CN109988280B - 一种活性氧响应性的可降解聚氨酯材料及其制备方法 - Google Patents
一种活性氧响应性的可降解聚氨酯材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种活性氧响应性的可降解聚氨酯材料及其制备方法，它包括可生物降解的聚酯二醇软段和由饱和脂肪族二异氰酸酯及活性氧响应性小分子二胺组成的硬段。该材料以聚ε‑己内酯二醇(PCL)或聚富马酸丙二醇酯(PPF)为大分子二元醇，以饱和脂肪族二异氰酸酯为原料，以活性氧响应性小分子二胺为扩链剂，采用二步扩链法制备。本发明制备的聚氨酯弹性体具有良好的生物相容性，且具有对活性氧的响应性，材料本身及降解产物对人体无害，能广泛应用于生物医药及组织工程等领域，可用于骨修复和心肌再生。
Description
技术领域
本发明涉及一种活性氧响应性的可降解聚氨酯材料及其制备方法，属于生物医用材料技术领域。
背景技术
聚氨酯材料由于其硬段和软段间的热力学不相容所产生的微相分离结构，赋予了它良好的力学性能，且其结构中大量极性氨基甲酸酯基团的存在为材料提供了良好的生物相容性，因此聚氨酯材料是一类非常具有医用价值的高分子材料。
目前许多科研工作者致力于生物响应性材料的研究，以期望解决生物材料的降解速率与体内组织再生速率的匹配问题。生物响应性高分子材料能够在生物体内微环境的变化时，改变材料本身的性能，触发材料结构发生断裂，造成响应性降解。活性氧作为生物因素一直备受关注，活性氧(ROS)响应性生物材料也大量涌现出来。
酮缩硫醇化合物能够对活性氧敏感，而对酸、碱和蛋白酶催化的降解具有良好的耐受性，有报道利用巯基乙胺为原料合成了ROS响应性的链接剂，再通过缩合反应得到活性氧响应性的聚合物作为DNA的运输载体，该聚合物对酸碱具有良好的稳定性，用于高浓度活性氧环境的癌症细胞的靶向基因传递。然而，迄今为止报道的大部分基于酮缩硫醇化合物的材料都是以纳米粒子的形式存在，多用于作为药物的传递载体。
本发明将酮缩硫醇二胺小分子化合物作为扩链剂引入聚氨酯材料中，制得的含有活性氧响应性的聚氨酯材料能够提供干预生物体内ROS变化的响应位点，具有良好的生物响应性和生物可降解性。该活性氧响应性的聚氨酯材料不仅能够保留聚氨酯材料优异的力学性能和良好的生物相容性，同时该材料为线型高分子，加热可以熔融且在适当溶剂中可以溶解，具有良好的可加工性能，可以加工成薄膜或支架材料，因此在骨修复、心肌再生等方面的具有重要的应用。
发明内容
本发明的目的是为了解决现有医用可降解聚氨酯材料的降解速率与体内组织再生速率的匹配问题，提供一种活性氧响应性的可降解聚氨酯材料及其制备方法。该材料具有优异的力学性能和良好的生物相容性，且具有设计性强的优点，可以通过调控软硬段比例来调节材料的力学性能和降解性能。
本发明的目的是通过以下技术方案实现的。
本发明的活性氧响应性的可降解聚氨酯材料，包括聚酯二醇软段和饱和脂肪族二异氰酸酯及活性氧响应性小分子二胺组成的硬段。
所述的活性氧响应性小分子二胺为酮缩硫醇二胺，其合成路线如下：
进一步的，所述的聚酯二醇为聚ε-己内酯二醇(PCL)或聚富马酸丙二醇酯(PPF)。
更进一步的，所述的聚ε-己内酯二醇(PCL)的数均分子量为2000。
更进一步的，所述的聚富马酸丙二醇酯的数均分子量为1000。
