CN107987308A - 一种基于淀粉颗粒的多室结构聚合物粒子的制备方法 - Google Patents

一种基于淀粉颗粒的多室结构聚合物粒子的制备方法 Download PDF

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CN107987308A
CN107987308A CN201711307315.0A CN201711307315A CN107987308A CN 107987308 A CN107987308 A CN 107987308A CN 201711307315 A CN201711307315 A CN 201711307315A CN 107987308 A CN107987308 A CN 107987308A
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成世杰
王硕
陈晨
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Qingdao University of Science and Technology
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Abstract

本发明公开了一种基于淀粉颗粒的具有多室结构聚合物粒子的制备方法。该方法以淀粉颗粒为初级粒子，结合淀粉表面聚合、附聚反应及淀粉酶催化水解等方法，制备了具有多室结构的聚合物粒子。通过改变单体种类、反应物用量和反应条件等，可以调控多室结构聚合物粒子的组成和结构。本发明提供的多室结构聚合物粒子的制备方法，利用淀粉廉价、环保的特点，不仅对合成的聚合物粒子没有污染，而且制备方法简单、成本低，可以应用于生物医药工程、材料科学、催化科学等诸多领域。

Description

一种基于淀粉颗粒的多室结构聚合物粒子的制备方法
技术领域
本发明涉及一种基于淀粉颗粒的多室结构聚合物粒子的制备方法，属于材料技术领域。
背景技术
多室化现象在自然界普遍存在，小至微生物结构，大至人类的生理结构，均可发现其重要作用。受这些现象的启发，多室结构的聚合物粒子可以用于多药递送、多催化剂协同、细胞仿生等，在生物医药工程、材料科学、生命科学、催化科学与农业科学等领域具有广泛的应用前景，已经引起科学界的广泛重视。
目前研究较多的是具有单室中空结构的聚合物粒子，具有多室结构的聚合物粒子的研究仍处于起步阶段。多室结构聚合物粒子的内部通常含有两个或两个以上的空腔，各空腔由聚合物膜相隔，各空腔可以独立封装不同组分的材料，并且可以通过外界刺激控制不同组分的缓释或协同作用。多室结构聚合物粒子不同于多孔中空结构聚合物粒子，多孔中空结构聚合物粒子具有从聚合物粒子内部到表面的孔道，粒子表面存在多个孔洞。而多室结构聚合物粒子的多室结构是被包覆在聚合物粒子内部，可以更有效地封装、隔离彼此各室结构中的装载物，更有效地控制多室结构中装载物的释放或协同作用。
多室结构聚合物粒子与单室中空结构聚合物粒子相比，可以在聚合物粒子内封装、携带多种材料；为多种材料提供反应空间；携带多种靶向或智能响应材料实现对多种外界条件做出多种智能化响应等，大大拓展了单室中空结构聚合物粒子的功能，推动了多药物靶向传递、复杂微反应器、细胞治疗、复杂传感器等领域的研究与发展。
受合成技术及材料技术等限制，具有多室结构的纳微米材料是近年才发展起来的一种新型多功能材料，关于具有多室结构的聚合物粒子的研究更少。根据已经发表的文献或专利，目前制备多室结构聚合物粒子的方法，主要包括自组装法、电喷法及微流体法等，这些方法普遍存在制备方法复杂、成本高、可重复性差、产率低、所制备材料的生物相容性差等问题，缺乏简单、廉价、稳定的制备技术严重限制了多室结构聚合物粒子的发展与应用。
淀粉是一种天然生物质资源，来源广泛、成本低廉、可生物降解、可再生，可以被生物体完全吸收而无毒副作用，淀粉分子之间相互作用可以形成结晶区，以颗粒状态存在。因淀粉来源不同，淀粉颗粒的形状和大小有差异。将淀粉用于合成具有多室结构聚合物粒子时，不会对合成的聚合物粒子造成污染。
