CN110237300A - 一种4d打印聚醚醚酮/铌酸盐复合材料及其制备方法 - Google Patents

一种4d打印聚醚醚酮/铌酸盐复合材料及其制备方法 Download PDF

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CN110237300A
CN110237300A CN201910498312.2A CN201910498312A CN110237300A CN 110237300 A CN110237300 A CN 110237300A CN 201910498312 A CN201910498312 A CN 201910498312A CN 110237300 A CN110237300 A CN 110237300A
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niobates
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闵永刚
刘荣涛
刘屹东
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Huimai Material Technology (guangdong) Co Ltd
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract

本发明公开了一种4D打印的聚醚醚酮/铌酸盐复合材料及其制备方法，主要用于生物医用领域创伤和骨骼修复如颅骨修复、脊椎体替换、生物支架等。聚醚醚酮粉体与铌酸盐粉末可以共混制成PEEK/铌酸盐复合材料或在聚醚醚酮(纤维、片材、棒材)表面包裹铌酸盐材料，在PEEK/铌酸盐复合材料表面包覆生物可降解高分子材料得到PEEK基复合材料，通过3D打印技术成型生物植入体形状结构。本发明中的聚醚醚酮复合材料具有促进植入体表面钙磷盐生成、骨细胞增殖分化、细胞粘附，无毒、生物相容性好、制备方法简单等特点。

Description

一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法
技术领域
本发明涉及一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，属生物医用材料领域
背景技术
聚醚醚酮(PEEK)属于一种具有较高的玻璃化转变温度和熔点、负载热变型温度高、高强度、高模量、高断裂韧性、耐水性以及优良的尺寸稳定性等特殊性能的材料，其作为生物材料可满足骨骼替代的材料强度、弹性模量等机械性能要求，但PEEK属于惰性不亲水材料，作为生物植入体在体内环境中不具有生物活性，容易引起细胞纤维化，从而进一步导致PEEK植入体部位产生肿块甚至发炎。
铌酸盐是一种具有钙钛矿结构的压电陶瓷材料，与人体骨骼类似，具有在外力作用下其内部极化分子重拍在表面产生微弱电荷，因此能够诱导并激发成骨细胞增殖分化，在植入体材料表面形成与骨骼成分一致的磷酸钙盐，从而增强植入体材料生物相容性和生物活性。
在PEEK表面包裹铌酸盐得到聚醚醚酮/铌酸盐复合材料，在其表面包覆生物可降解高分子材料，增加PEEK表面粗糙度和生物活性，从而促进植入体表面细胞增殖分化、粘附、生物相容性，满足生物医用材料国家标准，可作为重要医学材料用于临床使用。
发明内容
本发明的目的是提供一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，主要用于生物医用领域创伤和骨骼修复如颅骨修复、脊椎体替换、生物支架等。
为实现以上技术特点，本发明通过以下方式实现。
一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，由以下步骤组成：
120～150℃温度下将聚醚醚酮粉末与铌酸盐粉末干燥12h后，聚醚醚酮粉体与铌酸盐粉末可以共混制成聚醚醚酮/铌酸盐复合材料或在聚醚醚酮(纤维、片材、棒材)表面包裹铌酸盐材料，得到聚醚醚酮/铌酸盐复合材料，用于生物医疗植入体材料。
铌酸盐与聚醚醚酮混合比例为2:8～6:4。
铌酸盐包括铌酸钠、铌酸钾、铌酸锂、铌酸钠钾、铌酸钠锂、铌酸钾锂等其中的一种或任意两种的混合，混合比例为1:9～9:1。
聚醚醚酮粉体与铌酸盐粉末共混均匀后，烧结成型生物医用材料(如支架、棒材等)温度控制在350～450℃，腔室温度控制在130～280℃。
聚醚醚酮表面包裹的铌酸盐可通过等离子束溅射沉积、物理气相沉积等方法得到。
将得到聚醚醚酮/铌酸盐复合材料表面包裹生物可降解的高分子材料(如聚己内酯PCL、聚乳酸PLA和聚乙二醇PEG中的任一种及其混合物)，得到PEEK复合材料。
通过3D打印技术对替换的骨骼数据建模后设定参数成型所需生物植入体形状。
将得到PEEK复合材料的生物医用材料用无水乙醇清洗三次后再用丙酮清洗处理三次，晾干后经过紫外线杀菌处理后备用。
说明书附图
图1聚醚醚酮/铌酸盐共混得到的聚醚醚酮复合材料外面包裹的生物降解材料得到的棒状或片状，其中a表示聚醚醚酮，b表示铌酸盐，c表示生物降解高分子材料PCL、PLA、PEG中的一种或其混合物。
图2聚醚醚酮表面包裹铌酸盐的纤维装复合材料，其中a表示聚醚醚酮，b表示铌酸盐，c表示生物降解高分子材料PCL、PLA、PEG中的一种或其混合物。
具体实施方式
为进一步阐述本发明，下面给出实施例来说明，在下属实例中，提供了本发明若干实施方式和组成，然而本发明并不局限于采用下述方式实施，本领域技术人员在理解本发明的基础上对本发明所进行的变更、替换、改进依旧属于本发明的保护范围。
实施例1：
将聚醚醚酮与铌酸钠钾锂粉末分别在120℃下干燥12h，通过熔融共挤法得到纤维状聚醚醚酮/铌酸钠钾锂复合材料，其中熔融共挤腔室温度150℃，喷嘴温度360℃，将得到的聚醚醚酮/铌酸钠钾锂复合纤维材料表面包覆PLA/PEG得到PEEK复合材料，通过3D打印技术将PEEK成型所需的支架结构，用浓度为95％的无水乙醇冲洗三次后再用丙酮溶液清洗三次，经过紫外线杀菌处理后，进行体成骨细胞培养，对复合材料施加外力作用下与未经处理的聚醚醚酮纤维相比，聚醚醚酮复合材料纤维表面细胞增殖分化明显提高，细胞粘附性更佳，生物相容性更好。
实施例2：
将聚醚醚酮棒材在125℃下干燥12h，用浓度为95％的无水乙醇冲洗三次后再用丙酮溶液清洗三次自然晾干，通过离子束溅射沉积(IBAD)在聚醚醚酮棒材表面包裹铌酸钠钾，得到聚醚醚酮/铌酸钠钾锂复合材料，在其表面包裹PLA，用浓度为95％的无水乙醇冲洗三次后再用丙酮溶液清洗三次，得到醚醚酮复合材料，通过高温高压处理后使其结构更加紧密，经过紫外线杀菌处理后，进行体外骨细胞培养，对复合材料施加外力作用下，与未经处理的PEEK棒材相比，聚醚醚酮复合棒材表面细胞增殖分化明显提高，细胞粘附性更佳，生物相容性更好。

