CN107789677A - 一种超支化聚酰亚胺抗凝血抗菌材料的制备方法及应用 - Google Patents

一种超支化聚酰亚胺抗凝血抗菌材料的制备方法及应用 Download PDF

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CN107789677A
CN107789677A CN201710908102.7A CN201710908102A CN107789677A CN 107789677 A CN107789677 A CN 107789677A CN 201710908102 A CN201710908102 A CN 201710908102A CN 107789677 A CN107789677 A CN 107789677A
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徐祖顺
李庆
栗静
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Abstract

本发明公开了一种超支化聚酰亚胺抗凝血抗菌材料的制备方法，属于化工材料领域。本发明用2‑甲基丙烯酰氧乙基磷酸胆碱对氨基封端的超支化聚酰亚胺的表面进行接枝改性，形成超支化聚酰亚胺薄膜，制备的HBPI‑MPC薄膜生物相容性，抗凝血性以及抗菌性都更好。

Description

一种超支化聚酰亚胺抗凝血抗菌材料的制备方法及应用
技术领域
本发明属于化工材料领域，具体涉及一种超支化聚酰亚胺抗凝血抗菌材料的制备方法及应用。
背景技术
近年来，作为生物医用材料应用的抗凝血材料受到人们高度的重视和关注，其研究工作也取得了很大的进步。虽然现已研制出的许多高分子生物材料，如聚甲基丙烯酸甲酯(PMMA)、聚乙烯(PE)、聚丙烯(PP)、聚砜(PSF)、聚醚砜(PES)和聚酰亚胺(PI)等因有良好的机械性能和一定的生物相容性，可作为抗凝血材料应用；但决定高分子材料能否应用于生物医用材料的主要因素为该材料的抗凝血性是否足够好。虽然PMAA，PES，PI等可作为基体材料，但仍需要对其进行改性(生物相容性还不够好)。近年，用于材料表面改性的物质和技术得到飞速发展，在实际应用中可使高分子材料具有优异性能和特异生物性能，而性能相对较好的肝素化材料、聚磷酰胆碱和聚乙二醇等也不能完全满足临床医学对其应用性能的要求，主要是(1)抗凝血性能：长期植入人体的抗凝血活性不足；(2)抗菌性能：易引起细菌感染，从而导致各种并发症等。因此，研究提高抗凝血材料的抗凝血活性、抗菌性和改善血液相容性具有重要的意义。
早期的仿生表面涂层的研究方向是合成在烷基链上有炔基官能团的类天然脂质-二棕榈酰磷脂酰胆碱(DPPC)，二炔磷脂酰胆碱(DAPC)的合成可以通过紫外或γ-射线照射的方法来合成生物相容性良好的涂料。同时，还将研究方向延伸到将PC的活性小分子衍生物直接化学耦合到适当的功能化表面的方向。由日本主导的另一种方法是发展有磷脂基的单体和磷脂基的聚合物衍生物。
作为新型生物材料，Nakabayashi组通过开发甲基丙烯酸酯，2-甲基丙烯酰氧乙基磷酸胆碱(MPC)的作用证明了那些含脂基物质的潜在应用。研究者们认为，将有甲基丙烯酸烷基脂长链的MPC共聚到其他结构上可以更接近模仿的天然细胞膜脂质结构。这些材料有两亲性：高极性两性离子PC基团和疏水性烷基链。当这些材料溶解在适当溶剂中并通过物理方法以涂料的方式涂布在疏水材料时，该疏水材料会有极其稳定的生物相容性。人们对这些简单的共聚物做了大量的结构变化，包括引入能使之化学耦合到材料表面的特殊基团，引入尿烷侧链来增强聚氨酯和涂料之间的相互作用，掺杂交联剂来提高薄膜的物理性能，引入含阳离子的共聚物(可以接枝特殊官能团，如肝素)。另还有更复杂的方法包括通过共聚作用将大分子单体MPC和BMA反应合成PBMA-g-PMPC。
