CN113827783A - 一种人工骨用高度取向复合材料的制备方法 - Google Patents
一种人工骨用高度取向复合材料的制备方法 Download PDFInfo
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- CN113827783A CN113827783A CN202110230953.7A CN202110230953A CN113827783A CN 113827783 A CN113827783 A CN 113827783A CN 202110230953 A CN202110230953 A CN 202110230953A CN 113827783 A CN113827783 A CN 113827783A
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Abstract
本发明公开了一种人工骨用高度取向复合材料的制备方法,包含以下步骤:将高分子聚合物加入水或溶剂中溶解制得聚合物溶液;将钙盐加入水溶液中溶解后加入非金属材质的容器中,随后加入磷酸根离子溶液中,形成固体颗粒制得纳米羟基磷灰石;将聚合物溶液与纳米羟基磷灰石混合并搅拌制得混合溶液;在混合溶液的两侧放置电极板,并将两个电极板与电源接通形成电场;混合溶液粘度增加直至半固化或固化,水洗、干燥半固化或固化物获得取向被固定的复合材料;复合材料塑形;通过在电场作用下无机液晶纳米棒状分散体空间序列按照一定方向排布,在电场作用下,真空干燥或者冷冻去除溶剂,从而实现复合材料固化已取向的纳米羟基磷灰石空间有序结构固定。
Description
技术领域
本发明涉及医用复合材料领域,具体涉及一种人工骨用高度取向复合材料的制备方法。
背景技术
人骨主要是由胶原、骨粉和水分组成的,其中,骨粉的主要成分是羟基磷灰石晶体,羟基磷灰石拥有良好的生物相容性、生物活性、骨传导性和骨诱导性,被广泛的作为生物医学材料使用;作为植入物植入人体替代骨,例如骨钉、关节、种植牙等,不仅提供了骨骼和牙齿中的羟基磷灰石是三维有序的纳米自组装结构,而且具有高度组织化的层次结构,从而体现出的人骨力学和生物学性能极为卓越;
许多学者或技术人员在研究类骨胶原羟基磷灰石复合材料主要采用以下几种方法:把胶原材料和矿物晶体直接复合;在胶原纤维化的过程中实现矿物共沉淀;传统的溶液结晶成核生长过程,即把胶原基质材料浸泡于模拟体液中仿生矿化其中,第三种方法是在把胶原基质材料置于矿化诱导溶液(SBF或者mSBF)中发生HA的成核现象,这种方法成功地在胶原基质表面构建了随机分布的HA簇,但远远达不到胶原纤维间的矿化,并没有从真正意义上仿生骨结构;
胶原仿生骨的形成过程或者是骨的纳米结构传统胶原与羟基磷灰石复合材料通过胶原溶解与液体中制备成胶原溶液,在胶原溶液中加入钙盐离子与磷酸根离子,通过调节溶液酸碱度使混合体系开始沉淀,研磨后获得粉体,这种沉淀是随机的、无序的;羟基磷灰石在复合材料中的方向也是随机的、无序的,该复合材料各向同性的,他们的机械特性所在轴线中均是相同;
顾名思义,液晶就是液态晶体,也就是说具有结晶性的液体,物质的结晶性,是由组成物质的分子有着整齐与规则的排列,同时也具有液体的流动性与晶体的各向异性,形成一种兼有晶体和液体的部分性质的中间态,这种由固态向液态转化过程中存在的取向有序流体称为液晶,液晶具有光电效应,尤其是向列型液晶在电场作用下,可以控制光线的透过与截至;与有机液晶相比,无极液晶是各向异性的纳米颗粒分散在液相体现中形成稳定分散体,纳米羟基磷灰石具有有机液晶具有特殊的光、电效应,这些特性已在一些出版物中进一步描述和标准,所述出版物包括:
1.Junjun Tan等Acta Biomaterialia 116(2020)383–390;
