CN116178832B - 一种可降解型高分子材料及其制备方法和应用 - Google Patents
一种可降解型高分子材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于高分子材料技术领域，涉及一种可降解型高分子材料及其制备方法和应用。本发明配方主要包括按质量分数计的如下成分：可降解高分子共聚物16‑44.5wt％、聚烯烃50‑75wt％、发泡剂2‑3wt％、交联剂0.5‑1wt％、微凝胶酶缓释剂3‑5wt％、助剂。本发明利用微凝胶颗粒作为载体，仅在一定的温度或者pH环境变化下吸附/释放生物复合酶，用于在特定条件下高分子链的降解。同时保证了在正常工作范围内(例如常温、或中性pH时)酶被完整包裹在微球内，不需要改变高分子共聚物的交联结构，不影响材料的力学性能。
Description
技术领域
本发明属于高分子材料技术领域，涉及一种可降解型高分子材料及其制备方法和应用。
背景技术
聚合物材料的生产位于整个产业链的上游，可同时辐射下游医疗健康、运动防护、汽车及包装等各行各业，与日常生活息息相关。其中，发泡材料具备轻质、高弹、易加工的特点，主要用于泡沫鞋材、功能性棚膜、包装模具、热熔胶、电线电缆、玩具等领域。
目前，高分子材料制品多为难降解材料，在丢弃后，容易造成废料堆积、环境污染等问题，随着人们对环境保护和垃圾处理的日益关注，淀粉、纤维素等天然可再生材料在高分子材料制造中越来越受欢迎。申请号：CN201410487320.4公开了一种腐殖酸/EVA树脂共混改性可降解固态地膜，常规使用时即同时在进行降解，降低了材料的使用寿命。申请号：CN202010875123.5公开了一种皮革屑改性发泡鞋中底及其制备方法，其在发泡材料中引入大分子蛋白质，从而提高其可降解性，但改变了高分子的交联结构，导致力学性能发生改变。
然而，生物可降解聚合物材料对力学性能要求多而复杂，性能之间相互影响及制约，当一个性能得到改进时，通常会以牺牲另一个性能为代价。因此，材料的力学性能和可降解性难以得到同时满足，也成为该领域的一个长期挑战。
因此，亟需研发一种新的技术方案，提供具有良好降解性能的高分子材料，以解决现有技术中存在的问题。
发明内容
本发明旨在提供一种可降解型高分子材料。其中含有特殊的微凝胶酶释放剂，可以控制复合酶在不同pH、温度环境中对于可降解高分子材料的降解过程，从而实现降解速度快且降解率高，却不降低使用寿命的效果，具有良好的发展使用前景。
其通过以下技术方案实现：
本发明的一个目的在于，提供一种可降解型高分子材料，所述可降解型高分子材料包括质量分数如下的组分：
助剂；
所述微凝胶酶缓释剂由微凝胶颗粒与复合酶制备而成；
所述微凝胶颗粒由丙烯酸或丙烯酸酯类单体聚合而成。
进一步地，所述可降解高分子共聚物选自醋酸乙烯类共聚物、氨基酸类共聚物、乳酸类共聚物、戊二酸类共聚物的一种或多种。
进一步地，所述微凝胶颗粒的粒径为0.1-100μm。
进一步地，所述复合酶选自氧化还原酶、转移酶、水解酶、裂解酶和连接酶中的一种或多种。
进一步地，所述发泡剂选自二苯磺酰肼基醚类、偶氮二甲酰胺、偶氮二碳酸二异丙酯、碳酸氢钠、碳酸铵的一种或多种。
进一步地，所述交联剂选自过氧化二异丙苯、双叔丁基过氧化二异丙基苯的一种或多种。
助剂选自氧化锌、硬脂酸锌、硬脂酸、油酸锌、油酸、甘油、聚乙烯醇、硅酮的一种或多种。
本发明的另一个目的在于，提供上述可降解型高分子材料中的微凝胶酶缓释剂的制备方法，包括如下步骤：
微凝胶酶缓释剂的制备：