Claims (8)

1.一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，聚醚醚酮粉体与铌酸盐粉末可以共混制成聚醚醚酮/铌酸盐复合材料，或在聚醚醚酮(纤维、片材、棒材)表面包裹铌酸盐材料，在得到PEEK/铌酸盐复合材料表面包裹生物降解高分子材料。
2.根据权利要求1要求所述一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，铌酸盐与聚醚醚酮混合比例为1:9～9:1。
3.根据权利要求1要求所述一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，铌酸盐包括铌酸钠、铌酸钾、铌酸锂、铌酸钠钾、铌酸钠锂、铌酸钾锂等其中的一种或任意两种的混合，混合比例为2:9～6:4。
4.根据权利要求1要求所述一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，聚醚醚酮粉体与铌酸盐粉末共混均匀后，通过SLS高温烧结成型或熔融共挤出成型工艺烧结成型生物医用材料(如支架、棒材等)，温度控制在340～400℃，腔室温度控制在110～200℃。
5.根据权利要求1要求所述一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，铌酸盐可通过等离子束溅射成型、物理气相沉积方法包裹在聚醚醚酮表面。
6.根据权利要求1要求所述一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，生物降解高分子材料PCL、PLA、PEG中的一种或其混合物和衍生物。
7.根据权利要求1要求所述一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，铌酸盐表面厚度5nm～400nm。
8.根据权利要求1要求所述一种4D打印聚醚醚酮/铌酸盐复合材料及其制备方法，其特征在于，将得到聚醚醚酮/铌酸盐复合材料通过微波(Microwave)或高温高压(Autoclave)处理后使其紧密化。
CN201910498312.2A 2019-06-10 2019-06-10 一种4d打印聚醚醚酮/铌酸盐复合材料及其制备方法 Pending CN110237300A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112546292A (zh) * 2020-12-14 2021-03-26 华东理工大学 原料组合物、聚醚醚酮基复合材料及制备方法、应用
CN112625397A (zh) * 2020-12-14 2021-04-09 华东理工大学 Peek基复合材料、骨修复体、制备方法和应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112546292A (zh) * 2020-12-14 2021-03-26 华东理工大学 原料组合物、聚醚醚酮基复合材料及制备方法、应用
CN112625397A (zh) * 2020-12-14 2021-04-09 华东理工大学 Peek基复合材料、骨修复体、制备方法和应用
CN112625397B (zh) * 2020-12-14 2021-12-03 华东理工大学 Peek基复合材料、骨修复体、制备方法和应用

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WD01 Invention patent application deemed withdrawn after publication