CN114601963A - 一种可缓慢降解的高纯镁锚钉的制备方法及其应用 - Google Patents
一种可缓慢降解的高纯镁锚钉的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开一种可缓慢降解的高纯镁锚钉的制备方法，包括以下步骤：1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠0.2‑0.25mol/L、磷酸二氢钾0.12‑0.15mol/L、氯化钙0.2‑0.25mol/L；2）将高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热4‑6小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉；本发明使得镁锚钉在动物体内实现缓慢降解，且在动物体内具有良好的生物相容性。
Description
技术领域
本发明涉及医疗器械技术领域，具体涉及一种可缓慢降解的高纯镁锚钉的制备方法及其应用。
背景技术
锚钉是骨科领域中一类非常重要的内固定器械，通过固定韧带、肌腱和骨以进行修复效果。经过30多年的发展，不同材料与设计的锚钉广泛应用于临床，但都遵循一些共同的原则：一、最大限度地提高拔出强度；二、最大限度地减少急性医源性损伤；三、最大限度地减少长期应用中发生关节炎的可能性。
用于制备锚钉的材料主要有惰性金属（如钛及其合金）、PEEK和高分子可降解材料（如聚乙醇酸、聚乳酸的立体异构体等）。惰性金属在体内不能被降解吸收，而且其弹性模量远大于人骨，会产生应力遮挡效应，造成骨质疏松甚至内固定失败的风险，且长期植入可能释放各种有害离子，引发炎症、过敏的风险，所以多需要在骨愈合后再次手术取出，这不但提高了医疗支出、给患者带来二次伤害并且还增加了患者心理负担。PEEK材料在人体不能降解，且其强度低、脆性大等，限制了其临床应用。高分子可降解材料也存在诸多问题，如力学性能较低、应用范围局限、降解过程中会产生大量酸性小分子或低聚体从而对周围组织产生刺激导致比较严重的炎性反应，甚至积液、囊肿等，影响手术预后并降低患者的满意度。因此，为了克服以上材料在应用中的各种局限，采用新的材料制备锚钉是必要的。
镁及镁合金具有良好的生物相容性、力学性能和生物可降解性，而且其无害的降解产物可通过人体新陈代谢排出体外，是一种理想的锚钉制备材料。现主要限制其应用的重要因素是在机体复杂内环境下降解速度过快，影响早期固定强度，因此使其缓慢降解是实现临床应用的关键。
发明内容
本发明所要解决的技术问题是，克服以上现有技术的缺点：提供一种可缓慢降解的高纯镁锚钉的制备方法以及其应用。
本发明的技术解决方案如下：一种可缓慢降解的高纯镁锚钉的制备方法，包括以下步骤：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.2-0.25mol/L、磷酸二氢钾0.12-0.15mol/L、氯化钙 0.2-0.25mol/L；
2）将高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热4-6小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
作为优选，所述水热溶液中钙磷比为10︰6。
作为优选，所述高纯镁锚钉的镁含量为99.99wt.%以上。
作为优选，步骤2）中制得的所述可缓慢降解的高纯镁锚钉的羟基磷灰石涂层厚度为14-24μm。
本发明还提供所述可缓慢降解的高纯镁锚钉的应用，应用于骨科作为骨内植入物可以实现其在机体内环境下缓慢降解。
本发明的有益效果是：作为骨骼的主要无机成分，羟基磷灰石具有良好的生物相容性。通过表面改性使高纯镁锚钉表面涂覆羟基磷灰石可以实现其在机体内环境下缓慢降解。本发明通过对水热溶液配方的调整以及控制水热处理的条件实现在高纯镁锚钉表面形成紧密且厚度为14-24μm的羟基磷灰石涂层，使得镁锚钉在动物体内实现缓慢降解，且在动物体内具有良好的生物相容性。
附图说明
图1中：（a）为实施例1制备的具有羟基磷灰石涂层的高纯镁锚钉的横断面电镜扫描图；（b）为实施例1制备的具有羟基磷灰石涂层的高纯镁锚钉元素分析结果。
图2为对照实验中动物骨骼后12周的CT影像图。
图3为对照实验中锚钉局部骨组织硬组织切片示意图。
具体实施方式
下面用具体实施例对本发明做进一步详细说明，但本发明不仅局限于以下具体实施例。
实施例1
按照以下步骤制备可缓慢降解的高纯镁锚钉：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.25mol/L、磷酸二氢钾0.15mol/L、氯化钙 0.25mol/L。
2）将镁含量为 99.99wt.%的高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热4小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
图1为实施例1制备的高纯镁锚钉的羟基磷灰石涂层表征及元素分析；其中，左图（a）为实施例1制备的高纯镁锚钉的横断面电镜扫描图；右图（b）为实施例1制备的高纯镁锚钉元素分析结果。由高纯镁锚钉横断面电镜结果可知，羟基磷灰石涂层与镁基底结合紧密，未见明显缝隙存在，羟基磷灰石涂层厚度为18.71±3.36μm，由元素分析结果可知涂层中钙、磷元素特征峰明显。
动物体内降解对照实验
以成年母绵羊为实验动物，将动物随机分成两组，对照组植入镁含量为99.99wt.%的传统高纯镁锚钉（裸镁组），实验组植入由实施例1制备的涂覆羟基磷灰石涂层的高纯镁锚钉（羟基磷灰石涂层组）。将锚钉植入动物骨内，定期行CT检查观察锚钉降解情况及锚钉周围骨组织改变，后取出局部骨组织标本进行组织学研究。