S1、将所述丙烯酸或丙烯酸酯类单体聚合并造粒，形成所述微凝胶颗粒，将所述微凝胶颗粒分散在水溶液中，调节pH＜8，使得所述微凝胶颗粒收缩；
S2、然后加入复合酶，调节pH为8-14，使得所述微凝胶颗粒溶胀，使得所述复合酶吸附于所述微凝胶颗粒之上；
S3、再次调节pH＜8，使得所述微凝胶颗粒再次收缩，完成对所述复合酶的包裹，形成微凝胶酶缓释剂。
进一步地，所述丙烯酸或丙烯酸酯类单体选自：丙烯酸、丙烯酸酯、甲基丙烯酸酯、二甲基丙烯酸酯、甲基丙烯酸二甲氨基乙酯、聚乙二醇二丙烯酸酯、丙烯酸/丙烯酰胺类共聚物、苯乙烯马来酸酐共聚物的一种或多种。
进一步地，所述丙烯酸或丙烯酸酯类单体，与复合酶的质量比为2:1-5:1。
与现有技术相比，本发明提供的可降解型高分子材料具有如下有益效果：
本发明的可降解型高分子材料含有一种特殊设计的微凝胶酶缓释剂，其利用微凝胶颗粒作为载体，仅在一定的温度或者pH环境变化下吸附/释放生物复合酶，用于在特定条件下高分子链的降解。同时保证了在正常工作范围内(例如常温、或中性pH时)酶被完整包裹在微球内，不会导致材料使用寿命的减短，并且因不需要改变高分子共聚物的交联结构，不会影响材料的力学性能。
附图说明
图1示出了微凝胶颗粒与复合酶的相互作用原理示意图。
图2示出了微凝胶酶缓释剂结构示意图。
图3示出了实施例中的微凝胶颗粒的透射电子显微镜照片。
具体实施方式
为了更清楚地说明本发明的技术方案，举例如下实施例，但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所使用的试剂、材料等，如无特殊说明，均可从商业途径获得。
本发明实施例中的高分子共聚物为玉米淀粉与丙烯酸接枝共聚物，牌号为GPX Type VII。
本发明实施例中的聚烯烃为乙烯、丁烯、辛烯共聚物，牌号为：Exact 9061。
本发明实施例中的发泡剂为二苯磺酰肼基醚。
本发明实施例中的交联剂为过氧化二异丙苯。
本发明实施例中的助剂包括无机助剂、表面活性剂，所述无机助剂为氧化锌，所述表面活性剂为硬脂酸锌；所述无机助剂、表面活性剂的质量比为1:2。
本发明实施例中的微凝胶酶缓释剂的制备方法，包括如下步骤：
S1、将丙烯酸乙酯(167g,1.88mol)、甲基丙烯酸(83g,0.83mol)和二丙烯酸-1,4-丁二酯(2.5g,0.01mol)三种单体按照比例混合形成单体溶液；取31.5g所述单体溶液加入含有十二烷基硫酸钠(1.8g,0.006mol)的水(518g)中作为种子液，加入磷酸氢二钾(3.15g的7wt％水溶液)和过硫酸铵(10g的2wt％溶液)；80℃下，氮气环境中机械搅拌30min，然后在1.5h内匀速加入剩余的单体溶液，继续反应2h，经渗析、用水纯化后置于70℃干燥24h得到微凝胶颗粒；将100g所述微凝胶颗粒分散在300g水溶液中，调节pH＜8，使得所述微凝胶颗粒收缩；
S2、然后加入相对质量分数为50wt％的纯化的BC-脂肪酶和蛋白酶(质量比为1:1)，调节pH为10，使得所述微凝胶颗粒溶胀，使得所述复合酶吸附于所述微凝胶颗粒之上；
S3、再次调节pH＜8，使得所述微凝胶颗粒再次收缩，完成对所述复合酶的包裹，形成微凝胶酶缓释剂。
实施例1-4中可降解型高分子材料的各个成分和质量分数，如表1所示。
表1实施例1-4中各成分及其质量分数
图1示出了微凝胶颗粒与复合酶的相互作用原理示意图。微凝胶颗粒在环境刺激下发生溶胀后，与酶以物理吸附的方式结合，形成微凝胶酶缓释剂。
图2示出了微凝胶酶缓释剂结构示意图。
图3示出了实施例中的微凝胶颗粒的透射电子显微镜照片，粒径为100nm。