鉴于超支化聚合物独特的三维树状结构，末端含有大量端基官能团(可用于接枝修饰分子)，溶于溶剂后溶液粘度低和内部有空隙，使它在生物医用材料领域受到极大的青睐。
发明内容
现有应用于生物医用材料的高分子材料抗凝血性能不足够好，而性能相对较好的肝素化材料、聚磷酰胆碱和聚乙二醇等也不能完全满足临床医学对其应用性能的要求，主要是(1)抗凝血性能：长期植入人体的抗凝血活性不足；(2)抗菌性能：易引起细菌感染，从而导致各种并发症等。因此，研究提高抗凝血材料的抗凝血活性、抗菌性和改善血液相容性，设计一种超支化聚酰亚胺抗凝血抗菌材料具有重要的意义。
本发明拟在超支化聚酰亚胺(HBPI)的制备及性能研究的基础上，设计、制备出接枝2-甲基丙烯酰氧乙基磷酸胆碱(MPC)的改性超支化聚酰亚胺(HBPI-MPC)；探索这种HBPI-MPC材料的血液相容性[抗血小板粘附性]等性能并对其进行测试表征。
本发明的目的之一是提供一种超支化聚酰亚胺抗凝血抗菌材料的制备方法，首先合成氨基封端的超支化聚酰亚胺(AM-HBPI)，然后用2-甲基丙烯酰氧乙基磷酸胆碱(MPC)对其表面进行接枝改性，形成HBPI-MPC薄膜。
本发明的另一目的是提供一种超支化聚酰亚胺抗凝血抗菌材料的应用：该超支化聚酰亚胺薄膜可作为抗凝血抗菌材料。
与现有技术相比，本发明的优点为：本发明制备的HBPI-MPC薄膜生物相容性，抗凝血性以及抗菌性都更好，长期植入人体的抗凝血活性强，不易引起细菌感染和各种并发症等，可作为生物医用材料使用。
说明书附图
图1为HBPI薄膜与HBPI-15MPC薄膜的FTIR光谱分析。
图2为HBPI-MPC薄膜表面血小板粘附情况的SEM图：(a)HBPI，(b)HBPI-5MPC，(c)HBPI-10MPC，(d)HBPI-15MPC，(e)HBPI-20MPC。
图3为为HBPI-MPC薄膜的细菌粘附性测试的SEM图。
具体实施例
本发明的目的之一是提供一种超支化聚酰亚胺抗凝血抗菌材料的制备方法，首先合成氨基封端的超支化聚酰亚胺(AM-HBPI)，然后用2-甲基丙烯酰氧乙基磷酸胆碱(MPC)对其表面进行接枝改性，形成HBPI-MPC薄膜，并对其抗凝血性，抗菌性以及生物相容性进行表征，具体步骤如下：
(1)氨基封端的超支化聚酰亚胺(AM-HBPI)的制备：将1,3,5-三(4-氨基苯氧基)苯(TAPOB)和N-甲基吡咯烷酮(NMP)置于烧瓶中并磁力搅拌，冰浴冷却，在N2保护下，用恒压滴液漏斗将双酚A型二酐(BPADA)和N-甲基吡咯烷酮(NMP)的混合溶液在1～3h内缓慢滴入其中，滴加完毕后在常温下反应1～2h，滴加异喹啉，120℃反应3～5h，180～200℃反应16～24h，冷却至室温后，倒入无水乙醇，并清洗，产物在烘箱中80℃真空干燥24h，得到氨基封端的超支化聚酰亚胺(AM-HBPI)；
所述的1,3,5-三(4-氨基苯氧基)苯(TAPOB)和N-甲基吡咯烷酮(NMP)的质量比为1:20～26；
所述的双酚A型二酐(BPADA)和N-甲基吡咯烷酮(NMP)的混合溶液浓度为4％～6％；
所述的3,5-三(4-氨基苯氧基)苯(TAPOB)与双酚A型二酐(BPADA)的摩尔比为1:1。
(2)AM-HBPI薄膜接枝改性：将步骤(1)的AM-HBPI粉末溶解在N-甲基吡咯烷酮(NMP)中，搅拌均匀后加入2-甲基丙烯酰氧乙基磷酸胆碱(MPC)，室温搅拌24～26h得混合液，将上述混合液平铺在玻璃板上，置于干燥箱内干燥，100℃烘18～24h，除去溶剂，升温至120～160℃，并保温1～2h，再次升温至180～220℃，并保温1～2h，最后自然冷却，得到超支化聚酰亚胺薄膜(HBPI-MPC)；
所述的2-甲基丙烯酰氧乙基磷酸胆碱(MPC)与氨基封端的超支化聚酰亚胺(AM-HBPI)的摩尔比5～20％。