本发明提出了简单、廉价、稳定性好的制备多室结构聚合物粒子的方法，该方法建立在淀粉粒子表面聚合、附聚反应及淀粉酶催化水解的基础上，利用淀粉颗粒可以被淀粉酶降解成为小分子低聚糖并溶于水的特性，在不引入重金属元素等有毒物质的情况下，高效制备具有多室结构的聚合物粒子。首先在淀粉粒子表面进行聚合反应，形成以淀粉粒子为核、聚合物为壳的淀粉/聚合物粒子，然后通过加入附聚剂，使淀粉/聚合物粒子彼此吸附或吸附在附聚剂粒子表面，形成由多个淀粉/聚合物粒子聚集在一起组成的粒径较大的淀粉/聚合物粒子，然后加入淀粉酶溶液，在合适的温度及时间作用下，粒子的壳层被溶液逐渐溶胀后，淀粉酶渗入粒子中的淀粉颗粒周围，对淀粉颗粒进行催化水解，淀粉颗粒在淀粉酶的作用下水解成为小分子的低聚糖，小分子的低聚糖具有良好的水溶性，可以透过粒子壳层渗出进入溶液，在清洗过程中逐渐从粒子中渗出，原先淀粉颗粒占据的空间变成空腔，形成多室结构的聚合物粒子。
发明内容
本发明的目的在于提供一种基于淀粉颗粒的多室结构聚合物粒子的制备方法。
本发明提供的技术方案是：一种基于淀粉颗粒的多室结构聚合物粒子的制备方法，包括如下步骤：
(1)将淀粉颗粒与去离子水搅拌混合后得到淀粉乳状液，向淀粉乳状液中通入氮气15～30分钟后，加入单体搅拌0.5～1小时，将水浴温度调整到反应温度后，加入引发剂，在30～45℃反应温度下，反应2～12小时，反应结束后冷却至室温，得到核壳结构的淀粉/聚合物粒子乳液；
(2)将所述步骤(1)制备得到的核壳结构的淀粉/聚合物粒子乳液搅拌并升温至45～55℃，加入附聚剂，边加边搅拌，反应1～12小时，得到多粒子附聚的淀粉/聚合物粒子乳液；
(3)将所述步骤(2)制备得到的多粒子附聚的淀粉/聚合物粒子乳液加入淀粉酶溶液中，升温至40～85℃，缓慢搅拌，反应10～24小时，反应结束后，将反应产物冷却至室温，过滤后用去离子水反复清洗，得到具有多室结构的聚合物粒子。
所述淀粉为玉米淀粉、木薯淀粉、小麦淀粉、大麦淀粉、藜麦淀粉、马铃薯淀粉、大米淀粉、甘薯淀粉中的一种或多种。
所述引发剂为过硫酸钾、过硫酸铵、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化二苯甲酰、偶氮二异丁腈、异丙苯过氧化氢、硫代硫酸钠、亚硫酸氢钠中的一种或多种。
所述附聚剂为丁苯胶乳、羧基丁苯胶乳、苯丙胶乳、纯丙胶乳、乙酸、碳酸氢钠、纤维素中的一种或多种。
所述单体为乳酸、甲基丙烯酸甲酯、二异氰酸酯、癸酸、苯乙烯、丙烯酸、N-异丙基丙烯酰胺、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲苯丙烯甲胺基乙酯、N-乙烯基吡咯烷酮、乙二醇二甲基丙烯酸酯中的一种或多种。
所述淀粉酶为α-淀粉酶、β-淀粉酶、去接枝酶、葡萄糖淀粉酶中的一种或多种。
所述步骤(1)中，引发剂的加入量为所述淀粉质量的0.1％～5％，单体的加入量为所述淀粉质量的200％～500％；所述步骤(2)中，多粒子附聚的淀粉/聚合物粒子乳液的浓度为1％～65％；所述步骤(3)中，淀粉酶溶液的浓度为1％～20％。
与现有技术相比，本发明具有的有益效果是：
淀粉作为一种天然生物质资源，具有无毒、廉价、可降解等特性，可以被淀粉酶催化水解而无毒副作用，以淀粉颗粒作为合成多室结构聚合物粒子的初级粒子，可以改善合成粒子的生物相容性，推动其在生物、医药领域的应用。
本发明所采用的表面聚合、附聚、酶解等方法，均是在相关工业领域得到大规模应用的成熟技术或工艺，合理运用这些技术，可以实现简单、廉价、稳定的制备具有多室结构的聚合物粒子。
附图说明
图1为本发明实施例1制备得到的多室结构聚合物粒子的透射电镜照片。
图2为本发明实施例2制备得到的多室结构聚合物粒子的透射电镜照片。
图3为本发明实施例3制备得到的多室结构聚合物粒子的透射电镜照片。
图4为本发明实施例4制备得到的多室结构聚合物粒子的透射电镜照片。
