CN107982578B - 纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的制备方法 - Google Patents
纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的制备方法 Download PDFInfo
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Abstract
纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架的制备方法，属于骨组织工程领域，可用于骨组织再生与修复。这种纳米羟基磷灰石/环糊精基聚氨酯的复合多孔支架是利用β‑环糊精作为聚氨酯合成的软段成分，该软段与硬段成分脂肪族异氰酸酯（六亚甲基二异氰酸酯）进行加成反应，并进一步原位复合纳米羟基磷灰石得到多孔支架材料。其合成原料天然无毒，制备工艺简单，成本低廉。
Description
技术领域
本发明涉及纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架的制备方法，属于骨组织工程领域，可用于骨组织再生与修复。
背景技术
由坏疽或外伤引起的骨缺损是临床上常见的疾病，通常采用自体骨移植或异体骨移植的方法进行修复治疗。但上述两种方法存在骨源有限、感染风险高、增加病人痛苦、免疫排斥等问题，因此并非最佳的治疗方法。骨组织工程学为临床骨缺损的修复提供了全新的思路，其核心是建立由种子细胞和多孔支架材料构成的三维复合体，以实现对骨缺损的良好修复。支架材料是骨组织工程的重要组成部分，它为种子细胞提供黏附、增殖、分化的三维空间结构和生长模板，为细胞生存提供营养通道，从而引导受损骨组织的再生。人工合成的支架材料需从组分及结构两方面模拟天然骨组织。天然骨是由无机组分（主要是羟基磷灰石）结合有机组分（主要为胶原纤维和黏多糖蛋白）的复合材料。因此，制备羟基磷灰石和有机聚合物的复合多孔支架材料成为研究热点。近年来，聚氨酯因其良好的生物相容性、血液相容性、良好的机械性能、无毒、易加工等优点而广泛应用于生物医学领域。聚氨酯是由软、硬段组成的嵌段聚合物。含有羟基基团的软段与含有氰基基团的硬段发生反应生成聚氨酯，选择不同的软硬段或调节软硬段比例可得到理化性能不同的材料，因此制备聚氨酯材料时原料的选择至关重要。环糊精(cyclodextrin，CD)是淀粉在葡萄糖基转移酶的作用下降解而成的一类环状低聚糖。天然环糊精来源丰富，价格低廉且无毒，无致癌致畸性，已被广泛应用到药物、食品、纺织、包装、化妆品等行业。环糊精的三维构象类似平头圆锥体，具有一个疏水空腔和两个亲水边缘，分子结构中存在大量的羟基活性基团，可作为合成聚氨酯的原料。基于此本发明提出采用天然环糊精作为合成聚氨酯的软段，脂肪族六亚甲基二异氰酸酯作为聚氨酯硬段，以辛酸亚锡作为催化剂，水为发泡剂，由此方法合成的聚氨酯可保证没有毒性。本发明提出将纳米羟基磷灰石和环糊精基聚氨酯复合得到多孔骨组织工程支架具有良好的生物相容性及力学性能。
发明内容
本发明所要解决的技术问题是：提供制备工艺简单，成本低廉的纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的制备方法及应用。
纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的制备方法，其特征在于：采用β-环糊精作为聚氨酯合成的软段成分，六亚甲基二异氰酸酯（hexamethylene diisocyanate, HDI）作为硬段成分，并原位复合纳米羟基磷灰石得到多孔支架材料。
具体制备方法是：β-环糊精与六亚甲基二异氰酸酯在氮气保护下于70~80℃进行反应，β-环糊精与六亚甲基二异氰酸酯摩尔比为1:1~1:5，催化剂辛酸亚锡用量为0.1%~0.2%，并与质量分数占比为10-40%的纳米羟基磷灰石原位复合，反应持续进行4~6小时，90~110℃以水为发泡剂发泡1~2小时后得到纳米羟基磷灰石/环糊精基聚氨酯多孔支架材料。
本发明所用的纳米羟基磷灰石是以硝酸钙和磷酸三钠为原料湿法制得。
纳米羟基磷灰石制备方法是将钙磷摩尔比为1.67的硝酸钙和磷酸三钠，分别制成0.5 mol/L的水溶液，37oC下将磷酸三钠溶液滴于硝酸钙溶液中，滴定完毕后沉化3小时，去离子水洗净即可。
纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料具有三维多孔结构，孔径100 μm ~ 700 μm，孔隙率40% ~ 90%，抗压强度800 kPa~5000 kPa。
