CN105999401A - 一种基于羟基磷灰石的牙科抑菌修复材料及其制备方法 - Google Patents
一种基于羟基磷灰石的牙科抑菌修复材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及基于羟基磷灰石的牙科抑菌修复材料及其制备方法。它包括羟基磷灰石、以及负载在羟基磷灰石上的聚硅氧烷或聚苯乙烯‑聚硅氧烷共聚物、聚乙二醇或含PEG结构的聚合物，其中：聚硅氧烷或聚苯乙烯‑聚硅氧烷共聚物质量占羟基磷灰石质量的5％～30％，PEG或含PEG结构的聚合物质量占羟基磷灰石质量的5％～35％。该牙齿生长修复材料机械强度高、生物相容性好，并具有良好的抑菌性。
Description
技术领域
本发明属于牙科修复材料技术领域，具体涉及一种基于羟基磷灰石的牙科抑菌修复材料及其制备方法，其能较好的抑制口腔细菌的滋生。
背景技术
口腔是一个充满各种微生物的环境。每当人体进食时，随着食物进入口腔中的细菌会和食物中的糖类发生化学作用，产生腐蚀牙齿的酸性物质。如此以往，牙齿的表面的保护层就会被这些物质破坏，形成比较脆弱的菌斑，如果继续恶化下去则会形成牙洞，即蛀牙。蛀牙在严重的情况下，会导致牙齿的坏死和脱落。因此，寻求在缺失牙齿的牙槽里或残缺的牙齿表面生长修复具有类牙齿材料的抗菌牙齿材料十分必要。
在当前的牙齿生长抗菌修复材料中，专利号为201510525924公开了一种以主要成分为含银、铜、钙和磷的磷灰石晶体、氧化钛和氧化锌的无机材料用于牙齿抗菌修复材料。专利号为201510541054公开了一种以甲基丙烯酸酯类单体、稀释剂及环氧体系、引发剂和抗菌添加剂的用于牙齿抗菌修复树脂。专利号为200710019127公开一类季铵盐型抗菌材料在牙科抗菌修复材料的应用。但是这些材料在材料相容性和抗菌长效性上都有各自的不足。
发明内容
本发明专利的目的在于针对上述现有技术不足，提供一种加工工艺稳定、生产成本低廉、无污染排放、可在常规条件下组织生产的牙齿抑菌修复材料及其制备方法。该牙齿生长修复材料具有抗菌效果，较常规牙齿生长修复材料的生物相容性和使用寿命也大幅提升。
提供一种基于羟基磷灰石的牙科抑菌材料，它包括羟基磷灰石，以及负载在羟基磷灰石上的聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物、聚乙二醇(PEG)或含PEG结构的聚合物，其中：聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物质量占羟基磷灰石质量的5％～30％，PEG或含PEG结构的聚合物质量占羟基磷灰石质量的5％～35％。
按上述方案，所述聚硅氧烷为
n为20～200，
上述结构式中R1、R2独立选自-CH3或-CH＝CH2；
或为表示的嵌段中两种的共聚物；
上述结构式中R1、R2独立选自-CH3或-CH＝CH2，各嵌段的聚合度为20～200。
按上述方案，所述的基于羟基磷灰石的牙科抑菌材料还包括抗菌添加剂，所述的抗菌添加剂为辣椒素，用量占羟基磷灰石质量的0.01～0.25％。
按上述方案，所述含PEG结构的聚合物应包含如下结构，如式1所示：
式1
其中n≥7，
按上述方案，所述含PEG结构的聚合物为聚赖氨酸接枝的PEG，甲基丙烯酸甲酯接枝的PEG，十八胺聚氧乙烯醚(PEGO)，磺化芳纶接枝的十八胺聚氧乙烯醚(PEGO)等。
上述基于羟基磷灰石的牙科抑菌材料的制备方法如下：
将辣椒素溶解到乙醇溶液中，然后加入PEG或含PEG结构的聚合物，振荡一段时间后待辣椒素吸附饱和后取出；
将聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物，和吸附有辣椒素的PEG或含PEG结构的聚合物溶解在乙醇溶液中，然后将混合溶液以喷涂或旋涂的方法涂覆在羟基磷灰石表面，烘干除去溶剂后得到新型牙齿抗菌修复材料。
按上述方案，用磷酸三乙酯和硝酸钙为原料经水解合成羟基磷灰石溶液，经过烘箱烘干后得到羟基磷灰石的固体，然后将其高温熔融后压片得到平整片材，高温熔融温度1600-1800℃。
按上述方案，所述羟基磷灰石的制备方法：称取一定量的磷酸三乙酯溶解在无水乙醇中，配成0.1～2mol/L的溶液，然后缓慢滴加蒸馏水，强烈搅拌使磷酸三乙酯逐渐水解；称取一定量硝酸钙溶于无水乙醇，配成0.5～2mol/L的溶液，强烈搅拌至硝酸钙完全溶解；再将上述两种溶液混合搅拌1～4h，陈化24～40h，放入烘箱烘干溶剂经过高温固化去除溶剂后得到羟基磷灰石固体。
