CN106397727A - 一种高生物相容性的三嵌段共聚物及其制备方法和应用 - Google Patents
一种高生物相容性的三嵌段共聚物及其制备方法和应用 Download PDFInfo
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- CN106397727A CN106397727A CN201610792708.4A CN201610792708A CN106397727A CN 106397727 A CN106397727 A CN 106397727A CN 201610792708 A CN201610792708 A CN 201610792708A CN 106397727 A CN106397727 A CN 106397727A
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- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种高生物相容性的三嵌段共聚物，该三嵌段共聚物的通式为A‑b‑B‑b‑C，其中，A、B、C为嵌段结构，b为嵌段扩链剂，A代表高亲水性的软段材料，为聚乙二醇、聚丙二醇、聚醚胺中至少一种构成的嵌段；B代表刚性高疏水性的硬段材料，为聚碳酸酯、聚甲基丙烯酸甲酯中至少一种构成的嵌段；C代表柔性多聚物，为聚二甲基硅氧烷、聚(甲基丙烯酸‑2‑羟乙酯)中至少一种构成的嵌段。用该三嵌段共聚物制备的渗透膜拥有高度可控的小分子渗透率，良好的耐水耐热性和可调节的亲水性和生物相容性。
Description
技术领域
本发明涉及嵌段共聚物技术领域，具体涉及一种高生物相容性的三嵌段共聚物及其制备方法和应用。
背景技术
植入式生物传感器是指一种可以被部分或者全部植入人体的传感器设备，其可以在不需要外加试剂和预先分离处理体液或血液的条件下测定目标分析物分子的含量。植入式生物传感器的优点是可以连续性地测定体内某些随时间变化的重要生理和病理参数，比如血氧，血糖，病毒抗体等，从而更直接地反映被测对象的体征因环境变化、体力活动、饮食和药物而产生的变化。通常来讲，植入式传感器的感应部分需要与组织内的被分析物产生某种互动才可以检测到被分析物的存在，因此，植入式生物传感器与植入组织的互动可控性代表了植入式传感技术的主要特点和技术难度。由于人体内部环境，尤其是微观生物环境异常复杂，目前人类对植入式传感器与植入组织之间的相互作用了解有限。例如植入传感器的表面物质与人体成分的差异性会引发人体的异体排斥反应机制，从而生成一层主要由纤维蛋白组成的生物隔离层。隔离层会造成传感器与植入组织隔绝，使传感器与组织液的分子渗透和交换受到阻碍，传感器对分析物浓度的检测将失去准确性。因此如何减少异物排斥反应，提高传感器的生物相容性是提高传感器准确性和使用寿命的关键，这通常是由在传感器与组织接触的表面增加一层高生物相容性的薄膜来实现的。
生物相容性渗透膜对其成分有非常高的技术性要求，例如极低的细胞毒性，良好的亲水性和生物相容性，对目标分析物适当的渗透扩散性能和对潜在干扰物的阻隔性能，以及在给定的使用时间内耐水解，耐热和对其他降解机制的抗性等等。同时由于生产、运送和贮藏的要求，还需要该材料具有稳定的化学分子结构，使其在被使用之前的较长时间内保持稳定的性质。因此，目前的生物相容性渗透膜的选择非常有限。目前，此类渗透膜多采用聚乙二醇，聚(2-甲基丙烯酸羟乙酯)等被普遍认可的高生物相容性多聚物或其混合物制成，但多数对渗透扩散的可控性较差且耐水耐热性差，会受周围环境的影响产生性质变化，因而不利于生产和长期贮藏。
发明内容
