CN101602860A - 一种表面磷酸改性的聚氨酯纳米粉体及其制备方法 - Google Patents

一种表面磷酸改性的聚氨酯纳米粉体及其制备方法 Download PDF

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CN101602860A
CN101602860A CN200910032541.1A CN200910032541A CN101602860A CN 101602860 A CN101602860 A CN 101602860A CN 200910032541 A CN200910032541 A CN 200910032541A CN 101602860 A CN101602860 A CN 101602860A
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黄晓华
刘红科
朱丹
包建春
毛春
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Nanjing Normal University
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Abstract

本发明涉及一种表面化学改性的有机高聚物纳米粉体及其制备方法。本发明的磷酸改性的纳米粉体材料，是聚醚型聚氨酯或是聚酯型聚氨酯纳米粉体，粉体表面带有自组装的磷酸根基团。是通过以下方法制备：聚醚型聚氨酯或聚酯型聚氨酯纳米粉体，在磷酸缓冲体系中以物理吸附方式引入磷酸根基团。该方法能改善粉体的稳定性、分散性，改变其物理、化学和生物性能，以期实现其在生物医用领域的深刻而广泛的应用。本发明制得的表面改性的纳米粉体粉粒从50纳米至500纳米且尺寸可控，生理环境下其表面Zeta电位为负值，工艺路线简单，耗能少，无污染，为有机高聚物纳米粉体的表面改性提供了新思路，也为高聚物纳米医用材料的开发和利用拓宽了道路。