按上述方案，所述的烘干为真空干燥，真空干燥温度为80～140℃。
本发明的有益效果：
本发明制备得到的牙齿修复材料不仅机械强度高、生物相容性好，具有良好的抑菌性、低毒性且吸附在材料的辣椒素稳定不脱附又具有效用长久性。
本发明通过在类牙齿结构的羟基磷灰石表面涂覆聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物、PEG或含PEG结构的聚合物，聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物可提高涂料的弹性，防止抑菌材料和牙龈间相互挤压损害牙龈以及适当的力学强度使得牙齿不受外界作用而磨损，PEG或含PEG结构的聚合物能通过水化层的作用有效抑制蛋白质及细菌在表面的粘附，由此可使材料具有较高的抑菌性能。另外聚硅氧烷具有低表面能、低粗糙度以及低模量等特性而PEG末端的羟基使得膜表面呈亲水性。由此彼此相分离结构的疏水性聚硅氧烷和亲水性PEG联用使得牙齿表面具有双亲性，既具有亲水性又具有疏水性的特点，PEG形成的水化层使得亲油性细菌难以接触到膜表面，而聚硅氧烷的加入不仅能增加PEG与表面结合的附着力，并且其在水环境下又具有脱污性，能进一步使得环境细菌中的细菌更难粘附在材料表面。进一步地，本发明通过抗菌剂的添加，能更好地排除细菌，而且具有绿色环保、对人体低毒害的特点，能溶于乙醇等低毒性有机溶剂的特点。
附图说明
图1为实例3中sf-PPTA/PS-b-(PDMS-r-PVMS)的红外光谱图；
图2为实例1中不同吸附时间的辣椒素吸附质量曲线；
图3为实例2中不同吸附时间的辣椒素吸附质量曲线；
图4为实例3中不同吸附时间的辣椒素吸附质量曲线。从图2-4中观察得到当吸附时间在30min左右时三者基本达到饱和吸附量，并且辣椒素不随时间的延长而从上面脱附下来；
图5为实例1中所使用抑菌涂料后和未使用抑菌涂料羟基磷灰石材料表面的扫描电镜图；
图6为实例2中所使用抑菌涂料后和未使用抑菌涂料羟基磷灰石材料表面的扫描电镜图；
图7为实例3中所使用抑菌涂料后和未使用抑菌涂料羟基磷灰石材料表面的扫描电镜图；
图8为实例1中所使用抑菌涂料后的细菌粘附数量-时间的曲线图。图中：1未涂覆抑菌涂料的羟基磷灰石；2实施例1牙齿抑菌修复材料；
图9为实例2中所使用抑菌剂后的细菌粘附数量-时间的曲线图。图中：1未涂覆抑菌涂料的羟基磷灰石；2实施例1牙齿抑菌修复材料；
图10为实例3中所使用抑菌剂后的细菌粘附数量-时间的曲线图。图中：1未涂覆抑菌涂料的羟基磷灰石；2实施例1牙齿抑菌修复材料。
具体实施方式
这些实施例仅用于说明本发明而不用于限制本发明的范围。在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1：
(1)称取7.6g磷酸三乙酯加入到20mL无水乙醇中，将2.5mL蒸馏水以10滴/min的速度缓慢滴加到稀释液中，强烈搅拌24h，使磷酸三乙酯逐渐水解。称取23.6g硝酸钙溶于乙醇溶液中，配制成2mol/L的溶液，强烈搅拌使硝酸钙完全溶解。再把硝酸钙乙醇溶液和已经水解的磷酸三乙酯混合搅拌4h，陈化40h。经过高温1700℃熔融压片得到平整片材即羟基磷灰石基体。
(2)称取0.3g的聚乙二醇(PEG)(聚合度为50)加入到25mL溶有0.36mg辣椒素的乙醇溶液中，振荡30～60min后，待饱和吸附辣椒素后取出PEG。
(3)将上述0.3g吸附了辣椒素的PEG分散到10mL质量分数为10％(共聚物质量约为0.98g)的PDMS(聚二甲基硅氧烷，聚合度为100)的乙醇溶液中,
(4)采用喷涂的方法将(3)中的混合溶液涂覆到(1)中得到的3g羟基磷灰石上。放入温度为120℃的真空干燥箱里去除溶剂后得到新型牙齿抑菌修复材料。
实施例2：
(1)与实施例1中步骤(1)完全相同。
(2)称取1g的PEGO(十八胺聚氧乙烯醚)加入到50mL溶有10mg辣椒素的乙醇溶液中，振荡30～60min后，待饱和吸附辣椒素后取出PEGO。
(3)将上述0.5g吸附有辣椒素的PEGO溶解到15mL质量分数为10％(共聚物质量约为1.47g)的PDMS-PVMS共聚物(聚二甲基硅氧烷、聚甲基乙烯基硅氧烷的嵌段共聚物，各嵌段聚合度分别为25和75)乙醇溶液中。
(4)采用喷涂的方法将(3)中的混合溶液涂覆到(1)中得到的5g羟基磷灰石上。放入温度为120℃的真空干燥箱里去除溶剂后得到新型牙齿抑菌修复材料。