将上述可降解型高分子材料进一步制备可降解弹性体粒料，包括如下步骤：
L1、将上述所有的组分在高速混合机上(转速为60转/min，混合20min)进行充分混合均匀；
L2、然后将混合好的物料在双螺杆挤出机中反应制成粒料，螺杆的熔融温度为120℃，转速为60转/min，物料在螺杆中的停留时间为300s，经切粒机切粒，即可得到优异的可降解弹性体粒料。
基于实施例1设置其对比例，对比例1-2的成分如表2所示。
表2对比例1-2中各成分及其质量份数
对比例1-2与实施例1的区别在于：将实施例1中的微凝胶酶缓释剂成分替换为不含缓释功能的酶，其他成分和制备方法与实施例1相同；
所述酶1为BC-脂肪酶和蛋白酶。
所述酶2木质素降解酶。
测试例
对实施例和对比例制备的可降解弹性体粒料进行性能测试。
测试方法：
根据国际标准ASTM D2240进行力学性能测试。
测试结果如表3所示。
表3实施例1-4和对比例1-2性能测试结果
根据表3可以得出，本发明实施例1-4制备的可降解型高分子材料中含有微凝胶酶缓释剂，其性能明显优于对比例1-2，可以明显增加在堆肥条件下酶的高分子降解效率。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (9)
1.一种可降解型高分子材料，其特征在于，所述可降解型高分子材料包括质量分数如下的组分：
高分子共聚物 16-50 wt%
聚烯烃 40-75 wt%
发泡剂 2-3 wt%
交联剂 0.5-1 wt%
微凝胶酶缓释剂 3-5 wt%
助剂；
所述微凝胶酶缓释剂由微凝胶颗粒与复合酶制备而成；
所述微凝胶颗粒由丙烯酸或丙烯酸酯类单体聚合而成；
所述可降解型高分子材料的制备方法，包括如下步骤：
微凝胶酶缓释剂的制备：
S1、将丙烯酸或丙烯酸酯类单体聚合，形成微凝胶颗粒，将所述微凝胶颗粒分散在水溶液中，调节pH＜8，使得所述微凝胶颗粒收缩；
S2、然后加入复合酶，调节pH为8-14，使得所述微凝胶颗粒溶胀，使得所述复合酶吸附于所述微凝胶颗粒之上；
S3、再次调节pH＜8，使得所述微凝胶颗粒再次收缩，完成对所述复合酶的包裹，形成微凝胶酶缓释剂。
2.根据权利要求1所述可降解型高分子材料，其特征在于，所述高分子共聚物选自醋酸乙烯类共聚物、氨基酸类共聚物、乳酸类共聚物、戊二酸类共聚物中的一种或多种。
3.根据权利要求1所述可降解型高分子材料，其特征在于，所述微凝胶颗粒的粒径为0.1-100 μm。
4.根据权利要求1所述可降解型高分子材料，其特征在于，所述复合酶选自氧化还原酶、转移酶、水解酶、裂解酶和连接酶中的一种或多种。
5.根据权利要求1所述可降解型高分子材料，其特征在于，所述发泡剂选自二苯磺酰肼基醚类、偶氮二甲酰胺、偶氮二碳酸二异丙酯、碳酸氢钠、碳酸铵的一种或多种。
6.根据权利要求1所述可降解型高分子材料，其特征在于，所述交联剂选自过氧化二异丙苯、双叔丁基过氧化二异丙基苯的一种或多种。
7.根据权利要求1所述可降解型高分子材料，其特征在于，所述丙烯酸或丙烯酸酯类单体选自：丙烯酸、丙烯酸酯、甲基丙烯酸酯、二甲基丙烯酸酯、甲基丙烯酸二甲氨基乙酯、聚乙二醇二丙烯酸酯的一种或多种。
8.根据权利要求1所述可降解型高分子材料，其特征在于，所述丙烯酸或丙烯酸酯类单体，与复合酶的质量比为2:1-5:1。
9.权利要求1-8任一项所述可降解型高分子材料在鞋材、箱包、包装、防护器具、儿童用品领域的应用。
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