CN111848918A - 一种血管支架用可生物降解聚氨酯及其合成方法 - Google Patents

一种血管支架用可生物降解聚氨酯及其合成方法 Download PDF

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CN111848918A
CN111848918A CN202010599441.3A CN202010599441A CN111848918A CN 111848918 A CN111848918 A CN 111848918A CN 202010599441 A CN202010599441 A CN 202010599441A CN 111848918 A CN111848918 A CN 111848918A
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梅其勇
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Abstract

本发明提供了一种血管支架用可生物降解聚氨酯及其合成方法，所述可生物降解聚氨酯材料结构式如下所示：
Figure DDA0002558668620000011
其中R2为二异氰酸酯除去端异氰酸酯基团‑NCO后的部分；Rt为三异氰酸酯除去端异氰酸酯基团‑NCO后的部分；R3为芳香族二元酚链段；n为≥1的整数。本发明通过引入动态共价交联键不仅可以同时提高生物降解聚氨酯的强度和韧性，还保留了其加工性能，并赋予其自修复功能。提供的可生物降解聚氨酯的方法生产成本低，工艺简便，易于操作。该可生物降解聚氨酯材料可用作高性能环境友好性高分子材料，并可用于制备高性能生物降解血管支架，具有很高的应用价值。

Description

一种血管支架用可生物降解聚氨酯及其合成方法
技术领域
本发明属于聚氨酯及其合成技术领域，涉及一种血管支架用可生物降解聚氨酯其合成方法，特别涉及一种动态共价键交联的高强度、高韧性的自修复可生物降解聚氨酯的合成方法，以及通过该方法获得的生物降解聚氨酯。
背景技术
聚氨基甲酸酯，简称聚氨酯，其主链上具有氨基甲酸酯(-NHCOO-)重复结构单元。通过改变聚氨酯的结构和组成，聚氨酯可具有广泛的力学性能和加工性能。聚氨酯材料由于其优异的弹性、韧性以及耐磨性和耐候性，被用于制造泡沫塑料、纤维、弹性体、合成革、涂料、胶黏剂、铺装材料和医用材料等，广泛应用于交通、建筑、轻工、纺织、机电、航空、医疗卫生等领域，已成为世界第六大合成材料。聚酯型和聚碳酸酯型聚氨酯由于其特殊的软硬段微相分离结构，具有很好的组织相容性及生物可降解性，已被广泛地生物医学领域(如血管支架、人工心脏瓣膜、主动脉内球囊、软骨等)。
但是聚酯型的生物降解聚氨酯材料应用时，如用作血管支架时仍然面临着力学性能不足(脆性大、径向强度不足)，缺乏自修复功能，无法满足实际应用要求。
通过在聚氨酯的分子结构中引入刚性基团，可以有效的提高基材的物理强度。如专利CN 110305281 A通过引入咔唑衍生物胺类聚醚多元醇，形成多苯环分子结构，从而显著增强聚氨酯泡孔结构强度。专利CN 109679050 A提供了一种通过引入环氧树脂同时提高聚氨酯硬度和韧性的方法。对大分子链进行合理的设计和适当的交联是实现高分子材料高性能化非常有效的方法。CN 110643011 A和CN 110643015 A提供了一种高强度聚氨酯合成方法，该方法通过引入三官能度的单体或者扩链剂进行交联提高强度。但是这些聚氨酯均不可生物降解，缺乏生物相容性，不可用于生物医用。上述增韧增强的聚氨酯也不具有自修复功能。而且采用三官能度的单体或者扩链剂交联的聚氨酯不具有再加工性能。
发明内容
