分子掺杂剂为柠檬酸、哌啶胺、N-(2-羟乙基)-乙二胺、己二胺四甲叉膦酸或氨基三亚甲基膦酸。
2.如权利要求1所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤一，具体为：
在氮气保护氛围下，以1重量份壳聚糖、0.4-1重量份的肉桂醛为原料，甲醇为溶剂，反应时间6-18h；再向其中滴加1.5倍壳聚糖重量份的硼氢化钾水溶液，滴加完毕后继续反应12-24h，得壳聚糖衍生物。
3.如权利要求2所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤一中，还包括：用水和甲醇进行洗涤，冷冻干燥，得所述壳聚糖衍生物。
4.如权利要求1所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤二，具体为：
将步骤一得到的壳聚糖衍生物以及小分子掺杂剂、去离子水按比例1g:0.2-0.6g:20-40ml，混合反应，180-230℃，2-4h，得壳聚糖基聚合物点。
5.如权利要求4所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤二中，还包括：用95％乙醇溶液沉淀并洗涤，冷冻干燥，得所述壳聚糖基聚合物点。
6.如权利要求1所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤三，具体为：
将步骤二得到的壳聚糖基聚合物点与2,4-二羟基二苯甲酮混合，以质量分数1-2％的醋酸溶液和乙醇的混合液为溶剂，60～80℃，12-24h，得大分子光稳定剂。
7.如权利要求6所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤三还包括：
产物用乙醇洗涤，冷冻干燥，即得大分子光稳定剂。
8.如权利要求6所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤三中，壳聚糖基聚合物点与2,4-二羟基二苯甲酮的质量比为1:0.2-1.0；
首先，先将壳聚糖基聚合物点溶解于质量分数1-2％的醋酸溶液和乙醇的混合液，然后向其中分批加入2,4-二羟基二苯甲酮的乙醇溶液；
其中，质量分数1-2％的醋酸水溶液与乙醇的体积比为100:20-40。
9.如权利要求1所述的交联型大分子光稳定剂的制备方法，其特征在于，所述步骤四，具体为：
按1g/5-10ml比例将步骤三中得到的大分子光稳定剂分散于四氢呋喃溶液中，并置于紫外光下照射12-48h，即得交联型大分子光稳定剂。
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