(3)将步骤(2)的HBPI-MPC薄膜在去离子水中室温下震荡5～8h，除去膜表面未接枝的MPC，此震荡清洗步骤重复3次，最后将所得HBPI-MPC膜在室温下真空干燥至恒重。
本发明的另一目的是提供一种超支化聚酰亚胺抗凝血抗菌材料的应用：该超支化聚酰亚胺薄膜可作为抗凝血抗菌材料。
下面结合具体的实例，进一步阐述本发明。应理解，这些实例仅用于说明本发明而不用于限制本发明的范围。下面实例中未注明具体实施条件的实验方法，通常按照常规条件，或按照制造商所建议的条件。
实验所需溶剂配置：磷酸盐缓冲液(PBS)(pH＝7.4，0.01mol/L)的配制：分别精确称量0.27g KH2PO4，1.42g Na2HPO4，3.58g Na2HPO4·12H2O，8.00g NaCl，0.20gKCl溶解于去离子水，并转移至1L容量瓶中，定容后摇匀备用。
实施例1
(1)氨基封端的超支化聚酰亚胺(AM-HBPI)的制备：将0.399g(1mmol)1,3,5-三(4-氨基苯氧基)苯(TAPOB)和10ml N-甲基吡咯烷酮(NMP)置于100ml三口烧瓶中，磁力搅拌，冰浴冷却，在N2保护下，用恒压滴液漏斗将0.520g(1mmol)双酚A型二酐(BPADA)和10ml N-甲基吡咯烷酮(NMP)的混合溶液在2h内缓慢滴入其中，滴加完毕后在常温下反应1h，滴加6滴异喹啉，120℃反应5h，180℃反应18h，冷却至室温后，倒入无水乙醇，并清洗，产物在烘箱中80℃真空干燥24h，得到氨基封端的超支化聚酰亚胺(AM-HBPI)。
(2)AM-HBPI薄膜接枝改性：将0.6g的AM-HBPI粉末溶解在10mlNMP中，搅拌均匀后加入5mol％的2-甲基丙烯酰氧乙基磷酸胆碱(MPC)的水溶液(其中mol％＝n(MPC)/n(HBPI)*100％)，室温搅拌24h，将混合液平铺在干燥清洁的玻璃板上，然后置于干燥箱内干燥，100℃烘18h，除去溶剂；梯度升温120℃，180℃，分别保温1h，最后自然冷却，得到超支化聚酰亚胺薄膜(HBPI-MPC薄膜)。
(3)最后将步骤(2)的薄膜在去离子水中室温下震荡5小时，以除去膜表面未接枝的MPC，此震荡清洗步骤重复3次；最后，将所得HBPI-MPC膜在室温下真空干燥至恒重，命名为HBPI-5MPC。
实施例2
(1)氨基封端的超支化聚酰亚胺(AM-HBPI)的制备：方法同实施例1。
(2)AM-HBPI薄膜接枝改性：将0.6g的AM-HBPI粉末溶解在10mlNMP中，搅拌均匀后加入10mol％的2-甲基丙烯酰氧乙基磷酸胆碱(MPC)的水溶液(其中mol％＝n(MPC)/n(HBPI)*100％)，室温搅拌26h，将混合液平铺在干燥清洁的玻璃板上，然后置于干燥箱内干燥，100℃烘24h，除去溶剂；梯度升温160℃，220℃，分别保温2h，最后自然冷却，得到超支化聚酰亚胺薄膜(HBPI-MPC薄膜)。
(3)最后将步骤(2)的薄膜在去离子水中室温下震荡8小时，以除去膜表面未接枝的MPC，此震荡清洗步骤重复3次；最后，将所得HBPI-MPC膜在室温下真空干燥至恒重，命名为HBPI-10MPC。
实施例3
(1)氨基封端的超支化聚酰亚胺(AM-HBPI)的制备：方法同实施例1。
(2)AM-HBPI薄膜接枝改性：将0.6g的AM-HBPI粉末溶解在10mlNMP中，搅拌均匀后加入15mol％的2-甲基丙烯酰氧乙基磷酸胆碱(MPC)的水溶液(其中mol％＝n(MPC)/n(HBPI)*100％)，室温搅拌25h，将混合液平铺在干燥清洁的玻璃板上，然后置于干燥箱内干燥，100℃烘20h，除去溶剂；梯度升温140℃，200℃，分别保温1.5h，最后自然冷却，得到超支化聚酰亚胺薄膜(HBPI-MPC薄膜)。