针对现有技术的不足，本发明的目的是提供一种血管支架用高强度、高韧性、自修复的生物降解聚氨酯其合成方法。本发明提供了一种新的合成路线，通过引入动态共价交联键合成强度、韧性、自修复性能兼优的可生物降解聚氨酯材料的合成，用于制备可个人定制的血管支架等。引入的动态共价交联键不仅可以同时提高生物降解聚氨酯的强度和韧性，还保留了其加工性能，并赋予其自修复功能。
本发明的目的是通过以下技术方案实现的：
本发明提供了一种可生物降解聚氨酯，其结构式如下所示：
Figure BDA0002558668600000021
其中，R1为脂肪族聚合物二元醇链段；R2为二异氰酸酯除去端异氰酸酯基团-NCO后的部分；Rt为三异氰酸酯除去端异氰酸酯基团-NCO后的部分；R3为含芳香族二元酚链段；n为≥1的整数。
优选地，所述脂肪族聚合物二元醇链段中，脂肪族聚合物二元醇为脂肪族聚酯二元醇或者脂肪族聚碳酸酯二元醇中的至少一种。
优选地，所述脂肪族聚酯二元醇为C2-C12的脂肪族二元酸与C2-C12的脂肪族二元醇反应而得，或者为C4-C12的内酯在C2-C12的二元醇为引发剂的作用下开环聚合得到。或者为市售产品。
优选地，所述芳香族二元酚链段中，芳香族二元酚为邻苯二酚、间苯二酚、对苯二酚、双酚A，双酚S，双酚AF，双(4-羟苯基)二硫醚中的至少一种。
优选地，所述二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、聚合MDI、异亚丙基又(环己基异氰酸酯-4)、异佛尔酮二异氰酸酯、含磷异氰酸酯、六次甲基二异氰酸酯(HDI)、异丙叉基双(环己烷二异氰酸酯-4)、二环己基甲烷-4-4’-二异氰酸酯、2，2，4-三甲基己烷二异氰酸酯；所述三异氰酸酯为4，4'，4”三苯基甲烷三异氰酸酯。
更优选地，所述二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六次甲基二异氰酸酯(HDI)中的至少一种。
优选地，所述可生物降解聚氨酯材料的数均分子量为5,000—500,000，分子量分布为1～6。
本发明还提供了一种可生物降解聚氨酯的制备方法，其特征在于，包括以下步骤：
将脂肪族聚合物二元醇、芳香族二元酚、二异氰酸酯、三异氰酸酯混合后，在有机溶剂和催化剂条件下加热至40-200℃反应0.1-24小时，即得。
优选地，所述脂肪族聚合物二元醇、芳香族二元酚、二异氰酸酯、三异氰酸酯的混合摩尔比为1-8：0.02-30：0.1-1：0.7-89.7。
优选地，所述催化剂的用量为脂肪族聚合物二元醇质量的0-5％；更优选0.002-4％，最优选0.002-3％。
所述催化剂为有机胺、无机酸、金属、金属氧化物、金属氯化物、金属醋酸盐、有机金属化合物中的至少一种；所述有机金属化合物包括有机钛化合物、有机锗化合物、有机锡化合物、有机铝化合物、有机铁化合物。
更优选地，所述催化剂为三乙胺、二甲基十六胺、辛酸亚锡、氯化三丁基锡、二丁基锡二月桂酸酯、膦酸钙、氯化锂、无水乙酸锌、十一烯酸锌或锌皂中的至少一种。
优选地，所述反应温度为90-190℃，反应时间为0.5-5小时。
优选地，所述有机溶剂为氯仿、丙酮、二甲亚砜、N-N’-二甲基甲酰胺、苯、甲苯或二甲苯中的至少一种。其适量加入可降低反应温度。
本发明还提供了一种可生物降解聚氨酯在高分子医用材料中的应用。
优选地，所述应用包括可生物降解聚氨酯在制备血管支架中的应用。
现有技术相比，本发明具有如下的有益效果：
1、本发明通过在合成方法中引入动态共价交联键不仅可以同时提高生物降解聚氨酯的强度和韧性，还保留了其加工性能，并赋予其自修复功能。
2、本发明制备的聚氨酯的数均分子量具有高强度、高韧性、自修复的效果，其拉伸强度为20～120MPa；断裂伸长率20～2000％；拉伸强度的修复效率为60～98％；断裂伸长率修复效率为52～98％。
3、本发明提供的可生物降解聚氨酯的方法生产成本低，工艺简便，易于操作。该生物降解聚酯聚氨酯可用作高性能环境友好性高分子材料，并可用于制备高性能生物降解血管支架，具有很高的应用价值。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1为本发明实施例1制备得到的聚氨酯的的GPC谱图；