2.Masanari Nakayama等ACSAppl.Mater.Interfaces2019,11,19,17759–17765;
无机液晶体系在电场作用下,无机液晶颗粒按照一定方向取向,方向统一排列,但关闭电场,无机液晶颗粒取向变为无序。
发明内容
本发明要解决的技术问题是现有的复合材料远远达不到胶原纤维间的矿化,并没有从真正意义上仿生骨结构,本发明提供一种人工骨用高度取向复合材料的制备方法,通过在电场作用下无机液晶纳米棒状分散体空间序列按照一定方向排布,在电场作用下,真空干燥或者冷冻去除溶剂,从而实现复合材料固化已取向的纳米羟基磷灰石空间有序结构固定,具有宏观和微观的各向异性的复合材料;该复合材料可以用于骨钉、椎间融合、骨板的制作用以解决现有技术导致的缺陷。
生物医用复合材料,它是由两种或两种以上不同材料复合而成的生物医学材料,材料可以为两种或两种以上高分子材料复合,也可以为高分子材料与无极材料进行复合,复合材料从而提高或改善单一生物材料的性能,此类材料主要用于修复及替换人体组织、器官或增进其功能;
液晶,就是说具有结晶性的液体,物质的结晶性,是由组成物质的分子有着整齐与规则的排列,同时也具有液体的流动性与晶体的各向异性;形成一种兼有晶体和液体的部分性质的中间态,这种由固态向液态转化过程中存在的取向有序流体称为液晶,液晶具有光电效应,尤其是向列型液晶在电场作用下,可以控制光线的透过与截至;
取向,是指非晶聚合物或者无极材料的大分子链段、不规则无机材料颗粒或整个高分子链,结晶聚合物的晶带、晶片、晶粒等,或纤维状填料在外力作用下,沿外力作用的方向进行有序排列的现象;
液晶取向结构固定,为了使液晶形成具有光学意义的有序性,必须借助于外力,外力使液晶分子呈规律排列,一种小分子液晶或者胶束、纳米棒液晶,以单体或胶束等状态存在,永远都是活动的,分子液晶可以自发或在外界场干预下建立起各种结构,不同的结构具有不同的光学性质,然而,由于小分子液晶或者胶束、纳米棒液晶是活动的,建立起来的结构无法保持,限制了液晶的应用,可以通过特殊设计,将结构通过聚合或者固化的方式固化下来,从而可以实现多层有序稳定结构的组合使用。
本发明还提供一种人工骨用高度取向复合材料在制备骨钉、椎间融合、骨板中的应用。
为解决上述技术问题本发明提供以下的技术方案:
第一方面,一种人工骨用高度取向复合材料的制备方法,其特征在于,包含以下步骤:
步骤A1:将高分子聚合物加入水或溶剂中溶解,搅拌至高分子聚合物完全溶解且分散均一,制得聚合物溶液;
步骤A2:将钙盐加入水溶液中溶解后加入非金属材质的容器中(比如塑料杯、玻璃杯),随后缓慢加入磷酸根离子溶液中,形成白色固体颗粒,搅拌直至不产生固体颗粒为止,停止加入磷酸根离子溶液,沉淀、过滤、水洗、烘干制得纳米羟基磷灰石,此时纳米羟基磷灰石的尺寸为长20nm-100nm,优选为20nm-50nm,长径比为4-20,优选5-10,所述钙盐与所述磷酸根离子溶液中的钙磷摩尔比为1:1-1:2,优选为1.50-1.70;
步骤A3:将聚合物溶液与纳米羟基磷灰石混合并高速搅拌至分散均一,制得混合溶液,所述聚合物与所述纳米羟基磷灰石的质量比为10%-90%,优选35%-65%,进一步优选35%-45%,所述聚合物为有机聚合物或高分子聚合物;
步骤A4:在混合溶液的两侧分别放置电极板,并将两个电极板与电源接通形成电场,电场稳定后,电场强度为0.0001-50.0N/C,优选0.05-1.0N/C,电场持续时间为10s-10h,优选10min-60min,电源电压可以为5V-220V,优选10V-60V;
步骤A5:在电场的作用下混合溶液粘度增加直至半固化或固化,获得的高度取向胶原矿化物水洗、干燥得到取向被固定的复合材料,复合材料中的有机物与无机物的比例为10%-90%,优选35%—65%;
