CN106957266A - 一种含氟离子的牙科树脂单体及其制备方法和应用 - Google Patents

一种含氟离子的牙科树脂单体及其制备方法和应用 Download PDF

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CN106957266A
CN106957266A CN201710056421.XA CN201710056421A CN106957266A CN 106957266 A CN106957266 A CN 106957266A CN 201710056421 A CN201710056421 A CN 201710056421A CN 106957266 A CN106957266 A CN 106957266A
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dental resin
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fluoride
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朱蔚璞
孙雪飞
李晓东
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Zhejiang University ZJU
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Abstract

本发明公开了一种含氟离子的牙科树脂单体，结构式如下式(Ⅰ)所示，本发明还公开了所述含氟离子的牙科树脂单体的制备方法以及其在制备可重复充放氟离子的牙科树脂中的应用。本发明提供了一种含氟离子的牙科树脂单体，以其为含氟单体制备得到的牙科树脂可实现氟离子的长效缓释及重复充放，有效预防了龋齿的产生，且具有良好的抗菌性能。式中，R选自碳数为1～18的烷基，Q选自

Description

一种含氟离子的牙科树脂单体及其制备方法和应用
技术领域
本发明涉及牙科树脂的技术领域，具体涉及一种含氟离子的牙科树脂 单体及其制备方法和应用。
背景技术
龋齿及二次龋齿已成为当今不可忽视的口腔疾病之一，其主要是由口 腔内的细菌与糖类或者碳水化合物作用产生酸性物质腐蚀牙釉质随后逐 渐深入而造成的。在最初酸性物质腐蚀牙釉质导致脱矿的过程中，使用氟 化物可以帮助牙齿的自行重复充放，实现蛀牙的治疗。氟作为公认的防龋 元素，有包括降低牙釉质的酸性环境中的溶解性、促进牙釉质的再矿化、 抑制细菌对糖类的摄取等作用，已被广泛应用于各种口腔材料中。
常规应用于口腔中的材料大多需满足以下几点：一、良好的生物相容 性及低毒性；二、合适的机械强度；三、优良的抗菌性能。目前主要的防 龋含氟材料大多为由无机材料填充的树脂类复合材料，物理包埋一定含量 的无机氟化物，主要的使用方法：用酸液将牙釉质进行刻蚀，随后涂上粘 结剂，再将树脂填充后固化，有时还需要容器将树脂进行固定。其中的氟 离子通过与口腔环境中的浓度梯度进行释放，一般在最初的几小时内存在爆释的现象。因而其具有良好的机械强度及外观性能，也能进行一定时间 内氟离子的缓释。
如公开号为CN101129294A的中国专利文献中公开了一种纳米含氟 高强树脂牙科材料及其制备方法，该树脂牙科材料由甲基丙烯酸脂类单 体、引发剂和含氟的无机填料(经过超声分散得到纳米级的生物陶瓷粉和 硅粉)混合后再经光固化得到。该树脂牙科材料虽然具有抗细菌、抗龋齿， 机械强度及性能良好的优点，但由于加入了过多的无机填料(无机填料占 总重量的50～85％)，势必造成对牙釉质的贴合度不够高，且重复使用率 不高，在临床应用上还不够高效方便。
公开号为CN101703450A的中国专利文献公开了有助于抵御继发性 龋病害的含氟牙用复合树脂材料，该材料包括：树脂单体8～70％、稀释 剂5～25％、光引发剂0.25～2％、共引发剂0.5～3％、改性后的无机纳米填 料20～85％，其中，改性的无机纳米填料是由纳米无机粉体经硅烷偶联剂 处理得到，纳米无机粉体内含有重量分数为10～80％的介孔孔洞内负载了 可溶性无机氟盐的介孔二氧化硅微球。该树脂材料解决了常规简单掺杂氟 盐复合树脂材料存在的释氟过快，界面相容性差等问题。