(3)最后将步骤(2)的薄膜在去离子水中室温下震荡6.5小时，以除去膜表面未接枝的MPC，此震荡清洗步骤重复3次；最后，将所得HBPI-MPC膜在室温下真空干燥至恒重，命名为HBPI-15MPC。
实施例4
(1)氨基封端的超支化聚酰亚胺(AM-HBPI)的制备：方法同实施例1。
(2)AM-HBPI薄膜接枝改性：将0.6g的AM-HBPI粉末溶解在10mlNMP中，搅拌均匀后加入20mol％的2-甲基丙烯酰氧乙基磷酸胆碱(MPC)的水溶液(其中mol％＝n(MPC)/n(HBPI)*100％)，室温搅拌25h，将混合液平铺在干燥清洁的玻璃板上，然后置于干燥箱内干燥，100℃烘20h，除去溶剂；梯度升温140℃，200℃，分别保温1.5h，最后自然冷却，得到超支化聚酰亚胺薄膜(HBPI-MPC薄膜)。
(3)最后将步骤(2)的薄膜在去离子水中室温下震荡6.5小时，以除去膜表面未接枝的MPC，此震荡清洗步骤重复3次；最后，将所得HBPI-MPC膜在室温下真空干燥至恒重，命名为HBPI-20MPC。
我们对HBPI-15MPC的薄膜进行了FTIR光谱分析，具体结果见图1。从图1的a曲线中可以看出，2927cm-1(CH3多重峰)，1773cm-1(C＝O对称伸缩峰)，1721cm-1(C＝O不对称伸缩峰)，1378cm-1(C-N伸缩振动峰)，738cm-1(C＝O弯曲振动峰)为HBPI的典型特征吸收峰，由此说明HBPI已完全形成。在b曲线上新增了1215cm-1(P＝O吸收峰)，1073cm-1(P-O吸收峰)，947cm-1(-N+(CH3)3吸收峰)的吸收峰，证明了MPC分子已经通过迈克尔加成反应接枝到HBPI分子上。另外，在3350cm-1处出现的吸收峰为水峰，因为MPC分子易吸水，在测试过程中也吸收了一定量的水分，这也从侧面说明MPC分子接枝在HBPI分子上了。
我们对实施例1-4制备的HBPI-MPC薄膜进行体外血小板黏附性能测试，其方法为：①将新鲜血液(3.8％枸橼酸钠作抗凝剂)在2000r/min的速率下离心15min，收集上层富血小板血浆PRP。②将HBPI-MPC薄膜(0.5*0.5cm2)在PBS中浸泡24h(达到溶胀平衡)。③在37℃恒温下，将步骤②处理过的HBPI-MPC薄膜在PRP溶液中恒温1.5h。④将步骤③处理的HBPI-MPC薄膜用PBS多次冲洗，然后置于2.5％的戊二醛(以PBS作溶剂)中30min。⑤将步骤④处理的HBPI-MPC薄膜脱水(放入不同浓度的乙醇水溶液(50，60，70，80，90和100％)，每种溶液中浸泡30min)，室温下干燥。⑥将步骤⑤干燥的HBPI-MPC薄膜喷金，用SEM观察样品表面的血小板粘附情况，结果如图2。
以空白PI薄膜作为对照，从图2中可以观察到，空白PI薄膜表面黏附的血小板数量最多，并且多数血小板为变形和伸展状态，形貌发生了明显的变化，表明血小板可能已被激活。HBPI-5MPC和HBPI-10MPC对血小板黏附情况已经有所改善，表现为薄膜表面血小板吸附数量减少，血小板之间逐渐分离，不再发生聚集现象。当MPC添加量达到15％时，HBPI接枝薄膜对血小板的黏附性明显降低，当MPC达到20％时，HBPI接枝薄膜只黏附了很少的血小板细胞，并且血小板互相分离，血小板形态更接近圆形，说明其变形程度较低。由图2可知，抗血小板黏附的能力可能与MPC的接枝量有关。当MPC和PC基团引入HBPI薄膜后，薄膜表面形成类似细胞膜结构，随着MPC接枝量的增加，薄膜表面的MPC分子越多，HBPI-MPC薄膜表面的抗血小板黏附性也会降低，使得薄膜血液相容性得到了很好的改善。