在电场中,羟基磷灰石取向受电场影响,按照一定方向有序排列,这时真空缓慢干燥或冷冻干燥逐步去除溶剂,混合溶液粘度逐步变大,棒状纳米羟基磷灰石自由度逐步下降,混合液体至半固化或固化,棒状纳米羟基磷灰石取向方向逐步被固定,撤出电场,获得高度取向的复合材料;
步骤A6:复合材料塑形塑形,可以通过以下任意方式塑形成任务物理性状:压缩成形、浇注、注塑成型、拉挤成型、挤出成型、缠绕成型、机械加工。
上述的一种人工骨用高度取向复合材料的制备方法,其中:
步骤A1中的所述高分子聚合物为可生物降解的高分子聚合物;
所述溶剂为极性溶剂或非极性溶剂;
步骤A2中的所述羟基磷灰石为纳米羟基磷灰石;
步骤A4中的所述电极板为铁片或铜片或锌片或铝片或其他导电金属或由导电材质制成的其他电极片,亦可以选择电容,薄膜电容器等,电极板之间的间距为1mm-10000mm,优选为100mm-300mm;
可生物降解的高分子聚合物可以为均聚物、共聚物,包括无规共聚物、嵌段共聚物或接枝共聚物;可生物降解的高分子聚合物还可为线性聚合物、支化聚合物或树枝状聚合物;可生物降解的高分子聚合物还可具有天然或合成来源合适的可生物降解的高分子聚合物的实例包括但不限于诸如由以下制成的那些聚合物的聚合物:
聚氨酯、聚酸酐、聚合物药物、聚阿司匹林和蛋白质治疗剂及其共聚物和组合;
可生物降解的高分子聚合物可为共聚物或三聚物,例如:聚羟基链烷酸酯;诸如聚羟基丁酸酯(PHB);PHB/b-羟基戊酸酯共聚物(PHB/PHV);聚-b-羟基丙酸酯(PHPA);聚-对-二氧环己酮(PDS);聚-d-戊内酯-聚-ε-己内酯(capralactone)、聚(ε-己内酯-DL-丙交酯)共聚物;甲基丙烯酸甲酯-N-乙烯基吡咯烷酮共聚物;聚丙交酯(PLA)、聚-L-丙交酯(PLLA)、聚-DL- 丙交酯(PDLLA);聚乙交酯(PGA);乙交酯的共聚物、乙交酯/三亚甲基碳酸酯共聚物(PGA/TMC);聚丙交酯、乙交酯、己内酯、戊内酯、碳酸酯(例如,三亚甲基碳酸酯、四亚甲基碳酸酯等)、二氧杂环己酮(例如,1,4-二氧杂环己酮)、戊内酯、二氧杂环庚酮(l,dioxepanone)),如 l,4-二氧杂环庚-2-酮和l,5-二氧杂环庚-2-酮)、乙二醇、环氧乙烷、酯酰胺、γ-羟基戊酸酯(γ-ydroxyvalerate)、β-羟基丙酸酯、α-羟基酸、羟基丁酸酯(hydroxybuterate)、聚(原酸酯)、羟基链烷酸酯、酪氨酸碳酸酯、聚酰亚胺碳酸酯、聚亚氨基碳酸酯诸如聚(双酚 A-亚氨基碳酸酯)和聚(氢醌-亚氨基碳酸酯;
合适的天然可生物降解的高分子聚合物包括由以下制成的那些聚合物:胶原、甲壳质、透明质酸、壳聚糖、多糖、纤维素、聚(氨基酸)及其共聚物和衍生物以及组合;
根据本发明,聚羟基链烷酸酯;诸如聚羟基丁酸酯(PHB);PHB/b-羟基戊酸酯共聚物 (PHB/PHV);聚-b-羟基丙酸酯(PHPA);聚-对-二氧环己酮(PDS);聚-d-戊内酯-聚-ε-己内酯 (capralactone)、聚(ε-己内酯-DL-丙交酯)共聚物;甲基丙烯酸甲酯-N-乙烯基吡咯烷酮共聚物;聚缩酚肽;非对称-3,6-取代的聚-1,4-二氧六环-2,5-二酮;聚酯酰胺;草酸的聚酯;PLA的其他共聚物,诸如丙交酯/四甲基乙交酯共聚物、丙交酯/三亚甲基碳酸酯共聚物、丙交酯/d-戊内酯共聚物、丙交酯/ε-己内酯共聚物、L-丙交酯/DL-丙交酯共聚物、乙交酯/L- 丙交酯共聚物(PGA/PLLA)、聚丙交酯-共-乙交酯;PLA的三聚物,诸如丙交酯/乙交酯/三亚甲基碳酸酯三聚物、丙交酯/乙交酯/ε-己内酯三聚物、PLA/聚环氧乙烷共聚物;聚二氢吡喃;聚烷基-2-氰基丙烯酸酯;聚氨酯(PU);聚乙烯醇(PVA);多肽;聚原酸酯;聚碳酸酯;聚(酯酸酐);聚-b-苹果酸(PMLA):聚-b-链烷酸(alkanbic acid);聚磷酸酯及其混合物;以及天然聚合物,诸如糖;淀粉、纤维素和纤维素衍生物、多糖、纤维蛋白、透明质酸、胶原、壳聚糖、多肽以及蛋白质;