除了上述直接向高分子树脂中加入含氟的无机盐外，还有一种引入氟 的途径，即采用含氟单体，该法在国外已有研究和应用，如US4515910 的美国专利中采用含氟单体与甲基丙烯酸的聚合；又如US5037638的美国 专利中研发了一种含HF单体，虽然可以提高释放氟离子的能力，但聚合 性能还不能令人满意。
公开号为CN102060702A的中国专利文献中公开了一种可见光固化 含氟牙科树脂单体/复合材料及制备方法，该单体为单体双酚-A-双[3-甲基 丙烯酰氧基-2-(2-三氟乙酰氧基)丙基]醚或单体双酚-S-双[3-甲基丙烯酰 氧基-2-(2-三氟乙酰氧基)丙基]醚，具体是通过双酚A或双酚S与甲基 丙烯酸缩水甘油酯和三乙胺混合，经三氟乙酸酐和三乙胺作用制备得到。 再将其与其他丙烯酸酯类单体混合后经可见光固化得到一种可见光固化 含氟牙科树脂复合材料。该复合材料中通过含氟单体的聚合从而引入氟， 氟的引入可更加有效地预防龋齿的发生，但由于氟是通过C-F键键合在聚 合物的分子链中，因此无法实现氟离子的长效缓释及重复充放。
发明内容
本发明提供了一种含氟离子的牙科树脂单体，以其为含氟单体制备得 到的牙科树脂可实现氟离子的长效缓释及重复充放，有效预防了龋齿的产 生，且具有良好的抗菌性能。
具体技术方案如下：
一种含氟离子的牙科树脂单体，结构式如下式(Ⅰ)所示：
式中，R选自碳数为1～18的烷基，Q选自
本发明还公开了所述的含氟离子的牙科树脂单体的制备方法，具体 为：
以含氮的乙烯基单体和卤代烷烃为原料，经烷基化反应制备得到中间 产物，再经阴离子交换反应得到所述的含氟离子的牙科树脂单体；
所述的含氮的乙烯基单体选自1-乙烯基咪唑(NVI)、2-乙烯基吡啶、 4-乙烯基吡啶、甲基丙烯酸二甲氨基乙酯(DMAEMA)或丙烯酸二甲氨基乙 酯(DMAEA)；
所述的卤代烷烃选自碳数为1～18的1-氯代烷烃或1-溴代烷烃，优选 为1-氯代乙烷(Cl-C2)、1-溴代乙烷(Br-C2)、1-氯代丁烷(Cl-C4)、1- 溴代丁烷(Br-C4)、1-氯代辛烷(Cl-C8)、1-溴代辛烷(Br-C8)、1-氯代 十二烷(Cl-C12)、1-溴代十二烷(Br-C12)、1-氯代十八烷(Cl-C18)、1- 溴代十八烷(Br-C18)等。本发明中优选的卤代烷烃均为来源广泛且成本低廉的品种，但从烷基化反应的机理出发，其它碳数的卤代烷烃也是完全 适用于本发明的。
作为优选，所述的烷基化反应中，将等摩尔的含氮的乙烯基单体和卤 代烷烃混合，室温～60℃下反应完全，再经洗涤、干燥后得到中间产物。
作为优选，所述的阴离子交换反应以氟化银、氟化钠或氟化钾为离子 交换试剂；
所述的中间产物与离子交换试剂等摩尔混合。
进一步优选，所述的阴离子交换反应中，先将中间产物溶解在去离子 水中得到原料液Ⅰ，再将离子交换试剂溶解在去离子水中得到原料液Ⅱ， 最后将原料液Ⅰ与原料液Ⅱ混合，室温下反应完全，离心分离取上清液， 即得到所述的含氟离子的牙科树脂单体。
本发明还公开了所述的含氟离子的牙科树脂单体在制备一种可重复 充放氟离子的牙科树脂中的应用：
所述可重复充放氟离子的牙科树脂的原料组成包括丙烯酸酯类树脂 单体、稀释剂和光引发剂，还包括上述的含氟离子的牙科树脂单体。
作为优选，所述的丙烯酸酯类树脂单体选自双酚A-甲基丙烯酸缩水 甘油酯；
所述的稀释剂选自二甲基丙烯酸二缩三乙二醇酯；
所述的光引发剂选自樟脑醌和4-二甲氨基苯甲酸乙酯。
作为优选，其原料组成还包括粘度调节剂，所述的粘度调节剂选自无 水乙醇。
所述的可重复充放氟离子的牙科树脂可以作为粘接树脂使用，也可作 为填充树脂使用。当其用做填充树脂时，对其机械强度有一定的要求，因 此其原料组成还包括无机填料，所述的无机填料选自碳酸钙或磷酸钙。