Description

一种表面磷酸改性的聚氨酯纳米粉体及其制备方法
技术领域
本发明涉及表面磷酸改性的聚氨酯纳米粉体材料的合成制备。
技术背景
聚氨酯(Polyurethane，PU)指的是主链上含有氨基甲酸酯(-NHCOO-)特征基团的一类高聚物，由多异氰酸酯与聚醚型或聚酯型多元醇反应制得，-N＝C＝O+HO-→-NHCOO-，得到相应的聚醚型聚氨酯或聚酯型聚氨酯。自1937年被Bayer首次合成出以来，迅速在涂料、泡沫和弹性体各个领域得到广泛应用。其中聚氨酯弹性体自1967年Boretor和Pietrce等的动物实验表明，兼具良好的生物稳定性和抗凝血性，人们开始研制开发大量的聚醚型聚氨酯的生物医用材料，并形成了一系列具有实用价值的人工心脏瓣膜、人造血管等医用材料。
而粉体是工业制造的上游和基础原始材料，在汽车制造业、电子器件产业、日用化工工业，石油的催化裂化、分子筛、洗涤剂、净化剂、产品改性、金属冶炼、化工合成、航天航空、高温超导、机械制造，特别是高科技领域有着极其广泛的应用。纳米技术在90年代获得了突破性进展后，在生物医学领域的应用研究也不断得到扩展。粒度在几十至数千纳米范围内的粉体，被称为纳米粉体。目前关于有机高聚物的纳米粉体的研究热点是药物控释材料及基因治疗载体材料。经乳液聚合而成的纳米聚氨酯材料的颗粒尺度为几十至几百纳米，表面和体积两种特性效应使得纳米粒子的官能团密度加大，选择性吸附能力增加，达到吸附平衡的时间缩短，粒子的胶体稳定性提高。纳米聚氨酯材料在医学的免疫分析、药物控制释放载体、介入性诊断等方面具有很大的应用前景。
自乳化工艺是制备稳定的聚氨酯水性乳液常用的工业方法之一，其关键是在聚氨酯的分子骨架中通过亲水单体扩链引入亲水基团(多为可形成离子键的基团)，上述方法中使用的自乳化剂为带有正离子铵盐或负离子羧酸盐的二醇扩链剂。而破乳是将乳液破坏、分离两相，使分散相聚集的过程。工业上普遍使用的破乳方法之一是破乳剂的加入，介入两相之间，通过破坏乳液的界面稳定性而使得分散相聚集并从乳状液中析出。在此过程中，破乳剂的选择和乳液物化状态的控制十分重要，因为在分散相聚集析出过程中，往往由于反应条件不适而造成纳米粉体小尺寸形态的丧失。
制得的纳米粉体由于比表面积大，表面能高，极易造成团聚，不仅为制备、保存和应用带来巨大不便，而且会导致纳米材料失去其特有性能，成为材料应用开发和纳米技术继续发展的瓶颈。随着纳米技术的不断发展和纳米材料研究的不断深入，表面修饰或改性在解决纳米粒子分散性和稳定性，甚至物理、化学、生物性能的改进上得到了越来越广泛的重视和应用。
发明内容
针对上述技术背景中所提及的有机高聚物微纳米材料的稳定性、分散性欠佳和在生物体内使用时由于生物相容性不理想而带来的局限性，本发明提供了一种有机高聚物纳米超细粉体的表面磷酸改性的方法。
本发明公开了一种以聚氨酯为基材的表面磷酸改性的纳米粉体材料，是聚醚型聚氨酯或是聚酯型聚氨酯纳米粉体，粉体表面带有自组装的磷酸根基团。
所述的聚氨酯为基材的表面磷酸改性的纳米粉体材料，它的粒径在50纳米至500纳米，生理溶液中的表面电位为负。
本发明还公开了上述以聚氨酯为基材的表面磷酸改性的纳米粉体材料的制备方法，是聚醚型聚氨酯或聚酯型聚氨酯纳米粉体在磷酸缓冲体系中以物理性吸附方式于其表面引入磷酸根基团。
本发明方法中，所说的的聚醚型或是聚酯型聚氨酯的纳米粉体，是以常规制备聚氨酯水性乳液的聚醚(酯)二元醇和二异氰酸酯为原料，通过乳化工艺和破乳方法制得。
本发明方法具体操作如下：
以N-甲基二乙醇胺或二羧甲基丙酸作为亲水扩链剂，合成聚醚型或聚酯型聚氨酯的水性纳米乳液，在超声振荡下向上述合成的聚氨酯乳液中加入0.2mol/L pH＝7.0的磷酸缓冲溶液及甲苯(三者体积比为1∶1∶1)，超声作用下反应24h，静置，移除上层甲苯清液，下层乳液用去离子水透析浸洗，冷冻干燥，即可得到磷酸表面修饰的聚氨酯纳米粉末。
制得的磷酸表面修饰的聚氨酯微纳米粉末粒径在50纳米至500纳米，生理溶液中的表面电位为-3.2～-0.6V，凝血酶及凝血酶原时间表明其有较好的抗凝血性能。
本发明借鉴以聚氨酯树脂为基材，以水为分散介质的聚氨酯纳米乳液的制备，我们首先采用纳米乳液合成和化学破乳方法，在常温下实现了聚氨酯材料纳米粉体化后，继而利用静电吸附的方法对粉体表面进行磷酸化的物理修饰，获得粒径从50纳米到500纳米、粒径分散窄，结构和性能稳定的表面改性的聚氨酯纳米粉体，能够实现良好的生物相容性，为以微纳超细粉体为载体的药物开发、以微纳超细粉体为涂层的生物材料的研究，提供了更新的思路和更广的应用前景。
附图说明
图1为平均粒径分别200(A)和400nm(B)的磷酸表面修饰的聚氨酯纳米粉体的扫描电镜照片。
图2为由激光光散射测得的磷酸表面修饰的平均200nm粒径聚氨酯纳米粉体的粒径分布图。
图3为磷酸表面修饰的聚氨酯纳米粉体在生理环境下的Zeta电位图。
图4为磷酸表面修饰的聚氨酯纳米粉体的核磁共振氢谱(A)和磷谱(B)。
具体实施方法
在本发明中所使用的术语，除非有另外说明，一般具有本领域普通技术人员通常理解的含义。
下面结合具体的制备实施例和应用实施例，并参照数据进一步详细地描述本发明。应理解，这些实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
在以下的实施例中，未详细描述的各种过程和方法是本领域中公知的常规方法。所用试剂的来源、商品名以及有必要列出其组成成分者，均在首次出现时标明，其后所用相同试剂如无特殊说明，均以首次标明的内容相同。
实施例1、200nm左右粒径磷酸表面修饰的聚氨酯纳米粉体及其制备
将溶解在200ml乙酸乙酯中的二苯基甲烷二异氰酸酯(MDI)4.2g和熔融状态的聚四氢呋喃(PTMG，2000)7.5g倒入装有冷凝管、机械搅拌器、通氮气口、温度计的四颈烧瓶中，滴加二羟乙基丙酸(DMPA)的N-甲基吡咯烷酮(NMP)溶液(6％溶液，其中DMPA0.9g)，在氮气保护下，80℃温度下，机械搅拌反应3小时，加过量异丙醇或正丁醇封端，再加入三乙胺调节溶液PH至中性，滴加50ml含10％十二烷基磺酸钠的去离子水强烈搅拌乳化，得纳米水性乳液。在超声振荡下向上述合成的聚氨酯乳液中加入0.2mol/L pH＝7.0的磷酸缓冲溶液及甲苯(三者体积比为1∶1∶1)，超声振荡，反应24h，静置，移除上层甲苯清液，下层乳液用去离子水浸洗，冷冻干燥，即可得到磷酸表面修饰的聚氨酯微纳米粉末，平均粒径大小为234nm(见图1A)，粒径分布较窄(见图2)，生理溶液环境中带负电荷(见图3)，磷酸基团已构建在纳米材料上(见图4)，并且具有来延长凝血时间的良好抗凝血性能(见表1)。
表1为磷酸表面修饰的聚氨酯纳米粉体以及作为对照的肝素的凝血酶时间和凝血酶原时间
Figure G2009100325411D00041
实施例2、50nm，400nm，500nm左右粒径磷酸表面修饰的聚氨酯纳米粉体及其制备
将实施例1乳化过程中添加的表面活性剂量分别调整至20％，4％和2％浓度，其余试剂种类、用量和步骤均与实施例1同，得到平均粒径分别为50nm，400nm(见图1B)和500nm的磷酸表面修饰的聚氨酯纳米粉体。