还可使用任何上述聚合物的混合物及其各种形式;
可生物降解的高分子聚合物优选地在聚合物基体中体现,所述聚合物基体可任选地包含任何以上聚合物,任选地且优选地,它可包含选自由以下组成的组的聚合物:可生物吸收胶原、胶原蛋白、明胶;如果使用胶原,则基体优选地包含至少30%胶原,更优选地为50%,并且最优选地为至少70%胶原;如果使用非胶原蛋白,则基体优选地包含至少5%非胶原蛋白,更优选地为至少10%,最优选地为至少20%非胶原蛋白。
上述的一种人工骨用高度取向复合材料的制备方法,其中:
所述极性溶剂选取水、二氯甲烷、氯仿、四氯化碳、乙酸乙酯、丙酮、异丙醇、六氟异丙醇、丁酮、环己酮、乙酸丁酯、碳酸酯、乙腈、四氢呋喃、二氧六环、甲酰胺、乙酸、丙酸中的一种或几种混合;
所述非极性溶剂选取环己烷、甲苯、石油醚、石油烃、异辛烷中的一种;
所述水溶液为水或水的酸性溶液或水的碱性溶液;
所述电极板的厚度为0.6μm-100mm,优选0.6μm-10μm。
上述的一种人工骨用高度取向复合材料的制备方法,其中:
所述羟基磷灰石中掺杂有阳离子或阴离子或阴阳离子;
掺杂元素为以下中的一种或几种:锌、锶、镁、锰、硒、硅、氟、铁、碳酸根CO3 2-、SiO4 -、SeO4 4-、VO4 3-、Mn O4-,优选没有取代的羟基磷灰石。
上述的一种人工骨用高度取向复合材料的制备方法,其中:
所述羟基磷灰石中还加有以下中的一种或几种:磷酸钙、磷酸氢钙、碳酸钙、硅酸钙、氟磷灰石、磷酸三钙、生长因子、磷酸八钙陶瓷、磷酸四钙陶瓷、磷酸八钙陶瓷、焦磷酸钙(calciumpyrophosphate)、磷灰石型陶瓷、氢氧基磷灰石、氟化物磷灰石、碳酸盐磷灰石、类磷灰石矿物、替代磷灰石、钙缺乏磷灰石,如CaNaPO4及CaKPO4等的磷酸钙碱、或其组合;碳酸钙陶瓷可为合成材料,或者是类似珊瑚等的天然矿物,无水硫酸钙、二水硫酸钙、半水硫酸钙、或其组合。
羟基磷灰石可以为缺钙型羟基磷灰石,可以为富钙型羟基磷磷灰石,可以为几种复合,钙元素与磷元素的摩尔比为1.0-2.0,优选1.5-1.6;
羟基磷灰石的粒径长为5nm-400nm,优选20-100nm,长径比为3-500,优选4-50;
所述羟基磷灰石为以下形状中的任一种:针状、棒状、长片状、鳞片状、椭圆形状、条状、菱形状、线条状、盘状、柱状,优选为针状或棒状。
上述的一种人工骨用高度取向复合材料的制备方法,其中:
步骤A2中的所述羟基磷灰石的制备方法选取以下方法中的任一种:溶胶-凝胶法、水热法、超声波法、微乳液法、固相反应法、水热法、化学沉降法、自然烧法、模板法,优选水热法或化学沉降法;
步骤A3中所述聚合物溶液与所述纳米羟基磷灰石的混合方法选取以下方法中的任一种:溶液混合、熔融混合、拉挤混合,也可以是高分子溶液制备羟基磷灰石,然后进行混合;
步骤A4中所述电场为静电场或感应电场或涡旋电场、脉冲电场,优选静电场,静电场电场强度为0.0001-50.0N/C,优选0.05-1.0N/C。
诱导分散溶胶棒状纳米羟基磷灰石取向,通过赋予特性尺度纳米羟基磷灰石这种液晶相变行为与电学场效应相互作用,控制纳米棒状纳米羟基磷灰石的空间排列按同一方向,形成高度取向液晶网络,然后采用特殊的加工工艺在沉淀过程中保持棒状纳米羟基磷灰石空间排布方向不变,除去混合体系中的溶剂,混合体系由液体转变为固体,棒状纳米羟基磷灰石的有序排布方向被固定,建立起来的宏观纳米羟基磷灰石稳定有序组装的类骨仿生骨材料。
第二方面,一种人工骨用高度取向复合材料在制备骨钉、椎间融合、骨板中的应用。
