CN112546294A - 聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法及其产品和应用 - Google Patents
聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法及其产品和应用 Download PDFInfo
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Abstract
本发明涉及是一种聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法,通过固相反应法制备α‑磷酸三钙(α‑TCP),作为磷酸钙骨水泥粉末的主体成分;在粉末中添加一定比例的聚酸酐粉末充分混合均匀制备得到骨水泥粉末;将该粉末与含有磷酸氢二钠的固化液按一定固液比进行调和,固化得到磷酸钙骨水泥。通过控制聚酸酐的化学成分和比例,实现骨水泥生物降解速率的调控。本发明以聚酸酐为改性剂,其酸性降解产物能降低材料周围的pH值,促进磷酸钙的降解,实现骨水泥生物降解速率可控。所用材料生物相容性良好,制备方法简单,便于扩大生产,具有广泛的应用前景。
Description
技术领域
本发明涉及一种生物医用材料技术领域的方法,具体是一种聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法及其产品和应用。
背景技术
磷酸钙类骨水泥以其良好的生物相容性、骨传导性、骨诱导性和生物可降解性[Apelt D, Biomaterials, 2004],作为临床骨修复替代材料受到了很大的关注。但由于磷酸钙骨水泥固化形成的产物,如羟基磷灰石、缺钙型羟基磷灰石等,在体内降解速度较慢,临床上常常遇到材料降解速度与新骨生长速度不匹配的问题,延长了修复部位的自愈时间。
聚酸酐是美国FDA批准的可应用于临床的可降解生物材料,常用于药物的控制释放方面的研究和应用。合成的聚酸酐种类包括脂肪族聚酸酐、芳香族聚酸酐、不饱和聚酸酐、可交联聚酸酐等,其中脂肪族、芳香族共聚酸酐的降解速率可通过调节共聚单体的比例来控制。聚酸酐的体外降解为表面溶蚀机制,可实现长时间降解,降解产物呈酸性,能降低材料周围的pH值,从而进一步催化自身水解,其降解过程呈自加速现象。
发明内容
本发明目的在于提供一种聚酸酐改性的磷酸钙骨水泥的制备方法。
本发明的再一目的在于:提供一种上述方法制备的聚酸酐改性的磷酸钙骨水泥产品。
本发明的又一目的在于:提供一种上述产品的应用。
本发明目的通过下述方案实现:一种聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法,其特征在于通过固相反应法制备α-磷酸三钙(α-TCP),作为磷酸钙骨水泥粉末的主体成分;在粉末中添加一定比例的聚酸酐粉末充分混合均匀制备得到骨水泥粉末;将该粉末与含有磷酸氢二钠的固化液按一定固液比进行调和,固化得到磷酸钙骨水泥,通过控制聚酸酐的化学成分和比例,实现骨水泥生物降解速率的调控,包括以下步骤:
(1)按摩尔比2:1混合磷酸氢钙与碳酸钙,干燥后用马弗炉在1250-1400℃煅烧2-4h后取出,鼓风环境下急速冷却,之后用氧化锆球磨,乙醇为球磨介质,450rpm湿法球磨4h,80℃烘箱中干燥,得到粒径均一的α-TCP粉末;
(2)将所得的α-TCP粉末与聚酸酐粉末按质量比99:1-8:2进行混合,得到骨水泥粉末;
(3)将上述骨水泥粉末与固化液按固液比2-3g/mL进行调和,即可得到可控生物降解磷酸钙骨水泥,所述固化液为质量分数为2.5%的磷酸氢二钠溶液。
本发明针对以上背景与不足,提供了一种聚酸酐改性的磷酸钙骨水泥及其制备方法,通过控制改性剂聚酸酐的成分和骨水泥制备工艺,实现磷酸钙骨水泥生物降解性能的调控,克服其降解速度较慢的不足。
步骤(1)所述的磷酸氢钙与碳酸钙的混合方式为纯水介质中湿法球磨,球磨速度为400rpm,球磨时间为2-4h;干燥方式为置于80℃烘箱中干燥过夜。
步骤(2)所述的聚酸酐粉末包括脂肪族聚酸酐、芳香族聚酸酐、共聚聚酸酐、不饱和聚酸酐中的一种或两种及以上组合,所述混合方式为使用玛瑙球磨罐进行低速干法球磨。
步骤(3)所述可控生物降解磷酸钙骨水泥在0.01M PBS溶液中一个月内降解率在质量分数20%以上。
本发明还提供了一种聚酸酐改性的可控生物降解磷酸钙骨水泥,根据上述任一所述方法制备得到。
本发明也提供了一种聚酸酐改性的可控生物降解磷酸钙骨水泥在制备可控生物降解磷酸钙骨水泥材料中的应用。
本发明的优点在于:
1.本发明以聚酸酐为改性剂,其酸性降解产物能降低材料周围的pH值,促进磷酸钙的降解,实现骨水泥生物降解速率可控。
2.所用材料生物相容性良好,制备方法简单,便于扩大生产,具有广泛的应用前景。
附图说明
图1是所制备可控生物降解磷酸钙骨水泥的体外降解曲线;
图2是降解溶液pH变化曲线。
具体实施方式
以下实施例以发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围并不限于下述的实施例。