进一步的，所述的饱和脂肪族二异氰酸酯为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)或4,4’-二环己基甲烷二异氰酸酯(HMDI)中的一种。
进一步的，所述的活性氧响应性的可降解聚氨酯材料是以聚ε-己内酯二醇或聚富马酸丙二醇酯为大分子二元醇，以饱和脂肪族二异氰酸酯为原料，以活性氧响应性小分子二胺为扩链剂，采用二步扩链法制备得到。
进一步的，所述的活性氧响应性的可降解聚氨酯材料的方法，包括以下步骤：
1)将聚酯二醇加入到干燥的容器中，减压除去残余的水分，然后加入无水N,N-二甲基甲酰胺溶剂溶解，再加入二异氰酸酯及催化剂二月桂酸二丁基锡，在氮气保护下65-75℃反应3-4h，得到异氰酸酯基团封端的预聚物；其中二异氰酸酯中异氰酸酯基团的物质的量与聚酯二醇中羟基的物质的量之比为2:1，二月桂酸二丁基锡的物质的量为聚酯二醇的羟基的物质的量的0.2％；
2)在步骤1)制备的异氰酸酯基团封端的预聚物中加入活性氧响应性小分子二胺的稀释液，其中所述的活性氧响应性小分子二胺的稀释液是将活性氧响应性小分子二胺用无水N,N-二甲基甲酰胺溶剂按照10％g/mL的浓度稀释后获得；然后于70℃扩链反应至少7h，得到聚氨酯溶液，活性氧响应性小分子二胺的物质的量与聚酯二醇的物质的量相同，且均为二异氰酸酯物质的量的一半；
3)在步骤2)制备的聚氨酯溶液中加入无水乙醇并保持在70℃封端1h；
4)将经步骤3)处理后的聚氨酯溶液倒入无水乙醇中沉淀，离心、收集，将收集的聚氨酯固体再次溶于N,N-二甲基甲酰胺中，并再次倒入无水乙醇中沉淀，反复数次，最后将所得的聚氨酯固体从无水乙醇中转移到超纯水中，待乙醇除尽后，冷冻干燥，得到活性氧响应性的聚氨酯材料。
进一步的，所述的活性氧响应性的可降解聚氨酯材料能够用于加工成薄膜或支架材料，应用于生物医药及组织工程领域，用于骨修复和心肌再生。
与现有的医用聚氨酯相比，本发明制备的活性氧响应性的可降解聚氨酯材料具有以下优点：
1)本发明中，通过引入ROS响应性的扩链剂，为聚氨酯材料提供了体内组织环境响应性断裂的位点。
2)本发明中，以低聚物聚酯二醇作为软段，制备的聚氨酯材料具有聚酯二醇的可降解性和力学性能。
3)本发明中，可以通过改变软硬段比例，影响ROS响应性扩链剂的接入量，可相应的调控聚氨酯材料的降解速率；也可通过对配方进行设计，制备符合所需降解速率要求的聚氨酯材料。
4)本发明中，以饱和脂肪族二异氰酸酯作为硬段，使制得的聚氨酯材料的降解产物无致癌等毒副作用。
5)本发明中，得到的活性氧响应性的可降解聚氨酯材料为线性聚氨酯，能够再次溶解并加工成薄膜或多孔支架材料。
附图说明
图1为酮缩硫醇小分子二胺的分子式及1H NMR(CDCl3)谱图；
图2为实施例1中该ROS响应性聚氨酯材料的合成线路图；
图3为实施例2中该ROS响应性聚氨酯材料的合成线路图；
图4为实施例1中该ROS响应性聚氨酯材料的1H NMR(DMSO)谱图；
图5为实施例2中该ROS响应性聚氨酯材料的1H NMR(DMSO)谱图。
具体实施方式
以下结合实例进一步说明本发明的技术方案，但这些实例并不用来限制本发明。本发明的活性氧响应性的可降解聚氨酯材料的合成路线如图2，3。
实施例1
活性氧响应性的可降解聚氨酯材料(PCL/HDI 2:1)，包括软段和硬段，所述的软段是数均分子量为2000的聚ε-己内酯二醇，所述的硬段是脂肪族二异氰酸酯HDI以及ROS响应性酮缩硫醇二胺扩链剂。
具有如下结构