本发明目的是提供一种高生物相容性的三嵌段共聚物及其制备方法和应用，以解决现有技术的不足。
本发明采用以下技术方案：
一种高生物相容性的三嵌段共聚物，该三嵌段共聚物的通式为A-b-B-b-C，其中，A、B、C为嵌段结构，b为嵌段扩链剂，A代表高亲水性的软段材料，为聚乙二醇、聚丙二醇、聚醚胺中至少一种构成的嵌段；B代表刚性高疏水性的硬段材料，为聚碳酸酯、聚甲基丙烯酸甲酯中至少一种构成的嵌段；C代表柔性多聚物，为聚二甲基硅氧烷、聚(甲基丙烯酸-2-羟乙酯)中至少一种构成的嵌段。
进一步地，b为异氰酸酯类扩链剂，包括二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种。
进一步地，A嵌段的数均分子量在200-10000；B嵌段的数均分子量在1000-20000；C嵌段的数均分子量在1000-20000。
进一步地，三类嵌段和嵌段扩链剂的质量份数如下：A嵌段为1-10份，B嵌段为1-5份，C嵌段为1-5份，嵌段扩链剂的重量比例为1-3份。
进一步地，A-b,B-b,C-b之间通过脲或氨基甲酸酯基共价键连接。
上述高生物相容性的三嵌段共聚物的制备方法，包括如下步骤：
步骤一、将高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物，加入到有机溶剂中，在30-45℃下混合均匀；
步骤二、向步骤一的混合溶液中加入催化剂，并逐滴加入嵌段扩链剂，升温至55-70℃，反应12-20h；
步骤三、向步骤二的反应溶液中添加去离子水，反应12h-18h；
步骤四、冷却后，将反应产物冲洗、过滤、干燥，得到所述的三嵌段共聚物。
进一步地，步骤一的有机溶剂包括四氢呋喃或异丁醇，有机溶剂的体积和高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物总质量比为2-10ml:1g。
进一步地，步骤二的催化剂包括三乙烯二胺或者二丁基二异辛酸锡。
进一步地，步骤三的去离子水的体积和高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物总质量比为1-10ml:1g。
上述高生物相容性的三嵌段共聚物在制备植入式生物传感器生物相容性渗透膜中的应用。
本发明的有益效果：
1、本发明结合了三种类型的单一多聚分子的优点使得其嵌段共聚物具有可调节渗透率，可调节物理性能和较好的水解稳定性和耐热稳定性等特性，与将三类多聚分子简单混合相比，使用二异氰酸酯类等异氰酸酯类扩链剂将它们通过扩链反应结合可防止成膜过程中出现的微相位分离现象。
2、本发明三嵌段共聚物成膜后其物理化学性质更稳定，比单纯的聚醚类和聚酯类聚氨酯耐水解耐热性能更好。
3、由于第二类硬段嵌段的存在，成膜后的共聚物分子不易发生因分子排列重组而造成的薄膜表面性质变化，尤其是亲水性的变化。
4、该多嵌段共聚物的亲水性，渗透性能和物理强度可以通过调节每种嵌段在材料中的百分比实现连续调节。
附图说明
图1为耐水解性能比较。
图2为耐热性能比较。
图3为薄膜表面亲水性接触角度贮藏稳定性比较。
具体实施方式
下面结合实施例和附图对本发明做更进一步地解释。下列实施例仅用于说明本发明，但并不用来限定本发明的实施范围。