本发明通过将含氟离子的牙科树脂单体与双官能度的牙科树脂配置 成溶液，直接在牙釉质上通过紫外光固化，省去粘合剂等其他助剂；在保 持机械强度的同时，聚合物部分包含的疏水部分和亲水部分使得其在口腔 环境中有良好的稳定性；同时通过离子交换，可以完成材料中氟离子向口 腔环境内的释放以及得到外源性含氟物质的补充，实现氟离子的重复充放 功能，有效防止龋齿产生。
与现有技术相比，本发明具有以下突出优势：
本发明制备的含氟离子的牙科树脂单体中的氟离子是通过离子交换 法制备得到，以该单体为含氟单体制备的牙科树脂仅通过离子交换即可实 现氟离子向口腔环境内的释放及借助外源性含氟物质实现氟离子的储存 和重复充放，简便高效地实现了类似蓄电池的功能，达到长效抗龋的效果；
本发明制备的含氟离子的牙科树脂单体或含有氮杂环阳离子，或含有 季铵盐阳离子，以其为含氟单体制备得到的牙科树脂对造成龋齿的变形链 球菌有良好的抗菌效果；
以本发明制备的含氟离子的牙科树脂单体为含氟单体制备得到的牙 科树脂机械强度高，其聚合物链上同时具有亲水和疏水部分，在口腔环境 中稳定性较好；
本发明中制备牙科树脂的工艺简单、重复性好、普适性高，在医用紫 外灯下辐照即可快速实现树脂的固化，潜在的经济效益巨大。
附图说明
图1为实施例3制备的含氟离子的牙科树脂单体的核磁共振谱图；
图2为实施例14制备的含氟离子的牙科树脂单体的核磁共振谱图；
图3为本发明中制备含氟牙科树脂的反应示意图。
具体实施方式
下面通过实施例对本发明作进一步的说明，其目的仅在于更好的理解 本发明而非限制本发明保护的范围。
实施例1:NVI-F-C2牙科树脂单体的制备
向25mL的单口烧瓶中加入3.22g(0.05mol)1-氯代乙烷和4.7g (0.05mol)1-乙烯基咪唑，40℃下搅拌72h。产物用乙醚与乙酸乙酯混合 液沉淀三次，得到白色粉末状固体，于真空烘箱常温干燥24h。
向25mL的单口烧瓶中加入上述中间产物0.79g(0.005mol)加入 10mL去离子水溶解，将0.64g(0.005mol)氟化银溶解于15mL去离子水 中，在搅拌状态下后者逐滴加入前者水溶液中，室温下反应2h，低速离心 (3500r/min)30min，取上层清液冻干，得到目标单体。
实施例2～5
制备工艺同实施例1，区别仅在于将卤代烷烃分别替换为1-氯代丁烷、 1-氯代辛烷、1-氯代十二烷、1-氯代十八烷。
实施例6
制备工艺同实施例1，区别仅在于将卤代烷烃替换为1-溴代乙烷，烷 基化反应在室温下进行72h。
实施例7～10
制备工艺同实施例6，区别仅在于将卤代烷烃分别替换为1-溴代丁烷、 1-溴代辛烷、1-氯代十二烷、1-氯代十八烷。
实施例11
制备工艺同实施例1，区别仅在于将含氮的乙烯基单体替换为甲基丙 烯酸二甲氨基乙酯。
实施例12～15
制备工艺同实施例11，区别仅在于将卤代烷烃分别替换为1-氯代丁 烷、1-氯代辛烷、1-氯代十二烷、1-氯代十八烷。
实施例16～20
制备工艺同实施例11，区别仅在于将卤代烷烃分别替换为1-溴代乙 烷、1-溴代丁烷、1-溴代辛烷、1-溴代十二烷、1-溴代十八烷。
实施例21：含氟牙科树脂的制备
将双酚A-甲基丙烯酸缩水甘油酯和二甲基丙烯酸二缩三乙二醇酯以 25:75的质量比混合，加入树脂质量0.4％的樟脑醌和0.8％的4-二甲氨基苯 甲酸乙酯，以0.3％氟离子质量加入实施例3制备的含氟离子的牙科树脂 单体，加入0.5mL无水乙醇调节浓度，混合均匀后倒入模具，在365nm 紫外灯下辐照固化得到含氟牙科树脂。
使用过程中，由于存在浓度梯度，树脂材料中氟离子与口腔内唾液环 境中的氯离子等阴离子进行离子交换从而释放进入口腔，提高环境中氟含 量，实现抗龋杀菌等效果。此过程在数天到几周内可持续进行。日常使用 外源性含氟物质如含氟牙膏、含氟漱口水等可再次对树脂内的氟离子进行 补充，而后实现氟离子的再次释放，以此循环，即可在日常生活中利用含 氟树脂进行氟离子在口腔内的多次充放，实现长效抗龋。
实施例22
同实施例21，区别在于调节双酚A-甲基丙烯酸缩水甘油酯和二甲基 丙烯酸二缩三乙二醇酯以50:50的质量比混合。
实施例23
同实施例21，区别在于调节双酚A-甲基丙烯酸缩水甘油酯和二甲基 丙烯酸二缩三乙二醇酯以75:25的质量比混合。

