STRUCTURAL AND THERMODYNAMIC ANALYSIS OF ADHESION PROMOTING MONOMERS

本研究的目的是分析混合硅烷底漆处理后的丙烯酸树脂对玻璃板的粘接强度、底漆表面自由能、底漆与树脂单体的溶解度参数之间的关系，并研究牙与含官能团的各种丙烯酸单体之间的相互作用。结果表明：(1)在3-甲基丙烯氧基丙基三甲氧基硅烷（3-MPS）与1H、1H、2H、2H的最佳配比下，树脂与经混合硅烷处理过的板材的拉伸结合强度。非氟己基三甲氧基硅烷（LP-4）与3-MPS处理后的样品相比具有显著性的高，并且具有良好的抗水粘附性。(2)混合硅烷处理后的表面的拉伸结合强度与表面自由能之间存在相关性。(3)计算了硅烷、混合硅烷和树脂单体的溶解度参数。当混合硅烷形成的分子在表面的溶解度参数值接近于树脂单体的溶解度参数值时，可以获得较好的处理效果，但效果不完全是由参数决定的。(4)计算了含官能团的各种丙烯酸单体的溶解度参数值。该参数值与HPLC测定的丙烯酸单体保留时间呈线性关系，可作为表征单体分子极性的指标。而带侧链单体的值与时间没有关系。(5)以铁离子处理过的牛牙本质为柱进行亲和层析，与未处理柱相比，含羧基、磷酸基等官能团单体的色谱保留时间长，峰宽。(6)在钙离子存在的情况下，用电位滴定法测定了钙离子与羧基或磷酸基丙烯酸单体以及各种无机磷酸和有机膦酸的相互作用。磷化合物为邻位磷酸、热磷酸和聚磷酸，以及亚二膦酸、亚硝基膦酸和植酸。钙离子与无机基团的4-甲基丙烯酰氧基-乙基三ellitic酸、多磷酸和膦酸基团的nitrilotris（亚甲基膦酸）有较强的相互作用。少

The purpose of this investigation was to analyze the relationship between the adhesive strength of acrylic resin to the glass plate treated with the mixed silane primer and the surface free energy of the surface treated with the primer and the solubility parameter of the primer and the resin monomers and to study mutual interaction between teeth and various acrylic monomers with a functional group.The results were as follows : (1) The tensile bond strength of the resin to the plate treated with the mixed silane at the optimum ratio of 3-methacryloxypropyltrimethoxysilane (3-MPS) and 1H,1H,2H,2H.nonafluoro-hexyltrimethoxysilane (LP-4) was significantly high compared with 3-MPS treated specimen, and the specimens showed good water-resistant adhesion (2) There was the correlation between the tensile bond strength and the surface free energy of the surface treated with the mixedsilane. (3) The values of solubility parameters of the silanes, the mixed silane and the resin monomer were calcu … More lated. And when the value of the solubulity parameter of the molecules on the surface formed by the mixed silanes colsed to that of the resin monomer, a good treatment effect was obtained, but the effect was not attributed to the parameter only. (4) The values of the solubility parameter of various acrylic monomers with a functional group were calculated. There was a linear relationship between the values of the parameterand the retention time of the acrylic monomer measured by HPLC and the parameter was avairable as an indication that exhibited the polarity of the monomer molecule. However, there was no relationship between the value and the time of the monomer with side-chain. (5) By the affinty chromatography using the bovine dentin treated with ferric ions as an column, the chromatogram of the monomers with a functional group, such as carboxylic and phosphoric group, showed long retention time and a broad peak compared with that of the untreated column. (6) The interaction between calcium ion and the acrylic monomers with carboxylic or phosphoric group and various inorganic phosphoric acids and organic phosphonic acids was measured by potentiometric titration in the presence of calcium ion. The phosphorus compounds were ortho-, pyro- and poly-phosphoric acid, and methylenediphosphonic acid, nitrilotris(methylenephosphonic acid) and phytic acid. Strong interaction between calcium ion and 4-methacryloyloxy-ethyltrimellitic acid, polyphosphoric acid in the inorganic group, and nitrilotris(methylenephosphonic acid) in the phosphonic acid group was observed. Less