其制备包括以下步骤：
取数均分子量为2000的PCL 2.0213g加入到干燥的三口烧瓶中，计算得到该PCL的羟基的摩尔数为2.0213mmol，110℃减压蒸馏1h，除去残余的水分，通入氮气。降温到70℃后，加入20mL无水N,N-二甲基甲酰胺溶剂进行溶解，加入0.3320g HDI，0.004mmol催化剂二月桂酸二丁基锡，在氮气保护下于70℃反应3h。取0.192g酮缩硫醇二胺小分子，溶于2mL无水N,N-二甲基甲酰胺溶剂中，并逐滴加入到上述溶液中，并在70℃下扩链反应7h。加入0.3g无水乙醇反应1h进行封端。反应完毕后，将得到聚氨酯溶液倒入无水乙醇中进行沉淀，离心、收集，将收集的聚氨酯固体再次溶于N,N-二甲基甲酰胺中，并再次倒入无水乙醇中沉淀，反复3次。最终用超纯水反复洗涤，置换出聚氨酯中的无水乙醇，冷冻干燥24h，得到聚氨酯固体，测得聚合物的数均分子量为52.1kDa。将聚氨酯固体溶于氘代二甲亚砜(DMSO)中检测材料的核磁共振氢谱1H-NMR(附图4)，通过对分子结构中各种质子氢的归属，其中化学位移δ＝1.6ppm是聚氨酯结构中酮缩硫醇上甲基CH3质子氢的特征峰，δ＝1.25和2.93ppm为聚氨酯HDI链段结构中CH2质子氢的特征峰，δ＝2.27和3.96ppm为聚氨酯中PCL链段中-CHCH 2CO-和-CH2CH 2O-质子氢的特征峰，测试结果表明成功合成了ROS响应性PCL聚氨酯材料。
将制得的聚氨酯溶于六氟异丙醇中，浇入到聚四氟模具中，空气氛围下常温挥发48h，后于40℃真空干燥24h除去残余溶剂，得到聚氨酯薄膜。为考察本发明制备的聚氨酯的降解性能，进行了体外降解实验，降解条件为PBS缓冲液和1mmol/L双氧水溶液，将5mm×5mm的聚氨酯薄膜放入10mL菌种中，加入5mL溶液，37℃恒温水浴中震荡，14天后取出样品，用蒸馏水洗涤3次，冷冻干燥24h。将聚合物溶于N,N-二甲基甲酰胺中，通过凝胶渗透色谱(GPC)测定降解前后的分子量，浸泡在PBS中聚氨酯的数均分子量为48.5kDa，在1mmol/L双氧水溶液降解14天后，聚氨酯的数均分子量为12.8kDa。
为考察本发明制备的聚氨酯材料对细胞的毒性，将聚氨酯材料剪成1mm×1mm碎片，并把材料浸泡在培养基中(10mg/mL)，37℃条件下浸泡24h，将得到的浸提液用0.22.μm的微孔滤膜过滤灭菌。将内皮细胞以每孔5×103的密度接种于96孔的细胞培养板中，用正常的培养基培养24h，然后换成聚氨酯材料的浸提液继续进行细胞培养，培养1，2，4天后，用cck8法进行细胞活性的检测，细胞的存活率均高于85％，表明聚氨酯材料对细胞的毒性可以忽略。
实施例2
活性氧响应性的可降解聚氨酯材料(PPF/HDI 2:1)，包括软段和硬段，所述的软段是分子量为1000的聚富马酸丙二醇酯PPF，所述的硬段是脂肪族二异氰酸酯HDI以及ROS响应性酮缩硫醇二胺扩链剂。
具有如下结构：
其制备包括以下步骤：