本发明通过赋予特性尺度纳米羟基磷灰石这种液晶相变行为与电学场效应相互作用,控制纳米棒状纳米羟基磷灰石的空间排列按同一方向,形成高度取向液晶网络,然后采用特殊的加工工艺,将建立起来取向液晶结构空间排布中固化下来,纳米棒状羟基磷灰石不能自由移动,从而实现宏观纳米羟基磷灰石稳定有序组装的类骨仿生骨材料。
依据上述本发明一种人工骨用高度取向复合材料的制备方法提供的技术方案具有以下技术效果:
一种人工骨用高度取向复合材料的制备方法为通过在电场作用下无机液晶纳米棒状分散体空间序列按照一定方向排布,在电场作用下,真空干燥或者冷冻去除溶剂,从而实现复合材料固化已取向的纳米羟基磷灰石空间有序结构固定,具有宏观和微观的各向异性的复合材料;
该复合材料可以用于骨钉、椎间融合、骨板的制作。
附图说明
图1为光透射率测试仪的结构示意图;
图2为本发明一种人工骨用高度取向复合材料的制备方法的流程图;
图3为在电场作用条件下制备材料的扫描电镜图片;
图4为细胞成骨实验对比图。
具体实施方式
为了使发明实现的技术手段、创造特征、达成目的和功效易于明白了解,下结合具体图示,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。
基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
须知,本说明书所附图式所绘示的结构、比例、大小等,均仅用以配合说明书所揭示的内容,以供熟悉此技术的人士了解与阅读,并非用以限定本发明可实施的限定条件,故不具技术上的实质意义,任何结构的修饰、比例关系的改变或大小的调整,在不影响本发明所能产生的功效及所能达成的目的下,均应仍落在本发明所揭示的技术内容得能涵盖的范围内。
同时,本说明书中所引用的如“上”、“下”、“左”、“右”、“中间”及“一”等的用语,亦仅为便于叙述的明了,而非用以限定本发明可实施的范围,其相对关系的改变或调整,在无实质变更技术内容下,当亦视为本发明可实施的范畴。
现有名词解释如下:
骨板,通用方法在骨愈合期间或愈合之后使用骨板来将骨折或切断的骨的不同部位保持相对固定,肢体的骨具有头部的,骨的轴通常是细长圆柱,提供一种骨板,其连接到骨折骨的轴部或头部和轴部,以将两个或更多个骨块相对于彼此保持在基本上固定的位置,这样的骨板通常包括具有相对的基本上平行的侧的形状和在相对的两侧之间延伸的多个孔,其中孔适于接收针或螺钉以将板附接到骨碎片;
螺钉,螺钉用于骨固定,以起到固定骨块的作用,并且存在基于骨折的类型和将使用螺钉的方式的不同设计,螺钉随着骨的不同尺寸也具有不同尺寸,螺钉可单独用于保持骨折,也可与板、杆或钉子一起联合或搭配使用,在骨愈合过程中被吸收或者后螺钉可留在修补部位或通过手术移除;
引线/销针,引线通常用于将骨头连接在一起,它们通常用于将太小而不适合采用螺钉固定的骨块相对保持在一起,它们可与其他医疗器械的内固定搭配使用,但是它们可单独用于治疗小型骨的骨折,引线或销针可以在一侧,也可以在两侧上用于插入或钻入骨中用于骨之间连接的尖点;
颅骨修复中的锚钉,埋入骨质中固定撕裂腱性组织,以达到腱骨生物性愈合的目的,骨中的锚固部位和缝合线所穿过的锚钉,可以是环状,可以是多空,可以是圆形,也可以是方形,这将锚钉与缝合线连接,锚钉的直径通常在1.0至6.5mm范围内;
嵴椎,脊柱椎体间、横突间和(或)椎板间植骨融合。
骨固定植入物的其他非限制性、说明性实例可任选地包括板、板和螺钉系统以及外固定器。
任何上述骨固定植入物可任选地用于固定各种骨折类型,所述各种骨折类型包括但不限于四肢各类闭合性骨折骨缺损修复或难愈合部位骨折或开放性骨折缺损的二期修、非愈合性骨折、粉碎性骨折、近端和远端骨折、截骨部位、节段性骨折、具有骨损失的骨折、骨干骨折、牙槽嵴扩展、牙根切除、牙周骨缺损的充填,根尖切除和囊肿切除术后骨缺损、牙窝充填、引导骨再生材料一起用于充填种植体周围的骨缺等。
