混合溶剂对MDP与Y-TZP相互作用影响的热力学分析

Chemical Affinity of 10-methacryloyloxydecyl Dihydrogen Phosphate to Dental Zirconia in Different Mixed Solvents:Thermodynamic Calculation and Analysis

目的:溶剂是MDP和Y-TZP之间形成“P-O-Zr”键的必要条件,考察不同比例的乙醇/丙酮混合溶剂对MDP与Y-TZP相互作用的影响,为粘接产品开发选择溶剂提供依据。方法:分别构建MDP分子、四方相氧化锆晶体(Zr4O8簇)、MDP-Zr4O8的化学模型,使用分层计算方法对两者间的相互作用进行研究。在不同溶剂环境中(乙醇、丙酮的体积分数比分别为10∶0、9∶1、8∶2、7∶3、6∶4),采用热力学方法计算相互作用的吉布斯自由能和平衡常数。结果:总反应的吉布斯自由能分别为-204.43、-206.07、-207.72、-209.35、-210.96 kJ/mol,平衡常数分别为0.68×1036、1.32×1036、2.56×1036、4.96×1036、9.50×1036,说明MDP与Y-TZP在这些溶液环境中均能发生化学结合,且随丙酮浓度升高MDP与Y-TZP之间相互作用越大。结论:丙酮溶剂环境促进了MDP与Y-TZP之间的配位,从而提高了“P-O-Zr”键的强度。

Objective:To analyze the chemical affinity of 10-MDP to Y-TZP in different ratios of ethanol/acetone mixed solvent conditions.Methods:Various models were created for molecular MDP,tetragonal zirconia crystals,and MDP-Zr4O8 system.Configurations of these models were undertaken using the"Our-own N-layered integrated molecular orbital and molecular mechanics"(ONIOM)method.Interactions between MDP and Zr4O8 clusters were analyzed by calculation of their Gibbs free energy values and equilibrium constants in different solvent conditions(ethanol and acetone volume ratio were 10∶0,9∶1,8∶2,7∶3,6∶4).Results:Gibbs free energy(kJ/mol)of total reaction between MDP and Zr4O8 clusters were-204.43,-206.07,-207.72,-209.35,and-210.96 kJ/mol.The negative signs indicated that reactions could occur in different solvent conditions.Equilibrium constant of total reaction were 0.68×1036,1.32×1036,2.56×1036,4.96×1036,and 9.50×1036 in different solvent conditions,suggesting that the latter was more stable.Conclusion:Acetone solvent conditions promote coordination between MDP and Y-TZP,thereby increasing the strength of the"P-O-Zr"bond.