取数均分子量为1000的PPF 2.0368g加入到干燥的三口烧瓶中，计算得到PPF的羟基摩尔数为3.54mmol，110℃减压蒸馏1h，除去残余的水分，通入氮气。降温到70℃后，加入20mL无水N,N-二甲基甲酰胺溶剂进行溶解，加入0.5950g HDI，0.007mmol催化剂二月桂酸二丁基锡，在氮气保护下于70℃反应3h。取0.3430g酮缩硫醇二胺小分子，溶于3.5mL无水N,N-二甲基甲酰胺中，并逐滴加入到上述溶液中，并在70℃下扩链反应7h。加入0.5g无水乙醇反应1h进行封端。反应完毕后，将得到聚氨酯溶液倒入无水乙醇中进行沉淀，离心、收集，将收集的聚氨酯固体再次溶于N,N-二甲基甲酰胺中，并再次倒入无水乙醇中沉淀，反复3次。最终用超纯水反复洗涤，置换出聚氨酯中的无水乙醇，冷冻干燥24h，得到聚氨酯固体，测得聚合物的数均分子量为38.2kDa。将聚氨酯固体溶于氘代二甲亚砜(DMSO)中检测材料的核磁共振氢谱1H-NMR(附图5)，通过对分子结构中各种质子氢的归属，其中化学位移δ＝1.6ppm是聚氨酯结构中酮缩硫醇上甲基CH3质子氢的特征峰，δ＝1.25和2.93ppm为聚氨酯HDI链段结构中CH2质子氢的特征峰，δ＝6.73ppm为聚氨酯中PPF链段中双键上质子氢的特征峰，测试结果表明成功合成了ROS响应性PPF聚氨酯材料。
所得的聚氨酯浸泡在PBS溶液中14天后，数均分子量为36.8kDa，在1mmol/L双氧水溶液中降解14天后，聚氨酯的数均分子量的9.3kDa。且材料浸提液的细胞的存活率高于85％，表明聚氨酯材料对细胞的毒性可以忽略。
Claims (4)
1.一种活性氧响应性的可降解聚氨酯材料的制备方法，其特征在于，所述可降解聚氨酯材料包括聚酯二醇软段和由饱和脂肪族二异氰酸酯及活性氧响应性小分子二胺组成的硬段；所述的活性氧响应性小分子二胺为酮缩硫醇二胺，所述的聚酯二醇为聚ε-己内酯二醇或聚富马酸丙二醇酯；制备方法包括以下步骤：
1）将聚酯二醇加入到干燥容器中，减压除去残余的水分，然后加入无水N,N-二甲基甲酰胺溶剂溶解，再加入二异氰酸酯及催化剂二月桂酸二丁基锡，在氮气保护下65-75℃反应3-4h，得到异氰酸酯基团封端的预聚物；其中二异氰酸酯中异氰酸酯基团与聚酯二醇中羟基的摩尔比为2:1，二月桂酸二丁基锡的物质的量是聚酯二醇的羟基的物质的量的0.2 %；
2）在步骤1）制备的异氰酸酯基团封端的预聚物中加入活性氧响应性小分子二胺的稀释液，其中,所述的活性氧响应性小分子二胺的稀释液是将活性氧响应性小分子二胺按10%g/mL用无水N,N-二甲基甲酰胺溶剂进行稀释获得；然后于70℃扩链反应至少7h，得到聚氨酯溶液，活性氧响应性小分子二胺的物质的量与聚酯二醇的物质的量相同，且均为二异氰酸酯物质的量的一半；
3）在步骤2）制备的聚氨酯溶液中加入无水乙醇并保持在70℃封端1h；
4）将经步骤3）处理后的聚氨酯溶液倒入无水乙醇中沉淀，离心、收集，将收集的聚氨酯固体再次溶于N,N-二甲基甲酰胺中，并再次倒入无水乙醇中沉淀，反复数次，最后将所得的聚氨酯固体从无水乙醇中转移到超纯水中，待乙醇除尽后，冷冻干燥，得到活性氧响应性的可降解聚氨酯材料。
2.根据权利要求1所述的活性氧响应性的可降解聚氨酯材料的制备方法，其特征在于，所述的聚ε-己内酯二醇的数均分子量为2000。
3.根据权利要求1所述的活性氧响应性的可降解聚氨酯材料的制备方法，其特征在于，所述的聚富马酸丙二醇酯的数均分子量为1000。
4.根据权利要求1所述的活性氧响应性的可降解聚氨酯材料的制备方法，其特征在于，所述的饱和脂肪族二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯 或4,4’-二环己基甲烷二异氰酸酯中的一种。
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