CN112876696B - 一种生物医用聚甘油基水凝胶及其制备方法 - Google Patents

一种生物医用聚甘油基水凝胶及其制备方法 Download PDF

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CN112876696B
CN112876696B CN202110065569.6A CN202110065569A CN112876696B CN 112876696 B CN112876696 B CN 112876696B CN 202110065569 A CN202110065569 A CN 202110065569A CN 112876696 B CN112876696 B CN 112876696B
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hydrogel
polyglyceryl
biomedical
lactic acid
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武志峰
邹文军
罗莎莎
徐慧艳
蒋平平
张哲铭
冷炎
石朗晨
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Jiangnan University
Wuxi No 2 Peoples Hospital
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Abstract

本发明公开了一种生物医用聚甘油基水凝胶及其制备方法，属于生物医用材料和高分子化学领域。本发明将天然高分子和明胶加入到乳酸水溶液中，充分搅拌溶解；再向上述溶液中加入聚甘油和泊洛沙姆，充分搅拌混合；用NaOH水溶液滴加调节pH值至pH＝6.5‑7.5，体系静置，得到聚甘油基水凝胶。本发明的水凝胶的含水量高于80％，具有较好的透明度和机械强度。本发明的优点在于以羟基丰富的聚甘油为原料，使得水凝胶具有更高的吸水性和生物相容性，此外，采用乳酸替代传统的冰醋酸作为天然高分子的溶解助剂，使得水凝胶更为环保无毒，易降解被人体吸收，该有望成为新一类的生物医用材料。

Description

一种生物医用聚甘油基水凝胶及其制备方法
技术领域
本发明涉及一种生物医用聚甘油基水凝胶及其制备方法，属于生物医用材料和高分子化学领域。
背景技术
水凝胶(Hydrogel)是一类极为亲水的三维网络结构它在水中迅速溶胀并在此溶胀状态可以保持大量体积的水而不溶解。水凝胶在结构上与由纤维胶原蛋白、肽聚糖等生物大分子和水组成的细胞外基质十分相似。不仅如此，水凝胶可以通过引入生物友好型单体、大分子以及负载生物活性分子进行进一步的改性，从而具有功能性和生物相容性。因此，水凝胶已被广泛用于组织黏合剂、伤口敷料、药物载体、眼角膜、人工软骨等生物医用材料。
目前常见的水凝胶主要由天然高分子(壳聚糖、纤维素、海藻酸盐、淀粉等)、聚乙烯醇、聚乙烯吡咯烷酮、聚乙二醇、聚丙烯酸、聚丙烯酰胺等制备而成。通过调节原料组成和配比，可以获得种类繁多，性质各异的水凝胶产品。成功制备水凝胶需要满足两个基本条件：1)能够通过交联形成高分子三维网络；2)聚合物分子的主链或者侧基具有一定的轻水性。
聚甘油是由甘油分子经脱水后形成的多元醇，来源广泛，价格低廉，生物友好、这些性质使其在生物医药和日化等领域都具有很广泛的应用。因此，制备得到聚甘油基水凝胶能够拓宽水凝胶的制备，具有一定应用前景。
发明内容
为了实现上述目的，本发明以聚甘油、壳聚糖、明胶为主要原料，采用乳酸为溶解助剂，制备出一种生物医用聚甘油基水凝胶，本发明的聚甘油基水凝胶具有良好的吸水率、生物相容性以及环保性，具有良好的应用市场。
首先，本发明提供了一种生物医用聚甘油基水凝胶的制备方法，所述方法包括如下步骤：
(1)将天然高分子和明胶加入到乳酸水溶液中，充分搅拌溶解；
(2)再向上述溶液中加入聚甘油和泊洛沙姆，充分搅拌混合；
(3)用NaOH水溶液滴加调节pH值至pH＝6.5-7.5，体系静置，得到聚甘油基水凝胶。
在本发明的一种实施方式中，步骤(1)中的天然高分子包括壳聚糖、纤维素、海藻酸、淀粉、木质素、甲壳素中的一种或几种。
在本发明的一种实施方式中，步骤(1)中的天然高分子和明胶的质量比为1:2～2:1，乳酸和水的体积比为1:40～1:10，天然高分子与乳酸的质量比为0.3:1～10:1，搅拌溶解温度为40-60℃。
在本发明的一种实施方式中，步骤(2)中的聚甘油为十聚甘油或五聚甘油中的一种。
在本发明的一种实施方式中，步骤(2)中的聚甘油的质量为天然高分子和明胶总质量的30％～150％，泊洛沙姆为天然高分子和明胶总质量的2％～8％。
在本发明的一种实施方式中，步骤(3)中的NaOH水溶液的浓度为0.5M～2M，体系静置温度为30-60℃，静置时间为2-5h。
其次，本发明提供了上述制备方法制备得到的聚甘油基水凝胶。
再者，本发明提供了包含上述聚甘油基水凝胶的生物医用材料。
在本发明的一种实施方式中，所述生物医用材料包括组织黏合剂、伤口敷料、药物载体、眼角膜、人工软骨等。
最后，本发明提供了上述制备方法以及聚甘油基水凝胶在生物医学领域的应用。
本发明的有益效果：
(1)本发明的采用羟基丰富的聚甘油为原料制备水凝胶，不仅使其具有更好吸水率，吸水率高达80％以上而且具有更好的生物相容性；
(2)本发明以乳酸代替传统的冰醋酸作为天然高分子的溶解助剂，使得生成的水凝胶更环保亲和；
(3)本发明的甘油基水凝胶的原料均环保无毒，易降解被人体吸收，有望成为新一类的生物医用材料。
附图说明
图1实施例1制备得到的聚甘油基水凝胶的样品图。
图2实施例1制备得到的聚甘油基水凝胶的热重分析曲线图。
图3实施例1制备得到的聚甘油基水凝胶的傅里叶红外光谱图。
图4对比例1制备得到的聚甘油基水凝胶的样品图。
图5对比例2制备得到的聚甘油基水凝胶的样品图。
具体实施方式
下面结合实施例对本发明作进一步的描述，但本发明的实施方式不限于此。
实施例1
将0.5g壳聚糖和0.4g明胶加入到15mL乳酸水溶液中(其中，含有1mL乳酸)，50℃条件下充分搅拌溶解，再向该溶液重加入0.6g十聚甘油和0.05g泊洛沙姆，继续搅拌混合后，用1M的NaOH水溶液缓慢调节pH值至中性，然后40℃条件下，静置4h，得到聚甘油基水凝胶，样品如图1所示，成胶性好，透明度也较好，含水率高。
图2为聚甘油基水凝胶的热重分析曲线图，100-150℃的热失重为水分子的流失，可以看出该水凝胶的含水率超过80％。
图3的FT-IR图谱在3300cm-1附近出现强的羟基吸收峰，表明水凝胶主要通过羟基的氢键进行网络交联而成。
实施例2
将0.5g壳聚糖和0.8g明胶加入到20mL乳酸水溶液中(含有1mL乳酸)，50℃条件下充分搅拌溶解，再向该溶液重加入0.6g五聚甘油和0.05g泊洛沙姆，继续搅拌混合后，用1M的NaOH水溶液缓慢调节pH值至中性，然后40℃条件下，静置4h，得到聚甘油基水凝胶。该水凝胶含水率超过85％，透明性更好，但易破损。
实施例3
将0.5g淀粉和0.4g明胶加入到15mL乳酸水溶液中(含有1mL乳酸)，50℃条件下充分搅拌溶解，再向该溶液重加入0.6g十聚甘油和0.05g泊洛沙姆，继续搅拌混合后，用1M的NaOH水溶液缓慢调节pH值至中性，然后40℃条件下，静置4h，得到的聚甘油基水凝胶呈半透明状，颜色偏黄，质地较硬。
实施例4
将0.5g纤维素和1.0g明胶加入到15mL乳酸水溶液中(含有1mL乳酸)，60℃条件下充分搅拌溶解，再向该溶液重加入1.5g十聚甘油和0.1g泊洛沙姆，继续搅拌混合后，用0.5M的NaOH水溶液缓慢调节pH值至中性，然后60℃条件下，静置3h，得到的聚甘油基水凝胶。
对比例1
当将实施例1中的乳酸替换为冰醋酸时，其他步骤和条件与实施例1一致，制备得到聚甘油基水凝胶。样品如图4所示，成胶性较差好，透明度也较差。
可见，采用乳酸代替冰醋酸制备聚甘油水凝胶对于产品性能的提升有利。
对比例2
当将实施例1中不添加聚甘油，其他步骤和条件与实施例1一致，制备得到的样品如图5所示，基本难以成胶，样品也很浑浊。
可见，聚甘油的引入有可能增强了水凝胶中的三维氢键网络，同时提供了更多的亲水基团，从而有利于提升水凝胶的成胶性和含水率。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (6)