一种高生物相容性的三嵌段共聚物，该三嵌段共聚物的通式为A-b-B-b-C，其中，A、B、C为嵌段结构，b为嵌段扩链剂，A-b,B-b,C-b之间通过脲或氨基甲酸酯基共价键连接。A代表高亲水性的软段材料，为聚乙二醇、聚丙二醇、聚醚胺中至少一种构成的嵌段，该类嵌段具有良好的水溶性，可以让目标分析物分子自由渗透。B代表刚性高疏水性的硬段材料，为聚碳酸酯、聚甲基丙烯酸甲酯中至少一种构成的嵌段，该类嵌段提供了必要的物理强度和耐热耐水解的性能，使渗透膜的稳定性更佳。C代表柔性多聚物，为聚二甲基硅氧烷、聚(甲基丙烯酸-2-羟乙酯)中至少一种构成的嵌段，这类嵌段起到了一定的过渡作用使得前两类嵌段在混合和成膜时不易发生微相分离。A嵌段的数均分子量在200-10000；B嵌段的数均分子量在1000-20000；C嵌段的数均分子量在1000-20000。b代表嵌段扩链剂，为异氰酸酯类扩链剂，包括二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种。嵌段与嵌段之间由异氰酸酯类扩链剂通过扩链机制连接，从而生成稳定的聚氨酯或者聚脲类多嵌段共聚物。三类嵌段和嵌段扩链剂的质量份数如下：A嵌段为1-10份，B嵌段为1-5份，C嵌段为1-5份，嵌段扩链剂的重量比例为1-3份。
上述高生物相容性的三嵌段共聚物的制备方法，包括如下步骤：
步骤一、将高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物，加入到有机溶剂中，在30-45℃下混合均匀；有机溶剂包括四氢呋喃或异丁醇，有机溶剂的体积和高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物总质量比为2-10ml:1g。
步骤二、向步骤一的混合溶液中加入催化剂，并逐滴加入嵌段扩链剂，升温至55-70℃，反应12-20h；催化剂包括三乙烯二胺或者二丁基二异辛酸锡。
步骤三、向步骤二的反应溶液中添加去离子水，反应12h-18h；去离子水的体积和高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物总质量比为1-10ml:1g。
步骤四、冷却后，将反应产物冲洗、过滤、干燥，得到所述的三嵌段共聚物。
上述高生物相容性的三嵌段共聚物在制备植入式生物传感器生物相容性渗透膜中的应用。制备的渗透膜拥有高度可控的小分子渗透率，良好的耐水耐热性和可调节的亲水性和生物相容性，这主要是由含有两性分子的多嵌段共聚脲或者聚氨酯来实现的。
实施例1
原料：聚醚胺，数均分子量1000，质量为25g；聚碳酸酯二元醇，数均分子量5000，质量为10g；二氨基封端聚二甲基硅氧烷，数均分子量5000，质量为15g；四氢呋喃，100ml；二苯基甲烷二异氰酸酯，质量为12g；去离子水50ml。
步骤一、将聚醚胺、聚碳酸酯二元醇、二氨基封端聚二甲基硅氧烷，加入到四氢呋喃中，在40℃下混合均匀。
步骤二、向步骤一的混合溶液中加入三乙烯二胺，并逐滴加入二苯基甲烷二异氰酸酯，升温至65℃，反应12h。
步骤三、向步骤二的反应溶液中添加去离子水，反应12h。
步骤四、冷却后，将反应产物冲洗、过滤、干燥，得到所述的三嵌段共聚物。
实施例2
原料：氨基封端聚乙二醇，数均分子量2000，质量为20g；聚碳酸酯二元醇，数均分子量2000，质量为15g；聚甲基丙烯酸甲酯，数均分子量2000，质量为15g；二氨基封端聚二甲基硅氧烷，数均分子量8000，质量为15g；四氢呋喃，500ml；3g二苯基甲烷二异氰酸酯和9g二环己基甲烷二异氰酸酯；去离子水500ml。
步骤一、将氨基封端聚乙二醇、聚碳酸酯二元醇、聚甲基丙烯酸甲酯、二氨基封端聚二甲基硅氧烷，加入到四氢呋喃中，在30℃下混合均匀。
步骤二、向步骤一的混合溶液中加入三乙烯二胺，并逐滴加入二苯基甲烷二异氰酸酯和二环己基甲烷二异氰酸酯的混合液，升温至55℃，反应14h。
步骤三、向步骤二的反应溶液中添加去离子水，反应18h。
步骤四、冷却后，将反应产物冲洗、过滤、干燥，得到所述的三嵌段共聚物。
实施例3