图2为实施例1制备得到的聚氨酯自修复前后的应力-应变曲线。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
一、分子量及分子量分布
利用凝胶色谱仪(GPC，Waters公司)测定本发明提供的可生物降解聚氨酯的分子量及分子量分布。具有窄分子量分布的系列分子量的聚苯乙烯作为矫正标样，三氯甲烷作为淋洗相，测定温度为40℃。
二、本发明实施例中聚氨酯材料力学性能的测试样条均在Haake Minijet,(德国)上注射成型，拉伸强度、弯曲强度和冲击强度分别按照ISO 527、ISO 178和ISO 180的测试标准测定得到。
三、聚合物的生物降解性能测试按照GB/T 19277.1-2011测试得到。
另外，需要说明的是：
以下实施例中计算试样的修复效率，是通过先测试原始试样的拉伸强度σo、断裂伸长率εo和修复后试样的拉伸强度σh、断裂伸长率εh，再根据以下公式计算试样拉伸强度的修复效率和断裂伸长率的修复效率：
拉伸强度的修复效率＝(σh/σo)×100％；断裂伸长率的修复效率＝(εh/εo)×100％
实施例1
将聚己内酯二元醇(Mn＝3000)在40℃下干燥10h。将聚己内酯二元醇、双酚A、4，4'，4”三苯基甲烷三异氰酸酯、MDI按照摩尔比1：0.1：0.1：1.2共500g、2500mL的氯仿和0.2g辛酸亚锡依次加入到高纯氮置换过的5L的反应釜中。将上述反应体系加热到40℃，反应24h。将所得的聚合物溶液中加入过量的冷甲醇。经分离干燥得到本发明所述的可生物降解聚氨酯(GPC谱图如图1所示)，其结构式如下式I所示：
Figure BDA0002558668600000051
(式I)，其中m和n各为≥1的整数。
其数均分子量为50,300，分子量分布为2.6，拉伸强度为42MPa，断裂伸长率为150％，冲击强度为680J/m。
将本实施例中试样进行破坏修复测试，完全切断后在60℃下修复1h，进行拉伸测试。自修复前后的应力-应变曲线如图2所示，其力学性能及修复效率如下：拉伸强度39.9MPa；断裂伸长率144％；拉伸强度的修复效率为95％；断裂伸长率修复效率为96％。
本实施例制备的聚氨酯样品在2个月时的失重量为76wt％。
实施例2
将聚乳酸二元醇(Mn＝6000)在100℃下干燥3h。将该聚乳酸二元醇、双酚AF、4，4'，4”三苯基甲烷三异氰酸酯、HDI按照摩尔比8：1：0.2：3共1000g、1500mL DMF和10g的辛酸亚锡依次加入到高纯氮置换过的5L的反应釜中。将上述反应体系加热到60℃，反应10h，将所得的聚合物溶液中加入过量的冷甲醇。经分离干燥得到本发明所述的可生物降解的聚氨酯，其结构式如下式II所示：
Figure BDA0002558668600000052
(式II)，其中m和n各为≥1的整数。
其数均分子量为80,600，分子量分布为1.2，拉伸强度为120MPa，断裂伸长率为380％，冲击强度为590J/m。
将本实施例中试样进行破坏修复测试，完全切断后在60℃下修复1h，进行拉伸测试。其力学性能及修复效率如下：拉伸强度97MPa；断裂伸长率209％；拉伸强度的修复效率为81％；断裂伸长率修复效率为52％。
本实施例制备的聚氨酯样品在2个月时的失重量为61wt％。
实施例3
将聚碳酸丁二酯二元醇(Mn＝2000)在50℃下干燥8h。将该聚碳酸丁二酯二元醇、双酚S、4，4'，4”三苯基甲烷三异氰酸酯、HDI按照摩尔比8：30：0.1：0.7共2000g、500mL DMF和50g的辛酸亚锡依次加入到高纯氮置换过的5L的反应釜中。将上述反应体系加热到90℃，反应24h，将所得的聚合物溶液中加入过量的冷甲醇。经分离干燥得到本发明所述的可生物降解的聚氨酯，其结构式如下式III所示：
