Synthesis of Functional Phenolic Resins and Analysis of Their Formation Reaction by Computer

对酚醛树脂的合成、反应机理和溶液性质进行了研究，得到了以下结果。建立了高产率、高选择性的环状酚类低聚物杯芳烃的合成方法。杯芳烃通过酯化、醚化以及与丙烯酸树脂和环氧树脂的键合，具有广泛的应用前景。讨论了杯芳烃与有机分子的主客体相互作用及其包合物的结构。酚醛树脂的早期形成反应非常复杂，需要考虑一些元素反应。由于通常的有机方法无法获得各元素的反应速率，因此我们的计算机模拟方法被成功地应用。制备了分子结构明确的酚醛树脂，讨论了其在溶液中的分子构象。首先通过相平衡测定了一些酚醛树脂-溶剂体系的温度，然后讨论了分子在良好溶剂和溶剂中的构象。研究表明，由于酚羟基之间的分子内氢键作用和支化作用，酚醛树脂的分子收缩较大，不含任何酚羟基和支链的乙酰化邻甲酚树脂在一定条件下表现为一条稳定的链状结构。

The synthesis, the reaction mechanisms and the solution properties of the phenolic resins were studied and the following results were obtained.1. The synthetic method of calixarene, the cyclic phenolic oligomer, in high yield and in high selectivity were established. By the esterification and the etherification and by the bonding into acrylic resin and epoxy resin, calixarene became widely applicable. The host-guest interaction of calixarene for organic molecules and the structure of their clathrate complexes were discussed.2. The formation reaction of the phenolic resin in early stage is so complex that some elemental reactions had to be considered. Since it is impossible to obtain the rate of each elemental reaction by usual organic technique, our computer simulation method was successfully applied.3. The phenolic resins whose molecular structures were definite were prepared to discuss the molecular conformation in solution. At first, temperatures for some phenolic resin-solvent systems were determined from phase equilibrium measurements, and then the molecular conformation in a good solvent and in a slovent were discussed. It was known that the molecules of the phenolic resins shrink considerably because of the contribution of the intramolecular hydrogen bonding between phenolic hydroxyl groups and the branching, and therefore, acetylated o-cresol resin which has not any phenolic hydroxyl groups and any branches behave as an unperturbed chain in condition.