CN109337039A - 一种微米级聚合物空心微球的制备方法 - Google Patents

一种微米级聚合物空心微球的制备方法 Download PDF

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CN109337039A
CN109337039A CN201811094752.3A CN201811094752A CN109337039A CN 109337039 A CN109337039 A CN 109337039A CN 201811094752 A CN201811094752 A CN 201811094752A CN 109337039 A CN109337039 A CN 109337039A
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杨晓武
辛燕
李培枝
秋列维
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Shaanxi Jingge Special Catalytic Technology Co ltd
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Abstract

本发明涉及一种微米级聚合物空心微球的制备方法，将聚醚和多异氰酸酯混合均匀，升温并反应，得到聚氨酯与异氰酸酯混合物；冷却所得混合物，与水搅拌均匀，得到乳液；使用液氮冷却所得乳液，得到冰块状固体；将得到的冰块状固体真空干燥，干燥后得到空心微球。本发明通过对制备方法的优化，不使用催化剂，避免水分过早介入，引入冷却操作，使制备步骤精简，有害物残留少，且制得的空心微球形状结构规则，能够应用于生物材料和医用材料领域。

Description

一种微米级聚合物空心微球的制备方法
技术领域
本发明属于高分子材料技术领域，具体涉及一种微米级聚合物空心微球的制备方法。
背景技术
有空心特征的球状颗粒具有容纳其他物质的功能。特别是当球状颗粒的直径为微米级或纳米级的时候，这种微球便具备了密度小、比表面积大的特征，对其中的容纳物质具有遮盖能力强和负载能力高的特性。不填充其他物质的时候，可用作隔热隔音材料。填充药物等活性物时，可以控制释放和作为微型反应器使用。填充催化剂时，则可以大幅提高催化效率。所以微纳尺度的空心微球在先进材料的制备中发挥了重要作用。
中空微球的制备，通常是利用一个球形内核做模板，使聚合物在内核周围聚集生长，形成小球后移除内核。不同的聚合物需要用到不同的内核，而内核的移除方式差异很大，所以就会造成不同的空心微球性质各不相同。比如聚丙烯酸类微球形成时，需要先用含羧基单体聚合成内核，再用无羧基单体就在内核表面进一步反应形成壳体，最后利用碱使内核离子化并吸水膨胀从而形成中空微球。这个过程对单体配比具有较高要求，反应程序较多，容易出现差错。也有使用纳米级二氧化硅作为内核，在表面包裹一层聚合物，包裹过程完成后，利用氟化氢溶液溶解内核，这种空心微球的制备成功率较高，但是除去二氧化硅时必然导致大量的氟残留，影响了该类中空微球在生物领域的应用。在不同的微球形成过程中，都存在壳体形成过程复杂，内核移除困难的问题。
中国专利CN108192074公开了一种利用自乳化技术制备交联聚氨酯微球和/或聚氨酯空心微球的方法，不使用有机溶剂，但是为了或得复杂的网络状聚合物结构需使用官能度为3以上的聚合物以及有机金属催化剂。在该发明中的干燥过程中这些有机金属被保留在产品中，使得该产品无法应用于生物材料和医用材料。
发明内容
本发明的目的是提供一种微米级聚合物空心微球的制备方法，参与反应的原料种类少，中空微球形成过程简单。
本发明所采用的技术方案是：
一种微米级聚合物空心微球的制备方法，其制备步骤如下：
步骤一，将10份聚醚和15~20份多异氰酸酯混合均匀，升温至50~70℃，反应20~30min，得到聚氨酯与异氰酸酯混合物；
步骤二，冷却步骤一所得混合物，与混合物9~10倍质量的水搅拌均匀，得到乳液；
步骤三，使用液氮冷却步骤二所得乳液，得到冰块状固体；
步骤四，将步骤三得到的冰块状固体真空干燥，干燥压力为5~10Pa，干燥后得到空心微球。
步骤一中，聚醚为平均相对分子质量为350~450g/mol的聚乙二醇醚，一端为羟基，另一端为不活泼烷基。
步骤一中，多异氰酸酯为含有两个以上异氰酸酯基的异氰酸酯，为异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）或HDI三聚体。
本发明具有以下优点：
1.本发明的制备方法原料简单，只包括聚醚和异氰酸酯，不使用催化剂。
2.制备步骤少，操作简单，一共分为混合升温反应、乳化、冷却、干燥四个步骤，即可制备得到空心微球；加热升温过程是形成具有乳化能力的壳体材料的过程，之后与水混合，能够控制水解比例防止异氰酸酯的水解形成氨基酸，避免了因为提前乳化导致的乳液或悬浮液极不稳定。
3.引入冷却操作，未反应的异氰酸酯，在冻结成固体后，低压条件下升华气化，以气体形态通过壳层，留下空腔。冻结成冰块的水可以确保空心微球形成之前，球形颗粒与颗粒之间保持一定距离防止球形颗粒的黏连变形。