Figure BDA0002558668600000061
(式III)，其中m和n各为≥1的整数。
其数均分子量为24,600，分子量分布为5.2，拉伸强度为120MPa，断裂伸长率为20％，冲击强度为160J/m。
将本实施例中试样进行破坏修复测试，完全切断后在50℃下修复1h，进行拉伸测试。其力学性能及修复效率如下：拉伸强度72MPa；断裂伸长率19.6％；拉伸强度的修复效率为60％；断裂伸长率修复效率为98％。
本实施例制备的聚氨酯样品在2个月时的失重量为68wt％。
实施例4
将聚碳酸己二酯二元醇(Mn＝1000)在60℃下干燥6h。将该聚碳酸己二酯二元醇、双(4-羟苯基)二硫醚、4，4'，4”三苯基甲烷三异氰酸酯、HDI按照摩尔比8：1：0.1：89.7共1000g、3g的三乙胺依次加入到高纯氮置换过的5L的反应釜中。将上述反应体系加热到200℃，氮气保护下搅拌反应0.5h得到本发明所述的可生物降解的聚氨酯，其结构式如下式IV所示：
Figure BDA0002558668600000071
(式IV)，其中m和n各为≥1的整数。
其数均分子量为为920，100，分子量分布为1.5，拉伸强度为80MPa，断裂伸长率为1300％，样品冲不断。
将本实施例中试样进行破坏修复测试，完全切断后在30℃下修复12h，进行拉伸测试。其力学性能及修复效率如下：拉伸强度72MPa；断裂伸长率676％；拉伸强度的修复效率为90％；断裂伸长率修复效率为52％。
本实施例制备的聚氨酯样品在2个月时的失重量为66wt％。
实施例5
将聚丁二酸丁二酯二元醇(Mn＝3000)在100℃下干燥3h。将该聚丁二酸丁二酯二元醇、双酚A、4，4'，4”三苯基甲烷三异氰酸酯、HDI按照摩尔比8：2：0.2：8.7共1000g、5g的三乙胺依次加入到高纯氮置换过的5L的反应釜中。将上述反应体系加热到120℃，氮气保护下搅拌反应5h，得到本发明所述的可生物降解的聚氨酯，其结构式如下式V所示：
Figure BDA0002558668600000081
(式V)，其中m和n各为≥1的整数。
数均分子量为106，800，分子量分布为1.9，拉伸强度为61MPa，断裂伸长率为2000％，冲击强度为100J/m。
将本实施例中试样进行破坏修复测试，完全切断后在80℃下修复1h，进行拉伸测试。其力学性能及修复效率如下：拉伸强度47.58MPa；断裂伸长率1960％；拉伸强度的修复效率为78％；断裂伸长率修复效率为98％。
本实施例中的聚氨酯样品在2个月时的失重量为68wt％。
实施例6
将聚丁二酸乙二酯二元醇(Mn＝8000)在80℃下干燥3h。将该聚丁二酸乙二酯二元醇、双酚A、4，4'，4”三苯基甲烷三异氰酸酯、HDI按照摩尔比1：0.02：0.1：1.2共1000g、0.01g的二丁基锡二月桂酸酯依次加入到高纯氮置换过的5L的反应釜中。将上述反应体系加热到160℃，氮气保护下搅拌反应3h，得到本发明所述的可生物降解的聚酯-聚酯嵌段共聚物，其结构式如下式VI所示：
Figure BDA0002558668600000082
(式VI)，其中m和n各为≥1的整数。
其数均分子量为为48，500，分子量分布为2.6，拉伸强度为40MPa，断裂伸长率为690％，样品冲不断。
将本实施例中试样进行破坏修复测试，完全切断后在室温下修复24h，进行拉伸测试。其力学性能及修复效率如下：拉伸强度38MPa；断裂伸长率621％；拉伸强度的修复效率为95％；断裂伸长率修复效率为90％。
本实施例中的聚氨酯样品在2个月时的失重量为86wt％。
实施例7
该实施例用双螺杆挤出机采用熔融法进行制备，该双螺杆挤出机的参数设定如下：
Figure BDA0002558668600000091