实施例1:
将钙盐、油酸、三乙胺按照摩尔数2.5:5:4分别加入水与乙醇混合溶剂,水与乙醇质量比:1:3,充分搅拌溶解,溶解完毕待用Ⅰ,将磷酸钠溶于水中,搅拌溶解,溶解完毕待用Ⅱ,将II加入I中,搅拌,混合体系中逐步生成羟基磷灰石,不产生沉淀为止制备体系Ⅲ,以备待用;
将PAA聚丙烯酸溶解于水中,用氢氧化钠调节pH至7-8,获得溶液Ⅳ,将Ⅰ缓慢加入Ⅳ中,搅拌60分钟,放入超声波超声分散30分钟,两片电极板之间,电极板距离为10cm,电压为60V,放置时间为60分钟;
抽空至-0.01MPa至混合溶剂去除,撤除电场,取出容器内固体样品Ⅴ1,用少量水清洗,烘干;
将Ⅴ1压入模具尺寸50.8mm×12.7mm×1mm,以备测试。
实施例2:
将胶原溶于酸性水溶液中,加入钙盐和磷酸根盐,两者摩尔比为2:1,搅拌均匀获得混合液体Ⅰ,放入两片电极板之间,电极板距离为10cm,电场强度为3V/cm,用0.1mol强氧化钾溶液缓慢调节至中性,在电场环境下放置60分钟,进行冷冻干燥,压缩,制备产品Ⅴ1。
实施例3:
将胶原溶于酸性水溶液中,加入钙盐和磷酸根盐,两者摩尔比为2:1,搅拌均匀获得混合液体Ⅰ,放入两片电极板之间,电极板距离为10cm,电场强度为6V/cm,用0.1mol强氧化钾溶液缓慢调节至中性,在电场环境下放置60分钟,进行冷冻干燥,压缩,制备产品Ⅴ2。
实施例4:
将胶原溶于酸性水溶液中,加入钙盐和磷酸根盐,两者摩尔比为2:1,搅拌均匀获得混合液体Ⅰ,放入两片电极板之间,电极板距离为10cm,电场强度为9V/cm,用0.1mol强氧化钾溶液缓慢调节至中性,在电场环境下放置60分钟,进行冷冻干燥,压缩,制备产品Ⅴ3。
对比实验:
将胶原溶于酸性水溶液中,加入钙盐和磷酸根盐,两者摩尔比为2:1,搅拌均匀获得混合液体Ⅰ,进行冷冻干燥,压缩,制备产品Ⅴ0;
采用光学强度透过测试仪对实施例2、实施例3、实施例4进行测试,得到光透过强度百分比数值,如表1所示,对比可以看出,电场作用下的样品透光率由于未加入电场的样品,电场强度提高,透光的光强度越高;
项目 | 光透过强度% |
对比实验 | 10% |
实施例2 | 40% |
实施例3 | 60% |
实施例4 | 90% |
表1
实施例6:
将钙盐、油酸、三乙胺按照摩尔数2.5:5:4分别加入水与乙醇混合溶剂,水与乙醇质量比:1:3,充分搅拌溶解,溶解完毕待用Ⅰ,将磷酸钠溶于水中,搅拌溶解,溶解完毕待用Ⅱ。将II加入I中,搅拌,混合体系中逐步生成羟基磷灰石,不产生沉淀为止制备体系Ⅲ,将Ⅲ过滤将聚-L-丙交酯(PLLA)溶于氯仿中,搅拌均一,放入在电场强度为9V/cm的环境中使混合体系取向,在电场环境下在-0.1MPa真空去除溶剂。
实施例7:
将钙盐、油酸、氢氧化钠按照摩尔数2.5:5:2分别加入水与乙醇混合溶剂,水与乙醇质量比:1:3,充分搅拌溶解,溶解完毕待用Ⅰ,将磷酸钠溶于水中,搅拌溶解,溶解完毕待用Ⅱ,将II加入I中,搅拌,混合体系中逐步生成羟基磷灰石,不产生沉淀为止制备体系Ⅲ,将Ⅲ过滤将聚-L-丙交酯(PLLA)溶于氯仿中,搅拌均一,放入在电场强度为9V/cm的环境中使混合体系取向,在电场环境下在-0.1MPa真空去除溶剂获得产品,将产品压入模具尺寸50.8mm×12.7mm×1mm,以备测试。
实施例8:
将钙盐、油酸、乙二胺按照摩尔数2.5:5:2分别加入水与乙醇混合溶剂,水与乙醇质量比:1:3,充分搅拌溶解,溶解完毕待用Ⅰ,将磷酸钠溶于水中,搅拌溶解,溶解完毕待用Ⅱ,将II加入I中,搅拌,混合体系中逐步生成羟基磷灰石,不产生沉淀为止制备体系Ⅲ,将Ⅲ过滤将聚-L-丙交酯(PLLA)溶于氯仿中,搅拌均一,在-0.1MPa真空去除溶剂,将产品压入模具尺寸50.8mm×12.7mm×1mm,以备测试。