原料：氨基封端聚丙二醇，分子量500，质量15g；聚醚胺，分子量600，质量10g；聚(双酚A碳酸酯)，分子量为5000，质量25g；二氨基封端聚二甲基硅氧烷，分子量为20000，质量10g；聚(甲基丙烯酸-2-羟乙酯)，分子量为5000，质量5g；异丁醇150ml；六亚甲基二异氰酸酯，质量15g；去离子水150ml。
步骤一、将氨基封端聚丙二醇、聚醚胺、聚(双酚A碳酸酯)、二氨基封端聚二甲基硅氧烷、聚(甲基丙烯酸-2-羟乙酯)，加入到异丁醇中，在35℃下混合均匀。
步骤二、向步骤一的混合溶液中加入二丁基二异辛酸锡，并逐滴加入六亚甲基二异氰酸酯，升温至60℃，反应16h。
步骤三、向步骤二的反应溶液中添加去离子水，反应14h。
步骤四、冷却后，将反应产物冲洗、过滤、干燥，得到所述的三嵌段共聚物。
实施例4
原料：氨基封端聚乙二醇，数均分子量10000，质量30g；聚碳酸酯二元醇，数均分子量2000，质量5g；聚甲基丙烯酸甲酯，数均分子量2000，质量5g；聚(甲基丙烯酸-2-羟乙酯)，数均分子量20000，质量15g；异丁醇600ml；二环己基甲烷二异氰酸酯20g；去离子水300ml。
步骤一、将氨基封端聚乙二醇、聚碳酸酯二元醇、聚甲基丙烯酸甲酯、聚(甲基丙烯酸-2-羟乙酯)，加入到异丁醇中，在45℃下混合均匀。
步骤二、向步骤一的混合溶液中加入二丁基二异辛酸锡，并逐滴加入二环己基甲烷二异氰酸酯，升温至70℃，反应20h。
步骤三、向步骤二的反应溶液中添加去离子水，反应16h。
步骤四、冷却后，将反应产物冲洗、过滤、干燥，得到所述的三嵌段共聚物。
耐水解性能比较
将实施例1制备的三嵌段共聚物和聚(己二酸乙二醇酯)所制成的聚酯聚氨酯、环氧乙烷-环氧丙烷所制成的聚醚聚氨酯分别制备成薄膜，进行耐水解性能比较。薄膜制备过程如下：所测材料溶解于有机溶剂如四氢呋喃中，然后旋涂于玻璃片表面并加热至40℃直至溶剂全部蒸发，使所测材料在玻璃表面形成薄膜。
将各样本薄膜(每个样本约0.1g)分别浸泡在10mL的0.1M氯化钠溶液中，在室温下(25℃)保存，在0、5、10、15、20、25天时取出样本，用去离子水清洗并干燥，然后将样本溶于有机溶剂如四氢呋喃，使用尺寸排阻色谱法(SEC)等方式测量其分子量分布并计算数均分子量。将计算得出的数均分子量与未浸泡过的样本相比即得到“平均分子量/初始分子量”的比值，用百分比的形式表示。如图1所示，聚酯类聚氨酯浸泡后其平均分子量显著降低，表示其分子已部分分解，其耐水解性较差。实施例1所制备的新材料和聚醚类聚氨酯拥有较好的耐水解抗性。
耐热性能比较
将实施例1制备的三嵌段共聚物和聚(己二酸乙二醇酯)所制成的聚酯聚氨酯、环氧乙烷-环氧丙烷聚醚所制成的聚醚聚氨酯分别制备成薄膜，进行耐热性能比较。薄膜制备过程如下：所测材料溶解于有机溶剂如四氢呋喃中，然后旋涂于玻璃片表面并加热至40℃直至溶剂全部蒸发，使所测材料在玻璃表面形成薄膜。
将各样本薄膜(每个样本约0.1g)放在玻璃质培养皿中，放在60℃干燥箱内保存，在0、5、10、15、20周后取出一个样本，用去离子水清洗并干燥，然后将样本溶于有机溶剂如四氢呋喃，使用尺寸排阻色谱法(SEC)等方式测量其分子量分布并计算数均分子量。将计算得出的数均分子量与未浸泡过的样本相比即得到“平均分子量/初始分子量”的比值，用百分比的形式表示。
如图2所示，聚醚类聚氨酯浸泡后其平均分子量显著降低，表示其分子已因受热氧化而部分分解，其耐热性较差。实施例1所制备的新材料和聚脂类聚氨酯拥有较好的耐热分解抗性。
薄膜表面亲水性接触角度贮藏稳定性比较