图5为本发明实施例5制备得到的多室结构聚合物粒子的透射电镜照片。
具体实施方式
下面结合具体实施例对本发明作进一步说明，但本发明并不限于以下实施例
实施例1
将5g玉米淀粉颗粒与150g去离子水搅拌混合后得到淀粉乳状液，通入氮气15分钟后，加入20g甲基丙烯酸甲酯搅拌0.5小时，将水浴温度调整到30℃后，加入0.05g过硫酸铵，0.03g碳酸氢钠，在30℃反应温度下，反应12小时，反应结束后冷却至室温，得到核壳结构的淀粉/聚合物粒子乳液。
将制备得到的核壳结构的淀粉/聚合物粒子乳液搅拌并升温至45℃，缓慢加入0.5g丁苯胶乳附聚剂，边加边搅拌，反应3小时，得到多粒子附聚的淀粉/聚合物粒子乳液。取50ml多粒子附聚的淀粉/聚合物粒子乳液加入到500ml的1％α-淀粉酶溶液中，升温至40℃，缓慢搅拌，反应24小时，反应结束后，将反应产物冷却至室温，过滤后用去离子水反复清洗，得到具有多室结构的聚合物粒子。
实施例2
将3g木薯淀粉颗粒与120g去离子水搅拌混合后得到淀粉乳状液，通入氮气30分钟后，加入10g乳酸搅拌1小时，将水浴温度调整到40℃后，加入0.05g偶氮二异丁腈，在40℃反应温度下，反应2小时，反应结束后冷却至室温，得到核壳结构的淀粉/聚合物粒子乳液。
将制备得到的核壳结构的淀粉/聚合物粒子搅拌并升温至45℃，缓慢加入0.5g羧基丁苯胶乳附聚剂，边加边搅拌，反应1小时，得到多粒子附聚的淀粉/聚合物粒子乳液。将70ml多粒子附聚的淀粉/聚合物粒子乳液加入300ml的1％α-淀粉酶和5％葡萄糖淀粉酶溶液中，升温至40℃，缓慢搅拌，反应10小时，反应结束后，将反应产物冷却至室温，过滤后用去离子水反复清洗，得到具有多室结构的聚合物粒子。
实施例3
将10g藜麦淀粉颗粒与200g去离子水搅拌混合后得到淀粉乳状液，通入氮气25分钟后，加入30g丙烯酸甲酯搅拌0.5小时，将水浴温度调整到40℃后，加入0.2g异丙苯过氧化氢和0.1g亚硫酸氢钠，在40℃反应温度下，反应6小时，反应结束后冷却至室温，得到核壳结构的淀粉/聚合物粒子乳液。
将制备得到的核壳结构的淀粉/聚合物粒子乳液搅拌并升温至50℃，缓慢加入1.5g纤维素附聚剂，边加边搅拌，反应10小时，得到多粒子附聚的淀粉/聚合物粒子乳液。将20ml多粒子附聚的淀粉/聚合物粒子乳液加入1000ml的1％的α-淀粉酶和3％的去接枝酶溶液中，升温至65℃，缓慢搅拌，反应10小时，反应结束后，将反应产物冷却至室温，过滤后用去离子水反复清洗，得到具有多室结构的聚合物粒子。
实施例4
将3g小麦淀粉颗粒与120g去离子水搅拌混合后得到淀粉乳状液，通入氮气20分钟后，加入15g二异氰酸酯搅拌0.5小时，将水浴温度调整到45℃后，加入0.02g过硫酸钾和0.01g硫代硫酸钠，反应6小时，反应结束后冷却至室温，得到核壳结构的淀粉/聚合物粒子乳液。
将制备得到的核壳结构的淀粉/聚合物粒子乳液搅拌并升温至45℃，缓慢加入1.5g乙酸附聚剂，边加边搅拌，反应8小时，得到多粒子附聚的淀粉/聚合物粒子乳液。取20ml多粒子附聚的淀粉/聚合物粒子乳液分散于600ml的1％的α-淀粉酶的1％的β-淀粉酶溶液中，升温至70℃，缓慢搅拌，反应24小时，反应结束后，将反应产物冷却至室温，过滤后用去离子水反复清洗，得到具有多室结构的聚合物粒子。
实施例5
将10g马铃薯淀粉颗粒与200g去离子水搅拌混合后得到淀粉乳状液，通入氮气15分钟后，加入30g甲基丙烯酸乙酯搅拌0.5小时，将水浴温度调整到45℃后，加入0.5g过氧化二异丙苯，反应10小时，反应结束后冷却至室温，得到核壳结构的淀粉/聚合物粒子乳液。
将制备得到的核壳结构的淀粉/聚合物粒子乳液搅拌并升温至55℃，缓慢加入5g苯丙胶乳附聚剂，边加边搅拌，反应12小时，得到多粒子附聚的淀粉/聚合物粒子乳液。取10ml多粒子附聚的淀粉/聚合物粒子乳液分散于1000ml的1％的葡萄糖淀粉酶和3％的去接枝酶溶液中，升温至80℃，缓慢搅拌，反应10小时，反应结束后，将反应产物冷却至室温，过滤后用去离子水反复清洗，得到具有多室结构的聚合物粒子。