上述PEG衍生物PEGO的结构式如式2所示：
式2，(m+n＝15)
实施例3：
(1)与实施例1中步骤(1)完全相同。
(2)称取0.2g的sf-PPTA(结构式如式3所示)加入到20mL溶有5mg辣椒素的乙醇溶液中，振荡30～60min后，待饱和吸附辣椒素后取出sf-PPTA。
(3)将上述0.2g吸附有辣椒素的sf-PPTA溶解到10mL质量分数为8％(质量约为0.784g)的PS-b-(PDMS-r-PVMS)(聚苯乙烯、聚二甲基硅氧烷和聚甲基乙烯基硅氧烷三嵌段共聚物的乙醇溶液中,三种嵌段的聚合度分别为20、70和30。其合成步骤是苯乙烯单体引发聚合生成聚苯乙烯嵌段，然后加入六甲基环三硅氧烷单体引发聚合生成聚二甲基硅氧烷嵌段，接着加入1,3,5-三乙烯基-1,3,5-三甲基环三硅氧烷单体引发聚合生成聚甲基乙烯基硅氧烷嵌段，最后用甲醇封端结束聚合反应)。
(4)采用喷涂的方法将(3)中的混合溶液涂覆到(1)中得到的4g羟基磷灰石上。放入温度为120℃的真空干燥箱里去除溶剂后得到新型牙齿抑菌修复材料。
式3，(m+n＝15，n’＝20～60)
实例1、2、3中PEG、PEGO、sf-PPTA不同吸附时间的辣椒素吸附质量曲线分别见图2-4，图中观察得到：当吸附时间在30min左右时三者基本达到饱和吸附量，并且辣椒素不随时间的延长而从上面脱附下来；
实例1、2、3中所使用抑菌剂的细菌粘附数量-时间的曲线见图8-10。
将涂有实例1、2、3所使用的抑菌材料的羟基磷灰石片，放置到培养有细菌的培养皿里，37℃振荡24h隔时间段分别取出少量溶液测量细菌溶液光强密度来反映细菌的多少并记录实验结果，得到图8-10。从图中可以清楚的看出经过本发明所采用抑菌修复材料能较好的抑制细菌在羟基磷灰石上的生长；将浸泡24h后的羟基磷灰石取出经过漂洗晾干后用SEM观察其表面是否粘附有细菌，见图5-7。另外以未涂覆抑菌涂料的羟基磷灰石修复材料片做对照。从图中可以清楚地看到未涂覆抑菌涂料的羟基磷灰石修复材料片有大量棒状大肠杆菌粘附在羟基磷灰石材料表面，而本发明所采用的抑菌修复材料表面则没有细菌的粘附，说明本材料能较好地抑制细菌在材料表面地粘附与滋生。
Claims (7)
1.一种基于羟基磷灰石的牙科抑菌修复材料，其特征在于：它包括羟基磷灰石、以及羟基磷灰石上负载的聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物、聚乙二醇或含PEG结构的聚合物，其中：聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物质量占羟基磷灰石质量的5％～30％，PEG或含PEG结构的聚合物质量占羟基磷灰石质量的5％～35％。
2.根据权利要求1所述的基于羟基磷灰石的牙科抑菌修复材料，其特征在于：所述聚硅氧烷为
n为20～200，
上述结构式中R1、R2独立选自-CH3或-CH＝CH2，
或为表示的嵌段中两种的共聚物；
上述结构式中R1、R2独立选自-CH3或-CH＝CH2，各嵌段的聚合度为20～200。
3.根据权利要求1所述的基于羟基磷灰石的牙科抑菌修复材料，其特征在于：所述的基于羟基磷灰石的牙科抑菌材料还包括抑菌添加剂，所述的抗菌添加剂为辣椒素，用量占羟基磷灰石质量的0.01～0.25％。
4.根据权利要求1所述的基于羟基磷灰石的牙科抑菌修复材料，其特征在于：所述含PEG结构的聚合物包含如下结构，如式1所示：
其中n≥7。
5.根据权利要求1所述的基于羟基磷灰石的牙科抑菌修复材料，其特征在于：所述含PEG结构的聚合物为聚赖氨酸接枝的PEG，甲基丙烯酸甲酯接枝的PEG，十八胺聚氧乙烯醚或磺化芳纶接枝的十八胺聚氧乙烯醚。
6.权利要求1所述的基于羟基磷灰石的牙科抑菌修复材料的制备方法，其特征在于：步骤如下：
将辣椒素溶解到乙醇溶液中，然后加入PEG或含PEG结构的聚合物，振荡一段时间后待辣椒素吸附饱和后取出；
将聚硅氧烷或聚苯乙烯-聚硅氧烷共聚物，和吸附有辣椒素的PEG或含PEG结构的聚合物溶解在乙醇溶液中，然后将混合溶液以喷涂或旋涂的方法涂覆在以羟基磷灰石为牙齿基材的表面，烘干除去溶剂后得到新型牙齿抗菌修复材料。
7.根据权利要求6所述的基于羟基磷灰石的牙科抑菌修复材料的制备方法，其特征在于：所述的烘干为真空干燥，真空干燥温度为80～140℃。
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