根据GB/T9341-2008 GB,GB/T 1040.1-2006使用5000N的负荷传感器和三点抗弯夹具、拉力传感器,测试产品的最大载荷、弯曲强度和弹性模量,对实施例6-7所得的产品检测,检测数据如表2:
表2
实施例9:
将胶原溶于酸性水溶液中,加入钙盐和磷酸根盐,两者摩尔比为2:1,胶原与磷酸钙盐质量比为50:50,搅拌均匀获得混合液体Ⅰ,放入两片电极板之间,电极板距离为10cm,电场强度为3V/cm,用0.1mol强氧化钾溶液缓慢调节至中性,进行冷冻干燥,压缩,制备产品Ⅴ1-1。
实施例10:
将胶原溶于酸性水溶液中,加入钙盐和磷酸根盐,两者摩尔比为2:1,胶原与磷酸钙盐质量比为40:60,搅拌均匀获得混合液体Ⅰ,放入两片电极板之间,电极板距离为10cm,电场强度为3V/cm,用0.1mol强氧化钾溶液缓慢调节至中性,在电场环境下放置60分钟,进行冷冻干燥,压缩,制备产品Ⅴ1-2。
实施例11:
将胶原溶于酸性水溶液中,加入钙盐和磷酸根盐,两者摩尔比为2:1,胶原与磷酸钙盐质量比为35:65,搅拌均匀获得混合液体Ⅰ,放入两片电极板之间,电极板距离为10cm,电场强度为3V/cm,用0.1mol强氧化钾溶液缓慢调节至中性,在电场环境下放置60分钟,进行冷冻干燥,压缩,制备产品Ⅴ1-3。
细胞实验:
为了研究复合材料的生物相容性,采用体外细胞实验进行考察,对实施例8(实验8)、实施例9(实验9)、实施例10(实验10)采用MC3T3-E1(前成骨细胞)在10%牛血清、100当量/mL青霉素、100mg/ml链霉素的培养基进行培养,培养基环境为37℃,5%二氧化碳,培养基每两天更新一次,样品用75%乙醇浸泡30min进行灭菌,采用PBS溶液清洗。首先在5 ×104细胞接种灭菌样品为1×1cm2上,培养1、7、14天后,活性的测定采用分光光度法使用微孔板读数仪在405nm处四次对比观察,作为至少三个独立变量的平均值±标准差(SD)实验,各组间的统计分析如下:采用spss16.0软件进行单因素分析的基础上方差,细胞成骨实验对比如图4所示;
从图4与图3中可以看出,取向复合材料的吸光值一般都高于没有取向的复合材料,随着培养时间的增加,吸光值的差异越明显,说明具有良好生物相容性的取向复合材料,对细胞的增殖具有明显促进作用。通过吸光值对比来看,随着HA含量的增加对细胞的促进增殖作用越明显,在取向复合材料中,HA含量越高,复合材料表面上生长了更多的细胞。因此,取向复合材料的细胞相容性明显优于没有取向的复合材料,随着培养时间的延长,细胞增殖也较明显。
综上,本发明的一种人工骨用高度取向复合材料的制备方法,通过在电场作用下无机液晶纳米棒状分散体空间序列按照一定方向排布,在电场作用下,真空干燥或者冷冻去除溶剂,从而实现复合材料固化已取向的纳米羟基磷灰石空间有序结构固定,具有宏观和微观的各向异性的复合材料;该复合材料可以用于骨钉、椎间融合、骨板等的制作。
以上对发明的具体实施例进行了描述。需要理解的是,发明并不局限于上述特定实施方式,其中未尽详细描述的设备和结构应该理解为用本领域中的普通方式予以实施;本领域技术人员可以在权利要求的范围内做出各种变形或修改做出若干简单推演、变形或替换,这并不影响发明的实质内容。
Claims (10)
1.一种人工骨用高度取向复合材料的制备方法,其特征在于,包含以下步骤:
步骤A1:将高分子聚合物加入水或溶剂中溶解,制得聚合物溶液;
步骤A2:将钙盐加入水溶液中溶解后加入非金属材质的容器中,随后加入磷酸根离子溶液中,形成固体颗粒,搅拌直至不产生固体颗粒为止,沉淀、过滤、水洗、烘干制得纳米羟基磷灰石;步骤A3:将聚合物溶液与纳米羟基磷灰石混合并高速搅拌制得混合溶液;