Claims (7)

1.一种基于淀粉颗粒的多室结构聚合物粒子的制备方法，包括如下步骤：
(1)将淀粉颗粒与去离子水搅拌混合后得到淀粉乳状液，向淀粉乳状液中通入氮气15～30分钟后，加入单体搅拌0.5～1小时，将水浴温度调整到反应温度后，加入引发剂，在30～45℃反应温度下，反应2～12小时，反应结束后冷却至室温，得到核壳结构的淀粉/聚合物粒子乳液；
(2)将所述步骤(1)制备得到的核壳结构的淀粉/聚合物粒子乳液搅拌并升温至45～55℃，加入附聚剂，边加边搅拌，反应1～12小时，得到多粒子附聚的淀粉/聚合物粒子乳液；
(3)将所述步骤(2)制备得到的多粒子附聚的淀粉/聚合物粒子乳液加入淀粉酶溶液中，升温至40～85℃，缓慢搅拌，反应10～24小时，反应结束后，将反应产物冷却至室温，过滤后用去离子水反复清洗，得到具有多室结构的聚合物粒子。
2.根据权利要求1所述的基于淀粉颗粒的多室结构聚合物粒子的制备方法，其特征在于：步骤(1)中所述淀粉为玉米淀粉、木薯淀粉、小麦淀粉、大麦淀粉、藜麦淀粉、马铃薯淀粉、大米淀粉、甘薯淀粉中的一种或多种。
3.根据权利要求1所述的基于淀粉颗粒的多室结构聚合物粒子的制备方法，其特征在于：所述引发剂为过硫酸钾、过硫酸铵、过氧化二异丙苯、过氧化苯甲酸叔丁酯、过氧化二苯甲酰、偶氮二异丁腈、异丙苯过氧化氢、硫代硫酸钠、亚硫酸氢钠中的一种或多种。
4.根据权利要求1所述的基于淀粉颗粒的多室结构聚合物粒子的制备方法，其特征在于：所述附聚剂为丁苯胶乳、羧基丁苯胶乳、苯丙胶乳、纯丙胶乳、乙酸、碳酸氢钠、纤维素中的一种或多种。
5.根据权利要求1所述的基于淀粉颗粒的多室结构聚合物粒子的制备方法，其特征在于：所述单体为乳酸、甲基丙烯酸甲酯、二异氰酸酯、癸酸、苯乙烯、丙烯酸、N-异丙基丙烯酰胺、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲苯丙烯甲胺基乙酯、N-乙烯基吡咯烷酮、乙二醇二甲基丙烯酸酯中的一种或多种。
6.根据权利要求1所述的基于淀粉颗粒的多室结构聚合物粒子的制备方法，其特征在于：所述淀粉酶为α-淀粉酶、β-淀粉酶、去接枝酶、葡萄糖淀粉酶中的一种或多种。
7.根据权利要求1所述的基于淀粉颗粒的多室结构聚合物粒子的制备方法，其特征在于：所述步骤(1)中，引发剂的加入量为所述淀粉质量的0.1％～5％，单体的加入量为所述淀粉质量的200％～500％；所述步骤(2)中，多粒子附聚的淀粉/聚合物粒子乳液的浓度为1％～65％；所述步骤(3)中，淀粉酶溶液的浓度为1％～20％。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181067A (zh) * 2018-08-22 2019-01-11 四川之江高新材料股份有限公司 用于3d打印的含氟化石墨烯的聚乙烯混合物的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037632A (zh) * 2015-06-24 2015-11-11 青岛科技大学 一种具有核壳结构的淀粉基生物胶乳及其制备方法
CN105670249A (zh) * 2016-01-25 2016-06-15 中国科学院长春应用化学研究所 一种聚乳酸多孔材料及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037632A (zh) * 2015-06-24 2015-11-11 青岛科技大学 一种具有核壳结构的淀粉基生物胶乳及其制备方法
CN105670249A (zh) * 2016-01-25 2016-06-15 中国科学院长春应用化学研究所 一种聚乳酸多孔材料及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
WEIJUNTONG ET.AL.: "Layer-by-layer assembly of microcapsules and their biomedical applications", 《THE ROYAL SOCIETY OF CHEMISTRY》 *
段刚等: "《酶制剂应用技术问答 第2版》", 31 May 2014, 中国轻工业出版社 *
王向东等: "《发酵食品工艺》", 31 January 2011, 中国计量出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181067A (zh) * 2018-08-22 2019-01-11 四川之江高新材料股份有限公司 用于3d打印的含氟化石墨烯的聚乙烯混合物的制备方法
CN109181067B (zh) * 2018-08-22 2021-06-08 四川之江高新材料股份有限公司 用于3d打印的含氟化石墨烯的聚乙烯混合物的制备方法

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