季铵盐改性硅酸盐在齿科甲基丙烯酸酯基树脂材料中的应用研究
发布时间：2019-05-31 18:05
【摘要】：树脂材料是口腔医学临床实践中应用最广泛的一类医学材料。由于口腔为有菌环境这一特殊性，树脂材料的抗菌性能对于预防因细菌等微生物感染引起的口腔疾病（如龋齿，牙周病，，口腔感染性粘膜病等）具有重要实际意义。抗菌性树脂材料可以抑制或者杀灭粘附在材料表面的细菌以消除或者抑制树脂材料表面微生物生物膜的形成。传统抗菌性树脂材料通常依赖抗菌成分释放机制实现。但是，通过释放机制的抗菌策略，在起始的“突释期”（Burst-release Phase）内可释放足量的抗菌成分而获得一定的抗菌效果。但是在随后的尾期释放（Tail-release Phase）中常常因为浓度太低难以达到有效抗菌浓度，同时可能诱导细菌耐受性。另外，材料中抗菌成分的释放，最终可能导致材料机械性能的下降。 本论文报道利用凝胶-溶胶方法，合成一种可与甲基丙烯酸酯基树脂材料共聚和的抗菌性单体：季铵甲基丙烯酰氧基硅酸盐（QAMS）。在该合成体系前体物质中，正硅酸四乙酯（TEOS）为“锚”分子，连接具有广谱抗菌性能的三烷氧基硅烷SiQAC和具甲基丙烯酸酯基的3-MPTS。通过调整反应体系的pH和水含量，可控制QAMS的水解和缩合反应动力，以满足不同材料应用需求。将部分水解的QAMS-3PH整合入bis-GMA树脂系统后，bis-GMA/QAMS-3PH树脂材料具有对变形链球菌，内氏放线菌和白色念珠菌具有良好的抗菌效果；同时，树脂材料在水老化后，通过QAMS-3PH的继续水解缩合，材料表现出抗断裂性能的提升。全部水解的QAMS可溶解于MMA单体，从而整合于PMMA树脂系统，该树脂材料除表现出典型的长期接触杀菌效果外，其断裂韧度（Fracture Toughness）得到提升。最后，我们利用改良St ber方法，在水-乙醇反应体系中，以氨水为催化剂，在没有外加的表面活性剂的条件下，水解共聚合TEOS以及另外两个三烷氧基硅烷：SiQAC和3-MPTS，合成倍半硅氧烷-二氧化硅杂化物（SqSH）颗粒。通过改变反应前体物中TEOS与SiQAC/3-MPTS的比例，可得到不同弹性模量的SqSH颗粒。该颗粒除抗菌性能外，具有规则的板层状结构。
[Abstract]:Resin material is the most widely used medical material in clinical practice of stomatology. Because of the particularity of oral bacterial environment, the antibacterial properties of resin materials are of great practical significance for the prevention of oral diseases (such as dental caries, periodontal disease, oral infectious mucous membrane diseases, etc.) caused by microbial infections such as bacteria. Antibacterial resin materials can inhibit or kill bacteria attached to the surface of materials to eliminate or inhibit the formation of microbial membranes on the surface of resin materials. Traditional antibacterial resin materials usually rely on the release mechanism of antibacterial components. However, through the antibacterial strategy of release mechanism, a sufficient amount of antibacterial components can be released in the initial "sudden release period" (Burst-release Phase), and a certain antibacterial effect can be obtained. However, in the later release (Tail-release Phase), it is often difficult to reach the effective antibacterial concentration because the concentration is too low, and it may induce bacterial tolerance at the same time. In addition, the release of antibacterial components in the material may eventually lead to the decline of mechanical properties of the material. In this paper, a kind of antibacterial monomer, quaternary ammonium methacroloxy silicate (QAMS)., which can be synthesized by gel-sol method, which can be copolymerized with methacrylate based resin, is reported in this paper. In the precursor of the synthesis system, tetraethyl orthosilicate (TEOS) is an "anchor" molecule, which connects trialkoxysilane SiQAC with broad-spectrum antibacterial properties and 3 times MPTS with methacrylic group. By adjusting the pH and water content of the reaction system, the hydrolysis and condensation reaction kinetics of QAMS can be controlled to meet the application needs of different materials. After the partially hydrolyzed QAMS-3PH was integrated into the bis-GMA resin system, the bis-GMA/QAMS-3PH resin material had good antibacterial effect on Streptococcus mutans, Actinomyces nigris and candida albicans. At the same time, after water aging, through the continuous hydrolysis and condensation of QAMS-3PH, the fracture resistance of the resin material was improved. All the hydrolyzed QAMS can be dissolved in MMA monomer and thus integrated into PMMA resin system. In addition to the typical long-term contact germicidal effect, the fracture toughness (Fracture Toughness) of the resin material is improved. Finally, we used the improved St ber method to hydrolyze TEOS and two other trialkoxysilane: SiQAC and 3 / MPTS in the water-ethanol reaction system with ammonia water as catalyst and without additional surfactants. The (SqSH) particles of silsesquioxane-silica hybrid were synthesized. By changing the ratio of TEOS to SiQAC/3-MPTS in the reaction precursor, SqSH particles with different elastic modulus can be obtained. In addition to its antibacterial properties, the particles have a regular lamellar structure.