新材料为实施例1制备的三嵌段共聚物和PEG+PDMS共混物、PEG+PDMS共聚物进行薄膜表面亲水性接触角度比较。其中PEG+PDMS共混物是把聚乙二醇(PEG，仅含有A类嵌段的多聚物)和聚二甲基硅氧烷(PDMS，仅含有B类或者C类嵌段的多聚物)混合而制成的高分子材料，共聚物是把上述两种均聚物通过聚合反应生成聚脲或聚氨酯的双嵌段高分子材料。
亲水接触角实验方法为把所测材料溶解于有机溶剂如四氢呋喃中，然后旋涂于玻璃片表面并加热至40℃直至溶剂全部蒸发，使所测材料在玻璃表面形成薄膜，然后把薄膜样本保存在室温(约25℃)和室内常规相对湿度(约20％-40％)中。定期(例如每个月)将样本取出，在其上滴上一滴约0.05-0.1mL的去离子水，并使用接触角分析仪测定水滴与薄膜表面形成的角度，角度越小说明材料表面亲水性越高。
如图3所示，均聚物共混物和双嵌段共聚物在放置一段时间后，其表面亲水性有所降低，而实施例1中所制备的新材料的表面亲水性比较稳定，在室温下保存6个月依然不会有很大的改变。
Claims (10)
1.一种高生物相容性的三嵌段共聚物，其特征在于，该三嵌段共聚物的通式为A-b-B-b-C，其中，A、B、C为嵌段结构，b为嵌段扩链剂，A代表高亲水性的软段材料，为聚乙二醇、聚丙二醇、聚醚胺中至少一种构成的嵌段；B代表刚性高疏水性的硬段材料，为聚碳酸酯、聚甲基丙烯酸甲酯中至少一种构成的嵌段；C代表柔性多聚物，为聚二甲基硅氧烷、聚(甲基丙烯酸-2-羟乙酯)中至少一种构成的嵌段。
2.根据权利要求1所述的高生物相容性的三嵌段共聚物，其特征在于，b为异氰酸酯类扩链剂，包括二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或多种。
3.根据权利要求1所述的高生物相容性的三嵌段共聚物，其特征在于，A嵌段的数均分子量在200-10000；B嵌段的数均分子量在1000-20000；C嵌段的数均分子量在1000-20000。
4.根据权利要求1所述的高生物相容性的三嵌段共聚物，其特征在于，三类嵌段和嵌段扩链剂的质量份数如下：A嵌段为1-10份，B嵌段为1-5份，C嵌段为1-5份，嵌段扩链剂的重量比例为1-3份。
5.根据权利要求1所述的高生物相容性的三嵌段共聚物，其特征在于，A-b,B-b,C-b之间通过脲或氨基甲酸酯基共价键连接。
6.权利要求1-5任一权利要求所述的高生物相容性的三嵌段共聚物的制备方法，其特征在于，包括如下步骤：
步骤一、将高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物，加入到有机溶剂中，在30-45℃下混合均匀；
步骤二、向步骤一的混合溶液中加入催化剂，并逐滴加入嵌段扩链剂，升温至55-70℃，反应12-20h；
步骤三、向步骤二的反应溶液中添加去离子水，反应12h-18h；
步骤四、冷却后，将反应产物冲洗、过滤、干燥，得到所述的三嵌段共聚物。
7.根据权利要求6所述的高生物相容性的三嵌段共聚物的制备方法，其特征在于，步骤一的有机溶剂包括四氢呋喃或异丁醇，有机溶剂的体积和高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物总质量比为2-10ml:1g。
8.根据权利要求6所述的高生物相容性的三嵌段共聚物的制备方法，其特征在于，步骤二的催化剂包括三乙烯二胺或者二丁基二异辛酸锡。
9.根据权利要求6所述的高生物相容性的三嵌段共聚物的制备方法，其特征在于，步骤三的去离子水的体积和高亲水性的软段材料、刚性高疏水性的硬段材料、柔性多聚物总质量比为1-10ml:1g。
10.权利要求1-5任一权利要求所述的高生物相容性的三嵌段共聚物在制备植入式生物传感器生物相容性渗透膜中的应用。
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