Claims (5)

1、一种以聚氨酯为基材的表面磷酸改性的纳米粉体材料，其特征为：聚醚型聚氨酯或是聚酯型聚氨酯纳米粉体，粉体表面带有磷酸根基团。
2、根据权利要求1所述的表面磷酸改性的纳米粉体材料，其特征在于，它的粒径在50纳米至500纳米，生理溶液中的表面电位为负。
3、一种权利要求1所述的聚氨酯为基材的表面磷酸改性的纳米粉体材料的制备方法，其特征为：聚醚型聚氨酯或聚酯型聚氨酯纳米粉体，在磷酸缓冲体系中以物理性吸附方式于其表面引入磷酸根基团。
4、根据权利要求3所述的聚氨酯为基材的表面磷酸改性的纳米粉体材料的制备方法，其特征是：所说的的聚醚型或是聚酯型聚氨酯的纳米粉是通过乳化工艺和破乳方法制得。
5、根据权利要求4所述的聚氨酯为基材的表面磷酸改性的纳米粉体材料的制备方法，其特征是：以N-甲基二乙醇胺或二羧甲基丙酸作为亲水扩链剂，合成聚醚型或聚酯型聚氨酯的水性纳米乳液，在超声振荡下向上述合成的聚氨酯乳液中加入等体积的0.2mol/LpH＝7.0的磷酸缓冲溶液及甲苯，超声作用下反应24h，静置，移除上层甲苯清液，下层乳液用去离子水透析浸洗，冷冻干燥，即可得到磷酸表面修饰的聚氨酯纳米粉末。
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