步骤A4:在混合溶液的两侧分别放置电极板,并将两个电极板与电源接通形成电场;
步骤A5:在电场的作用下混合溶液粘度增加直至半固化或固化,水洗、干燥半固化或固化物获得取向被固定的复合材料;
步骤A6:复合材料塑形。
2.如权利要求1所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:
步骤A1中的所述高分子聚合物为可生物降解的高分子聚合物;
所述溶剂为极性溶剂或非极性溶剂;
步骤A2中的所述羟基磷灰石为纳米羟基磷灰石;
步骤A4中的所述电极板为铁片或铜片或锌片或铝片或由导电材质制成的其他电极片。
3.如权利要求2所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:
所述极性溶剂选取氯仿、乙酸乙酯、丙酮、异丙醇中的一种;
所述非极性溶剂选取环己烷、甲苯、石油醚中的一种;
所述水溶液为水或水的酸性溶液或水的碱性溶液;
所述电极板的厚度为0.6μm-100mm。
4.如权利要求3所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:所述羟基磷灰石中掺杂有阳离子或阴离子或阴阳离子;
掺杂元素为以下中的一种或几种:锌、锶、镁、锰、硒、硅、氟、铁、碳酸根CO3 2-、SiO4 -、SeO4 4-、VO4 3-、MnO4-。
5.如权利要求4所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:
所述羟基磷灰石中还加有以下中的一种或几种:磷酸钙、磷酸氢钙、碳酸钙、硅酸钙、氟磷灰石、磷酸三钙、生长因子、磷酸八钙。
6.如权利要求5所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:
所述羟基磷灰石为以下形状中的任一种:针状、棒状、长片状、鳞片状、椭圆形状、条状、菱形状、线条状、盘状、柱状;
所述羟基磷灰石的长为5nm-400nm,长径比为3-500。
7.如权利要求1-6任一项所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:
步骤A2中所述钙盐与所述磷酸根离子溶液中的钙磷摩尔比为1:1-1:2;
步骤A3中所述聚合物与所述纳米羟基磷灰石的质量例为10%-90%,所述聚合物为有机聚合物或高分子聚合物;
步骤A5中所述复合材料中的有机物与无机物的比例为10%-90%。
8.如权利要求7所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:
步骤A2中的所述羟基磷灰石的制备方法选取以下方法中的任一种:溶胶-凝胶法、水热法、超声波法、微乳液法、固相反应法、水热法、化学沉降法、自然烧法、模板法;
步骤A3中所述聚合物溶液与所述纳米羟基磷灰石的混合方法选取以下方法中的任一种:溶液混合、熔融混合、拉挤混合;
步骤A4中所述电场为静电场或感应电场或涡旋电场、脉冲电场;
步骤A6中所述复合材料塑形的方法选取以下方法中的任一种:压缩成形、浇注、注塑成型、拉挤成型、挤出成型、缠绕成型、机械加工。
9.如权利要求6所述的一种人工骨用高度取向复合材料的制备方法,其特征在于:
步骤A4中所述电场的电场强度为0.0001-50.0N/C,电场持续时间为10s-10h,电源电压可以为5V-220V;
步骤A4中两个所述电极板之间的间距为1mm-10000mm。
10.如权利要求1-9任一项所述的一种人工骨用高度取向复合材料在制备骨钉、椎间融合、骨板中的应用。
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