将所用聚丁二酸丁二酯二元醇(Mn＝3000)在100℃下干燥3h。将聚丁二酸丁二酯二元醇、双酚A、4，4'，4”三苯基甲烷三异氰酸酯、HDI、催化剂三乙胺分别通过进料器与计量泵加入双螺杆反应器，通过调节进料器与计量泵的频率来控制物料，聚丁二酸丁二酯二元醇、双酚AF、4，4'，4”三苯基甲烷三异氰酸酯、HDI的摩尔比为8：1：1：1.3，共2000g，催化剂的用量为预聚物总质量的5％，双螺杆挤出、冷却、切粒，得到本发明提供的可生物降解的聚氨酯，其结构式为式V所示。
其数均分子量为78，600，分子量分布为1.9，拉伸强度为35MPa，断裂伸长率为700％，冲击强度为620J/m。
将本实施例中试样进行破坏修复测试，完全切断后在40℃下修复6h，进行拉伸测试。其力学性能及修复效率如下：拉伸强度31.5MPa；断裂伸长率623％；拉伸强度的修复效率为90％；断裂伸长率修复效率为89％。
本实施例中的聚氨酯样品在2个月时的失重量为60wt％。
本发明具体应用途径很多，以上所述仅是本发明的优选实施方式。应当指出，以上实施例仅用于说明本发明，而并不用于限制本发明的保护范围。对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进，这些改进也应视为本发明的保护范围。

Claims (10)

1.一种可生物降解聚氨酯，其特征在于，其结构式如下所示：
Figure FDA0002558668590000011
其中，R1为脂肪族聚合物二元醇链段；R2为二异氰酸酯除去端异氰酸酯基团-NCO后的部分；Rt为三异氰酸酯除去端异氰酸酯基团-NCO后的部分；R3为含芳香族二元酚链段；n为≥1的整数。
2.根据权利要求1所述的可生物降解聚氨酯，其特征在于，所述脂肪族聚合物二元醇链段中，脂肪族聚合物二元醇为脂肪族聚酯二元醇或者脂肪族聚碳酸酯二元醇中的至少一种。
3.根据权利要求2所述的可生物降解聚氨酯，其特征在于，所述脂肪族聚酯二元醇为C2-C12的脂肪族二元酸与C2-C12的脂肪族二元醇反应而得，或者为C4-C12的内酯在C2-C12的二元醇为引发剂的作用下开环聚合得到。
4.根据权利要求1所述的可生物降解聚氨酯，其特征在于，所述芳香族二元酚链段中，芳香族二元酚为邻苯二酚、间苯二酚、对苯二酚、双酚A，双酚S，双酚AF，双(4-羟苯基)二硫醚中的至少一种。
5.根据权利要求1所述的可生物降解聚氨酯，其特征在于，所述二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、聚合MDI、异亚丙基又(环己基异氰酸酯-4)、异佛尔酮二异氰酸酯、含磷异氰酸酯、六次甲基二异氰酸酯、异丙叉基双(环己烷二异氰酸酯-4)、二环己基甲烷-4-4’-二异氰酸酯、2，2，4-三甲基己烷二异氰酸酯中的至少一种；所述三异氰酸酯为4，4'，4”三苯基甲烷三异氰酸酯。
6.根据权利要求1所述的可生物降解聚氨酯，其特征在于，所述可生物降解聚氨酯材料的数均分子量为5,000—500,000，分子量分布为1～6。
7.一种根据权利要求1所述的可生物降解聚氨酯的制备方法，其特征在于，包括以下步骤：
将脂肪族聚合物二元醇、芳香族二元酚、二异氰酸酯、三异氰酸酯混合后，加热至40-200℃反应0.1-24小时，即得。
8.根据权利要求7所述的可生物降解聚氨酯的制备方法，其特征在于，所述脂肪族聚合物二元醇、芳香族二元酚、二异氰酸酯、三异氰酸酯的混合摩尔比为1-8：0.02-30：0.1-1：0.7-89.7。
9.根据权利要求7所述的可生物降解聚氨酯的制备方法，其特征在于，所述催化剂的用量为脂肪族聚合物二元醇质量的0-5％；
所述催化剂为有机胺、无机酸、金属、金属氧化物、金属氯化物、金属醋酸盐、有机金属化合物中的至少一种。
10.一种根据权利要求1所述的可生物降解聚氨酯在高分子医用材料中的应用。
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