我们对实施例1-4制备的HBPI-MPC薄膜进行了复钙时间测试，其方法为：①将HBPI-MPC薄膜(10mm*10mm)在生理盐水中浸泡24h(达到溶胀平衡)。②37℃恒温水浴，在步骤①处理的HBPI-MPC薄膜中分别加入1.5ml血浆中，然后分别加入0.2ml CaCl2(0.1025mol/L)，秒表计时，当出现纤维状物时停止计时，结果见表1，表1为HBPI-MPC薄膜的复钙时间(RT)。RT的测定原理为：在没有Ca+的血浆中重新加入Ca+，内源性凝血过程重现的时间，RT越大，表明该材料的抗凝血性能越好。由上可以看出，随着MPC接枝量的增加，由空白HBPI薄膜的RT＝300s增长到HBPI-MPC薄膜的RT＝551s，表示其抗凝血性有所改善，说明MPC的加入能有效的改善HBPI的生物相容性。
表1 HBPI-MPC薄膜的复钙时间(RT)
我们对实施例1-4制备的HBPI-MPC薄膜进行了抗细菌黏附性测试，其方法为：①将HBPI-MPC薄膜分别加入0.5个麦氏浊度的革兰氏染色阳性球菌和革兰氏染色阴性杆菌细菌液(生理盐水作溶剂)中，37℃恒温水浴，1h。②将步骤①处理的HBPI-MPC薄膜用PBS多次清洗，然后用2.5％的戊二醛固定，脱水，用SEM观察，结果见图3。图3为HBPI-MPC薄膜的细菌粘附性测试的SEM图片，通过统计图片中的细菌数来判断材料的抗菌性。已有大量研究表明，带有季铵盐结构的高分子材料有优异的抗菌性能，且高分子抗菌材料具有使用寿命长，可重复使用等优势。因MPC分子中含有季铵盐结构，因此HBPI-MPC接枝改性材料也具有了相对于空白HBPI较好的抗菌性。

Claims (2)

1.一种超支化聚酰亚胺抗凝血抗菌材料的制备方法，其特征在于：用2-甲基丙烯酰氧乙基磷酸胆碱对氨基封端的超支化聚酰亚胺的表面进行接枝改性，形成超支化聚酰亚胺薄膜，具体步骤如下：
(1)氨基封端的超支化聚酰亚胺的制备：将1,3,5-三(4-氨基苯氧基)苯和N-甲基吡咯烷酮置于烧瓶中并磁力搅拌，冰浴冷却，在N2保护下，将双酚A型二酐和N-甲基吡咯烷酮的混合溶液在1～3h内缓慢滴入其中，滴加完毕后在常温下反应1～2h，然后滴加异喹啉，120℃反应3～5h，180～200℃反应16～24h，冷却至室温后，加入无水乙醇，并清洗，产物80℃真空干燥24h，制得氨基封端的超支化聚酰亚胺；
所述的1,3,5-三(4-氨基苯氧基)苯和N-甲基吡咯烷酮的质量比为1:20～26；
所述的双酚A型二酐和N-甲基吡咯烷酮的混合溶液的浓度为4％～6％；
所述的1,3,5-三(4-氨基苯氧基)苯与双酚A型二酐的摩尔比为1:1；
(2)氨基封端的超支化聚酰亚胺薄膜接枝改性：将步骤(1)的氨基封端的超支化聚酰亚胺粉末溶解在N-甲基吡咯烷酮中，搅拌均匀后加入2-甲基丙烯酰氧乙基磷酸胆碱，室温搅拌24～26h得混合液，将上述混合液平铺在玻璃板上，置于干燥箱内干燥，100℃烘18～24h，升温至120～160℃并保温1～2h，再次升温至180-220℃，最后自然冷却，得到超支化聚酰亚胺薄膜；
所述的2-甲基丙烯酰氧乙基磷酸胆碱与氨基封端的超支化聚酰亚胺的摩尔比5～20％；
(3)将步骤(2)的超支化聚酰亚胺薄膜放置在去离子水中于室温下震荡5～8h，除去膜表面未接枝的2-甲基丙烯酰氧乙基磷酸胆碱，此震荡清洗步骤重复3次，最后将所得超支化聚酰亚胺薄膜在室温下真空干燥至恒重。
2.一种超支化聚酰亚胺抗凝血抗菌材料的应用：其特征在于：该超支化聚酰亚胺薄膜可作为抗凝血抗菌材料。
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Denomination of invention: Preparation and application of a hyperbranched polyimide anticoagulant antibacterial material

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