【学位授予单位】：华中科技大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：R783.1
本文编号：2489916
[Abstract]:Resin material is the most widely used medical material in clinical practice of stomatology. Because of the particularity of oral bacterial environment, the antibacterial properties of resin materials are of great practical significance for the prevention of oral diseases (such as dental caries, periodontal disease, oral infectious mucous membrane diseases, etc.) caused by microbial infections such as bacteria. Antibacterial resin materials can inhibit or kill bacteria attached to the surface of materials to eliminate or inhibit the formation of microbial membranes on the surface of resin materials. Traditional antibacterial resin materials usually rely on the release mechanism of antibacterial components. However, through the antibacterial strategy of release mechanism, a sufficient amount of antibacterial components can be released in the initial "sudden release period" (Burst-release Phase), and a certain antibacterial effect can be obtained. However, in the later release (Tail-release Phase), it is often difficult to reach the effective antibacterial concentration because the concentration is too low, and it may induce bacterial tolerance at the same time. In addition, the release of antibacterial components in the material may eventually lead to the decline of mechanical properties of the material. In this paper, a kind of antibacterial monomer, quaternary ammonium methacroloxy silicate (QAMS)., which can be synthesized by gel-sol method, which can be copolymerized with methacrylate based resin, is reported in this paper. In the precursor of the synthesis system, tetraethyl orthosilicate (TEOS) is an "anchor" molecule, which connects trialkoxysilane SiQAC with broad-spectrum antibacterial properties and 3 times MPTS with methacrylic group. By adjusting the pH and water content of the reaction system, the hydrolysis and condensation reaction kinetics of QAMS can be controlled to meet the application needs of different materials. After the partially hydrolyzed QAMS-3PH was integrated into the bis-GMA resin system, the bis-GMA/QAMS-3PH resin material had good antibacterial effect on Streptococcus mutans, Actinomyces nigris and candida albicans. At the same time, after water aging, through the continuous hydrolysis and condensation of QAMS-3PH, the fracture resistance of the resin material was improved. All the hydrolyzed QAMS can be dissolved in MMA monomer and thus integrated into PMMA resin system. In addition to the typical long-term contact germicidal effect, the fracture toughness (Fracture Toughness) of the resin material is improved. Finally, we used the improved St ber method to hydrolyze TEOS and two other trialkoxysilane: SiQAC and 3 / MPTS in the water-ethanol reaction system with ammonia water as catalyst and without additional surfactants. The (SqSH) particles of silsesquioxane-silica hybrid were synthesized. By changing the ratio of TEOS to SiQAC/3-MPTS in the reaction precursor, SqSH particles with different elastic modulus can be obtained. In addition to its antibacterial properties, the particles have a regular lamellar structure.
【学位授予单位】：华中科技大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：R783.1
【参考文献】
相关期刊论文 前1条
1 王晓荣,叶湘玉,牛百平;青少年产生正畸治疗需求动机的影响因素[J];实用口腔医学杂志;1998年03期
本文编号：2489916
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