4.制备过程有害物残留少，过程中涉及的有害小分子为异氰酸酯，异氰酸酯是对羟基活泼物质，即使没有通过真空干燥这一步骤彻底清除，也会在存储过程中与活泼氢或者与空气中的水发生反应而失去毒性。
5.制得的空心微球形状结构规则，由于制备过程中使用了液态内核，且清除彻底，所得空心微球内壁和外表都呈现规则表面，方便微球中空腔体积估算。
附图说明
图1为实施例一微米级聚合物空心微球微观形貌。
具体实施方式
下面将结合具体实施例对本发明作进一步详细的描述，但本发明的实施方式包括但不限于以下实施例表示的范围。
本发明的制备制备方法如下：
步骤一，将10份聚醚和15~20份多异氰酸酯混合均匀，升温至50~70℃，反应20~30min，得到聚氨酯与异氰酸酯混合物；
步骤二，冷却步骤一所得混合物，与混合物9~10倍质量的水搅拌均匀，得到乳液；
步骤三，使用液氮冷却步骤二所得乳液，得到冰块状固体；
步骤四，将步骤三得到的冰块状固体真空干燥，干燥压力为5~10Pa，干燥后得到空心微球。
步骤一中，聚醚为平均相对分子质量为350~450g/mol的聚乙二醇醚，一端为羟基，另一端为不活泼烷基。
步骤一中，多异氰酸酯为含有两个以上异氰酸酯基的异氰酸酯，为异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）或HDI三聚体。
本发明的制备原理是，以水为连续相，以异氰酸酯为油相，以异氰酸酯和聚醚反应所得聚氨酯为表面活性剂形成乳液。异氰酸酯是油相液体，聚氨酯中的异氰酸酯带入的基团与聚氨酯结构相似，所以能将异氰酸酯乳化。由于乳化剂不是小分子，乳化后异氰酸酯液滴周围是厚实的壳层结构，这可以确保空心微球形成后有足够的强度能稳定存放。厚实的壳层结构也同时可以阻止水分与异氰酸酯自由接触，延缓异氰酸酯因水的存在而快速变质。少量的水分与异氰酸酯接触形成的聚氨酯结构可以作为对壳层结构强度的补充。未反应的异氰酸酯，在冻结成固体后，低压条件下升华气化。以气体形态通过壳层，留下空腔。冻结成冰块的水可以确保空心微球形成之前，球形颗粒与颗粒之间保持一定距离防止球形颗粒的黏连变形。
下面通过具体实施例对本发明做详细地说明。
实施例1
称取15份六亚甲基二异氰酸酯HDI与10份聚乙二醇醚，其中聚乙二醇醚的平均相对分子质量为350g/mol，聚醚一端为羟基，一端为甲基，将两者混合均匀在60℃条件下反应30min。将所得混合物冷却至室温，加水225g，搅拌形成乳液。将乳液用液氮迅速冷却成固体。将所得固体置于真空干燥器中，设定压力为5Pa，经过24h干燥后，所得固体即为聚合物空心微球。微球直径1~5μm，壳体厚度为300~500nm，如图1所示。
实施例2
称取20g异佛尔酮二异氰酸酯IPDI与10g聚乙二醇醚，其中聚乙二醇醚的平均相对分子质量为450g/mol，聚醚一端为羟基，一端为乙基，将两者混合均匀在60℃条件下反应30min。将所得混合物冷却至室温，加水300g，搅拌形成乳液。将乳液用液氮迅速冷却成固体。将所得固体置于真空干燥器中，设定压力为5Pa，经过30h干燥后，所得固体即为聚合物空心微球。微球直径1~10μm，壳体厚度为200~600nm。
实施例3
称取15gHDI三聚体与10g聚乙二醇醚，其中聚乙二醇醚的平均相对分子质量为350g/mol，聚醚一端为羟基，一端为甲基，将两者混合均匀在60℃条件下反应20min。将所得混合物冷却至室温，加水250g，搅拌形成乳液。将乳液用液氮迅速冷却成固体。将所得固体置于真空干燥器中，设定压力为10Pa，经过24h干燥后，所得固体即为聚合物空心微球。微球直径1~5μm，壳体厚度为300~500nm。
以上实施例1为最佳实施例。
本发明的内容不限于实施例所列举，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。

Claims (3)

1.一种微米级聚合物空心微球的制备方法，其特征在于：
包括以下步骤：
步骤一，将10份聚醚和15~20份多异氰酸酯混合均匀，升温至50~70℃，反应20~30min，得到聚氨酯与异氰酸酯混合物；
步骤二，冷却步骤一所得混合物，与混合物9~10倍质量的水搅拌均匀，得到乳液；
步骤三，使用液氮冷却步骤二所得乳液，得到冰块状固体；
步骤四，将步骤三得到的冰块状固体真空干燥，干燥压力为5~10Pa，干燥后得到空心微球。
2.根据权利要求1所述的一种微米级聚合物空心微球的制备方法，其特征在于：
步骤一中，聚醚为平均相对分子质量为350~450g/mol的聚乙二醇醚，一端为羟基，另一端为不活泼烷基。
3.根据权利要求1或2所述的一种微米级聚合物空心微球的制备方法，其特征在于：
步骤一中，多异氰酸酯为含有两个以上异氰酸酯基的异氰酸酯，为异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）或HDI三聚体。
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