本发明与现有技术相比具有以下的主要优点：
其一，采用本方法制备骨组织工程多孔支架所使用的原料均对人体无毒无害。
其二，本制备方法简单易行，无污染，原料价格低廉、易得。
其三，环糊精基聚氨酯与纳米羟基磷灰石复合作为骨组织工程多孔支架材料既具有良好的生物相容性，又具有良好的力学性能。
总之，本发明原料天然无毒，制备工艺简单，成本低廉，应用于骨组织工程领域，应用前景广阔。
附图说明
图1：纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的扫描电镜图片；
图2：MC3T3-E1细胞与纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料共培养5天后的扫描电镜图片。
具体实施方式
以下结合由附图所示实施例的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。在不脱离本发明上述技术思想情况下，根据本领域普通技术知识和惯用手段做出的各种替换或变更，均应包括在本发明的范围内。
实施例1
采用β-环糊精与六亚甲基二异氰酸酯在氮气保护下于70~80℃进行反应，将β-环糊精溶于30mL二甲基甲酰胺，搅拌均匀后逐滴加入六亚甲基二异氰酸酯，β-环糊精与六亚甲基二异氰酸酯摩尔比为1:1~1:5，催化剂辛酸亚锡用量为0.1%~0.2%，加入催化剂的同时加入10wt%纳米羟基磷灰石（此处指纳米羟基磷灰石的质量占反应物总质量的10%），反应持续进行4~6小时，90~110℃以水为发泡剂发泡1~2小时后，使用丙酮清洗以去除未反应的原料及低分子量物质，去离子水清洗后37℃烘干得到10wt%纳米羟基磷灰石/环糊精基聚氨酯复合多孔支架材料。
实施例2
采用β-环糊精与六亚甲基二异氰酸酯在氮气保护下于70~80℃进行反应，将β-环糊精溶于30mL二甲基甲酰胺，搅拌均匀后逐滴加入六亚甲基二异氰酸酯，β-环糊精与六亚甲基二异氰酸酯摩尔比为1:1~1:5，催化剂辛酸亚锡用量为0.1%~0.2%，加入催化剂的同时加入15wt%纳米羟基磷灰石（此处指纳米羟基磷灰石的质量占反应物总质量的15%），反应持续进行4~6小时，90~110℃以水为发泡剂发泡1~2小时后，使用丙酮清洗以去除未反应的原料及低分子量物质，去离子水清洗后37℃烘干得到15wt%纳米羟基磷灰石/环糊精基聚氨酯复合多孔支架材料。
实施例3
采用β-环糊精与六亚甲基二异氰酸酯在氮气保护下于70~80℃进行反应，将β-环糊精溶于30mL二甲基甲酰胺，搅拌均匀后逐滴加入六亚甲基二异氰酸酯，β-环糊精与六亚甲基二异氰酸酯摩尔比为1:1~1:5，催化剂辛酸亚锡用量为0.1%~0.2%，加入催化剂的同时加入30wt%纳米羟基磷灰石（此处指纳米羟基磷灰石的质量占反应物总质量的30%），反应持续进行4~6小时，90~110℃以水为发泡剂发泡1~2小时后，使用丙酮清洗以去除未反应的原料及低分子量物质，去离子水清洗后37℃烘干得到30wt%纳米羟基磷灰石/环糊精基聚氨酯复合多孔支架材料。
Claims (2)
1.纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的制备方法，其特征在于：采用β-环糊精作为聚氨酯合成的软段成分，用六亚甲基二异氰酸酯作为硬段成分，原位复合纳米羟基磷灰石得到纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料；纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的制备方法：β-环糊精与六亚甲基二异氰酸酯在氮气保护下于70~80℃进行反应，β-环糊精与六亚甲基二异氰酸酯摩尔比为1:1~1:5，催化剂辛酸亚锡用量为0.1%~0.2%，与纳米羟基磷灰石原位复合，反应持续进行4~6小时，90~110℃水为发泡剂发泡1~2小时后得到具有三维多孔结构，孔径100μm ~ 700 μm，孔隙率40% ~ 90%，抗压强度800 kPa~5000 kPa的纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料。
2.根据权利要求1所述的纳米羟基磷灰石/环糊精基聚氨酯复合多孔骨组织工程支架材料的制备方法，其特征在于：所用纳米羟基磷灰石是以硝酸钙和磷酸三钠为原料湿法制得。
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