CN104945587B - 一种降解速度可控的聚氨酯及其合成方法 - Google Patents

一种降解速度可控的聚氨酯及其合成方法 Download PDF

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CN104945587B
CN104945587B CN201510336895.0A CN201510336895A CN104945587B CN 104945587 B CN104945587 B CN 104945587B CN 201510336895 A CN201510336895 A CN 201510336895A CN 104945587 B CN104945587 B CN 104945587B
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王克敏
张楠
陈佳杰
殷红
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Abstract

本发明属于新材料技术领域，一种降解速率可控的聚氨酯，其结构式如下：其制备方法，a.将IPDI加入三口烧瓶中，用有机溶剂将其溶解，置于‑15～0℃的环境中，并滴加20ml溶有聚乙二醇的有机溶剂溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物，并滴定‑NCO的含量；b.取中间产物和2,6‑二甲基醇‑1‑硝基苯加入三口烧瓶中，用三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，即得到目标产物。本发明的有益效果是，本发明在聚氨酯的主链上引入可光降解的基团，该类聚氨酯同时具有水解、光降解的特性，使得其的水解速度能通过光降解来控制，这一特性拓宽了在组织工程支架、药物缓释等领域的应用前景。

Description

一种降解速度可控的聚氨酯及其合成方法
技术领域
本发明属于新材料技术领域，具体涉及一种降解速度可控的聚氨酯及其制备方法。
背景技术
每年都有着数以万计的患者因为缺乏合适的供体和有效的器官替代物而死亡，同时各类的外科修复手术费用高达百亿美元。组织工程就是在这种大背景下应运而生的新兴交叉学科，结合生命科学与工程学的基本理论，解决组织或器官缺损所致的功能障碍或丧失的治疗问题，提高人类的生存质量。组织工程学的基本原理和方法是将在体外培养、扩增的正常组织细胞种植到具有良好生物相容性且在体内可逐步降解吸收的组织工程多孔支架上，形成细胞-架复合物，细胞在支架上增殖、分化，然后将此复合物植入机体组织病损部位，在体内继续增殖并分泌细胞外基质，伴随着材料的逐步降解，形成新的与自身功能和形态相适应的组织或器官，从而达到修复病损组织或器官的目的。
现如今，聚氨酯材料被广泛应用于生物医学领域，是因为聚氨酯拥有着优良的抗凝血性能、良好的生物相容性；毒性测试结果符合医用要求，无致畸变作用，无过敏反应；有着优良的弹性、韧性及耐磨性能。但是由于聚氨酯的降解周期比较长，大大限制了其的应用范围。对于如何能有效地调控聚氨酯的降解速度并保持聚氨酯的性能，是本领域亟待解决的问题。
发明内容
本发明要解决的技术问题是：克服现有技术中聚氨酯降解周期长的不足，提供一种降解速率可控的聚氨酯及其合成方法。
本发明解决其技术问题所采用的技术方案是：一种降解速率可控的聚氨酯，其结构式如下：
上述的降解速率可控的聚氨酯的制备方法，步骤如下，
a.将IPDI加入三口烧瓶中，用有机溶剂将其溶解，置于-15～0℃的环境中，并滴加20ml溶有聚乙二醇的有机溶剂溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物，并滴定-NCO的含量；
b.取中间产物和2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料。
进一步地，步骤a所述的有机溶剂为三氯甲烷、甲苯、硝基苯、丙酮中的一种。
作为优选，所述的聚乙二醇分子量为800～20000。
作为优选，所述的IPDI与聚乙二醇摩尔比为1：0.5。
作为优选，所述的中间产物与所述的2,6-二甲基醇-1-硝基苯摩尔比为1:1
本发明的有益效果是，本发明在聚氨酯的主链上引入可光降解的基团，该类聚氨酯同时具有水解、光降解的特性，使得其的水解速度能通过光降解来控制，这一特性拓宽了在组织工程支架、药物缓释等领域的应用前景。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是实施例1中聚氨酯的核磁图；
图2实施例1中聚氨酯不同光照时间的紫外吸收图；
图3是实施例1中双降解材料在光照和不光照条件下降解曲线。
具体实施方式
实施例1
a.将1摩尔分数的IPDI加入三口烧瓶中，用20ml三氯甲烷将其溶解，置于-15℃的环境中，并滴加20ml溶有0.5摩尔分数聚乙二醇800的三氯甲烷溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物；