1.一种生物医用聚甘油基水凝胶的制备方法，其特征在于，所述方法包括如下步骤：
（1）将天然高分子和明胶加入到乳酸水溶液中，充分搅拌溶解；
（2）再向上述溶液中加入聚甘油和泊洛沙姆，充分搅拌混合；
（3）用NaOH水溶液滴加调节pH值至pH=6.5-7.5，体系静置，得到聚甘油基水凝胶；
其中，步骤（1）中的天然高分子为壳聚糖，天然高分子和明胶的质量比为1:2~2:1，乳酸和水的体积比为1:40~1:10，天然高分子与乳酸的质量比为0.3:1~10:1，搅拌溶解温度为40-60℃；
步骤（2）中的聚甘油为十聚甘油或五聚甘油中的一种，聚甘油的质量为天然高分子和明胶总质量的30%~150%，泊洛沙姆为天然高分子和明胶总质量的2%~8%。
2.根据权利要求1所述的一种生物医用聚甘油基水凝胶的制备方法，其特征在于，步骤（3）中的NaOH水溶液的浓度为0.5M~2M，体系静置温度为30-60℃，静置时间为2-5h。
3.权利要求1或2所述的一种生物医用聚甘油基水凝胶的制备方法制备得到的聚甘油基水凝胶。
4.包含权利要求3所述的聚甘油基水凝胶的生物医用材料。
5.根据权利要求4所述的生物医用材料，其特征在于，所述生物医用材料包括组织黏合剂、伤口敷料、药物载体、眼角膜、人工软骨。
6.权利要求1或2所述的一种生物医用聚甘油基水凝胶的制备方法或权利要求3所述的聚甘油基水凝胶在生物医学领域的应用。
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