图2为对照实验中动物骨骼后12周的CT影像图。由图2的CT结果提示与裸镁组相比，羟基磷灰石涂层组所植入锚钉术后12周结构完整，锚钉周围空腔小，表明涂层能在12周内明显减缓锚钉在实验动物体内的降解。
图3为对照实验中锚钉局部骨组织硬组织切片示意图。由图3的术后12周局部组织切片提示，羟基磷灰石涂层组锚钉与周围骨组织结合更紧密，周围骨组织结构正常，裸镁组锚钉周围骨组织结构疏松，表明羟基磷灰石涂层组锚钉在12周内组织相容性好，未出现明显降解及对周围骨组织代谢产生不利影响。
综上所述，本发明制备的涂覆羟基磷灰石涂层的高纯镁锚钉能在动物体内实现缓慢降解，且在动物体内具有良好的生物相容性。
实施例2
按照以下步骤制备可缓慢降解的高纯镁锚钉：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.25mol/L、磷酸二氢钾0.12mol/L、氯化钙 0.2mol/L。
2）将镁含量为 99.99wt.%的高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热6小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
实施例3
按照以下步骤制备可缓慢降解的高纯镁锚钉：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.25mol/L、磷酸二氢钾0.13mol/L、氯化钙 0.22mol/L。
2）将镁含量为 99.99wt.%的高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热4小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
实施例4
按照以下步骤制备可缓慢降解的高纯镁锚钉：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.2mol/L、磷酸二氢钾0.12mol/L、氯化钙 0.2mol/L；所述水热溶液中钙磷比为10︰6。
2）将镁含量为 99.99wt.%的高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热5小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
实施例5
按照以下步骤制备可缓慢降解的高纯镁锚钉：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.2mol/L、磷酸二氢钾0.15mol/L、氯化钙 0.25mol/L。
2）将镁含量为 99.99wt.%的高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热4小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
实施例6
按照以下步骤制备可缓慢降解的高纯镁锚钉：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.2mol/L、磷酸二氢钾0.14mol/L、氯化钙 0.23mol/L。
2）将镁含量为 99.99wt.%的高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热6小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
以上仅是本发明的特征实施范例，对本发明保护范围不构成任何限制。凡采用同等交换或者等效替换而形成的技术方案，均落在本发明权利保护范围之内。
Claims (5)
1.一种可缓慢降解的高纯镁锚钉的制备方法，其特征在于，包括以下步骤：
1）将乙二胺四乙酸二钠、磷酸二氢钾、氯化钙溶解于去离子水中，滴加氢氧化钠至pH=9.0得到水热溶液；所述水热溶液中各组分浓度为：乙二胺四乙酸二钠 0.2-0.25mol/L、磷酸二氢钾0.12-0.15mol/L、氯化钙 0.2-0.25mol/L；
2）将高纯镁锚钉置于步骤1）制备的水热溶液中，在110℃的温度下加热4-6小时，得到具有羟基磷灰石涂层的可缓慢降解的高纯镁锚钉。
2.根据权利要求1所述的可缓慢降解的高纯镁锚钉的制备方法，其特征在于，所述水热溶液中钙磷比为10︰6。
3.根据权利要求1所述的可缓慢降解的高纯镁锚钉的制备方法，其特征在于，所述高纯镁锚钉的镁含量为99.99wt.%以上。
4.根据权利要求1所述的可缓慢降解的高纯镁锚钉的制备方法，其特征在于，步骤2）中制得的所述可缓慢降解的高纯镁锚钉的羟基磷灰石涂层厚度为14-24μm。
5.一种权利要求1-4中任意项制备的可缓慢降解的高纯镁锚钉的应用，其特征在于，应用于骨科作为骨内植入物。
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| CN104888271A (zh) * | 2015-05-11 | 2015-09-09 | 同济大学 | 一种生物可降解镁合金表面锶羟基磷灰石涂层的制备方法 |
| CN108004527A (zh) * | 2017-11-22 | 2018-05-08 | 同济大学 | 一种用于镁合金材料的锌掺杂羟基磷灰石涂层的制备方法 |
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