实施例1
一种聚酸酐改性的可控生物降解磷酸钙骨水泥,通过固相反应法制备α-磷酸三钙(α-TCP),作为磷酸钙骨水泥粉末的主体成分;在粉末中添加一定比例的聚酸酐粉末充分混合均匀制备得到骨水泥粉末;将该骨水泥粉末与含有磷酸氢二钠的固化液按一定固液比进行调和,固化得到磷酸钙骨水泥,通过控制聚酸酐的化学成分和比例,实现骨水泥生物降解速率的调控,按以下步骤制备:
(1)α-TCP的制备:按摩尔比2:1将磷酸氢钙与碳酸钙混合,使用纯水为介质湿法球磨,转速400rpm,球磨时间4h,球磨珠与粉末质量比为2:1、原料混合液置于80℃烘箱中干燥过夜后,将干燥后的粉末置于马弗炉1400℃煅烧2h后取出,鼓风环境下急速冷却后,将冷却后的粉末以无水乙醇为介质湿法球磨,转速450rpm用氧化锆球磨罐球磨6h,使用纯水为介质湿法球磨,球磨珠与粉末质量比为4:1,粉末悬浊液置于80℃烘箱中充分干燥,制备得到粒径均匀的α-TCP粉末;
(2)体外降解试验:
配制0.01M PBS(pH7.2-7.4)缓冲溶液。将固化后的骨水泥样品置于60℃烘箱干燥24h,冷却后称重。浸入上述PBS缓冲溶液,其中样品质量/溶液体积为1g/50mL,在一段时间后取出用超纯水清洗表面,置于60℃烘箱干燥24h,冷却后称重。每个配方至少测试5个以上样品。绘制时间-剩余质量百分比曲线。
将(1)中制备的α-TCP与聚癸二酸、1,3-双羧基对苯丙醇共聚物(聚酸酐p(CPP-co-SA))按质量比9:1进行混合,混合方式为在玛瑙球磨罐中150rpm干法球磨,得到骨水泥粉末;
将骨水泥粉末与质量分数为2.5%的磷酸氢二钠溶液按2g/mL进行调和,即可得到可控生物降解磷酸钙骨水泥,参照标准ASTM C191测定初凝时间为11 min,通过(2)所述方法测试其体外降解试验,结果如图1所示,记录pH变化曲线如图2所示。
实施例2
一种聚酸酐改性的可控生物降解磷酸钙骨水泥,与实施例步骤(1)相同,按以下步骤制备:
将实施例1(1)中制备的α-TCP与聚癸二酸酐按质量比9:1进行混合,混合方式为在玛瑙球磨罐中150rpm干法球磨,得到骨水泥粉末;
将骨水泥粉末与质量分数为2.5%的磷酸氢二钠溶液按2g/mL进行调和,参照标准ASTM C191测定初凝时间为11 min。
实施例3
一种聚酸酐改性的可控生物降解磷酸钙骨水泥,与实施例步骤(1)相同,按以下步骤制备:
将实施例1(1)中制备的α-TCP与聚酸酐p(CPP-co-SA)按质量比95:5进行混合,混合方式为在玛瑙球磨罐中150rpm干法球磨,得到骨水泥粉末;
将骨水泥粉末与质量分数为2.5%的磷酸氢二钠溶液按2g/mL进行调和,参照标准ASTM C191测定初凝时间为10min。
Claims (6)
1.一种聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法,其特征在于通过固相反应法制备α-磷酸三钙(α-TCP),作为磷酸钙骨水泥粉末的主体成分;在粉末中添加一定比例的聚酸酐粉末充分混合均匀制备得到骨水泥粉末;将该骨水泥粉末与含有磷酸氢二钠的固化液按一定固液比进行调和,固化得到磷酸钙骨水泥,通过控制聚酸酐的化学成分和比例,实现骨水泥生物降解速率的调控,包括以下步骤:
(1)按摩尔比2:1混合磷酸氢钙与碳酸钙、干燥后,在马弗炉1250-1400℃煅烧2-4h后取出,鼓风环境下急速冷却后,用氧化锆球磨,400~450rpm湿法球磨4h,80℃烘箱中干燥,得到粒径均匀的α-TCP粉末;
(2)将所得的α-TCP粉末与聚酸酐粉末按质量比99:1~8:2进行混合,得到骨水泥粉末;
(3)将上述骨水泥粉末与固化液按固、液比2-3g/mL进行调和,所述固化液为质量分数为2.5%的磷酸氢二钠溶液,即可得到可控生物降解磷酸钙骨水泥。
2.根据权利要求1所述聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法,其特征在于,步骤(1)中,所述的磷酸氢钙与碳酸钙的混合方式为纯水介质中湿法球磨,球磨速度为400rpm,球磨时间为2-4h;干燥方式为置于80℃烘箱中干燥过夜。
3.根据权利要求1所述聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法,其特征在于,步骤(2)所述的聚酸酐粉末包括脂肪族聚酸酐、芳香族聚酸酐、共聚聚酸酐、不饱和聚酸酐中的一种或两种及以上组合。所述混合方式为使用玛瑙球磨罐进行低速干法球磨。
4.根据权利要求1所述聚酸酐改性的可控生物降解磷酸钙骨水泥的制备方法,其特征在于,步骤(3)所述可控生物降解磷酸钙骨水泥在0.01M PBS溶液中一个月内降解率在质量分数20%以上。
5.一种聚酸酐改性的可控生物降解磷酸钙骨水泥,其特征在于根据权利要求1-4任一所述方法制备得到。
6.一种根据权利要求5所述聚酸酐改性的可控生物降解磷酸钙骨水泥在制备可控生物降解磷酸钙骨水泥材料中的应用。
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