b.取1摩尔分数的中间产物和1摩尔分数的2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用50ml的三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料，其核磁图如图1所示。
如图2所示，为双降解材料在紫外光照射0s、10s、30s、5min、15min、30min后所得的紫外吸收光谱图，从图中可以看出，在290nm附近存在着硝基的紫外吸收峰，并随着照射时间的增加，其紫外吸收峰强度逐渐增大，且波长逐渐向波长增大的方向移动，说明分子链上的光响应基团发生了降解，即改产物是具有光响应性的特性。
如图3所示，取两组上述制备的聚氨酯材料，一组每天以光强50mW/cm2进行15min的照射后再放入培养基水解，另一组不光照直接放入培养基进行水解。在第一天、第三天、第六天、第十天、第十三天、第十六天、第二十天、第二十五天以及第三十天取出，干燥并称重。
从图中可以看出，光照过样品的水解速度明显快于未光照的样品。说明该材料具有明显的双降解性质。
实施例2
a.将1摩尔分数的IPDI加入三口烧瓶中，用20ml甲苯将其溶解，置于-10℃的环境中，并滴加20ml溶有0.5摩尔分数聚乙二醇1000的甲苯溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物；
b.取1摩尔分数的中间产物和1摩尔分数的2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用50ml的三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料。
实施例3
a.将1摩尔分数的IPDI加入三口烧瓶中，用20ml硝基苯将其溶解，置于-10℃的环境中，并滴加20ml溶有0.5摩尔分数聚乙二醇2000的硝基苯溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物；
b.取1摩尔分数的中间产物和1摩尔分数的2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用50ml的三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料。
实施例4
a.将1摩尔分数的IPDI加入三口烧瓶中，用20ml丙铜将其溶解，置于-5℃的环境中，并滴加20ml溶有0.5摩尔分数聚乙二醇6000的丙铜溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物；
b.取1摩尔分数的中间产物和1摩尔分数的2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用50ml的三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料。
实施例5
a.将1摩尔分数的IPDI加入三口烧瓶中，用20ml三氯甲烷将其溶解，置于-5℃的环境中，并滴加20ml溶有0.5摩尔分数聚乙二醇10000的三氯甲烷溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物；
b.取1摩尔分数的中间产物和1摩尔分数的2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用50ml的三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料。
实施例6
a.将1摩尔分数的IPDI加入三口烧瓶中，用20ml甲苯将其溶解，置于0℃的环境中，并滴加20ml溶有0.5摩尔分数聚乙二醇20000的甲苯溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物；
b.取1摩尔分数的中间产物和1摩尔分数的2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用50ml的三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料。

Claims (2)

1.一种降解速率可控的聚氨酯的制备方法，其特征在于：所述制备方法步骤如下：
a.将IPDI加入三口烧瓶中，用有机溶剂将其溶解，置于-15～0℃的环境中，并滴加20ml溶有聚乙二醇的有机溶剂溶液，半小时滴加完，搅拌反应24h，旋蒸，得到中间产物；其中，所述的聚乙二醇分子量为800～20000，所述的IPDI与聚乙二醇摩尔比为1：0.5；
b.取中间产物和2,6-二甲基醇-1-硝基苯加入三口烧瓶中，用三氯甲烷溶解，在50℃下回流48小时，将产物旋蒸，则得到降解速度可控的聚氨酯材料；其中，所述的中间产物与所述的2,6-二甲基醇-1-硝基苯摩尔比为1:1；所述降解速度可控的聚氨酯结构式为：
2.根据权利要求1所述的降解速率可控的聚氨酯的制备方法，其特征在于：步骤a所述的有机溶剂为三氯甲烷、甲苯、硝基苯、丙酮中的一种。
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