Claims (10)

1.一种含氟离子的牙科树脂单体，其特征在于，结构式如下式(Ⅰ)所示：
式中，R选自碳数为1～18的烷基，Q选自
2.一种根据权利要求1所述的含氟离子的牙科树脂单体的制备方法，其特征在于，以含氮的乙烯基单体和卤代烷烃为原料，经烷基化反应制备得到中间产物，再经阴离子交换反应得到所述的含氟离子的牙科树脂单体；
所述的含氮的乙烯基单体选自1-乙烯基咪唑、2-乙烯基吡啶、4-乙烯基吡啶、甲基丙烯酸二甲氨基乙酯或丙烯酸二甲氨基乙酯；
所述的卤代烷烃选自碳数为1～18的1-氯代烷烃或1-溴代烷烃。
3.根据权利要求2所述的含氟离子的牙科树脂单体的制备方法，其特征在于，将等摩尔质量的含氮的乙烯基单体和卤代烷烃混合，室温～60℃下反应完全，再经洗涤、干燥后得到中间产物。
4.根据权利要求2所述的含氟离子的牙科树脂单体的制备方法，其特征在于，所述的阴离子交换反应以氟化银、氟化钠或氟化钾为离子交换试剂。
5.一种可重复充放氟离子的牙科树脂，其原料组成包括丙烯酸酯类树脂单体、稀释剂和光引发剂，其特征在于，还包括如权利要求1所述的含氟离子的牙科树脂单体。
6.根据权利要求5所述的可重复充放氟离子的牙科树脂，其特征在于，所述的丙烯酸酯类树脂单体选自双酚A-甲基丙烯酸缩水甘油酯；
所述的稀释剂选自二甲基丙烯酸二缩三乙二醇酯；
所述的光引发剂选自樟脑醌和4-二甲氨基苯甲酸乙酯。
7.根据权利要求5所述的可重复充放氟离子的牙科树脂，其特征在于，其原料组成还包括粘度调节剂。
8.根据权利要求7所述的可重复充放氟离子的牙科树脂，其特征在于，所述的粘度调节剂选自无水乙醇。
9.根据权利要求5所述的可重复充放氟离子的牙科树脂，其特征在于，其原料组成还包括无机填料。
10.根据权利要求9所述的可重复充放氟离子的牙科树脂，其特征在于，所述的无机填料选自碳酸钙或磷酸钙。
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CN110724229A (zh) * 2019-10-23 2020-01-24 浙江理工大学 一种抗菌剂的制备方法及产物
CN113164229A (zh) * 2018-11-19 2021-07-23 3M创新有限公司 具有离子交换涂层的牙科矫治器

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CN108329265A (zh) * 2018-01-17 2018-07-27 北京化工大学 一种含咪唑离子的光固化单体及其在自修复材料中的应用
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CN113164229A (zh) * 2018-11-19 2021-07-23 3M创新有限公司 具有离子交换涂层的牙科矫治器
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CN110724229B (zh) * 2019-10-23 2021-12-03 浙江理工大学 一种抗菌剂的制备方法及产物

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