自交联不饱和聚酯的分子结构设计与自交联固化性能研究

Self crosslinkable unsaturated polyesters are going to be prepared to solve the air pollution problem caused by the monomer volatilization in the unsaturated polyester industry, which can be self crosslinked without the addition of vinyl monomers. After analyzing the molecular structure systematically, we design to synthesize a series of unsaturated polyesters with the double bonds on the side chain,significantly different from the traditional ones with double bonds on the main chain.By adjusting the type and amount of the substituent group of double bonds, and by adjusting the length and flexibility of the side chain, unsaturated polyesters with higher self crosslinking activity are expected to be synthesized. Meanwhile, unsaturated polyesters, with the double bonds connecting with electron-withdrawing substituents, such as carbonyl group, and with electron-donating groups on the side chain, such as hydroxyl or thiol group, are designed to be prepared. The electron deficient unsaturated double bonds can crosslink with hydroxyl groups through the nucleophilic addition reaction. As a result, unsaturated polyesters with electron deficient double bonds and hydroxyl or thiol groups on the side chain can self crosslink without additional monomers. Furthermore, the influence rule of the molecular structure on the self curing activity will be investigated systematically, the molecular structure characteristics advantageous to self crosslinkation will be clarified, and the synthesis procedure of the self crosslinkable unsaturated polyesters will be defined. At last, the self curing process, the curing mechanism and the resin properties after self crosslinkation will be systematically studied for the further application. Due to this significant research on self crosslinkable unsaturated polyesters and the new curing process without crosslinking monomers, it is expected that the air pollution caused by monomer volatilization in unsaturated polyester industry will be greatly improved.

摘要 本课题拟制备具有"自交联能力"的新型不饱和聚酯，在不添加交联单体的情况下，自交联固化成型，从而解决不饱和聚酯工业中交联单体挥发对空气的污染问题。通过分子结构设计，将传统位于分子主链的不饱和双键调整为侧链双键，通过对双键取代基种类与数量、侧链长度与柔性的调整,制备具有自交联活性的不饱和聚酯。同时设计制备双键与拉电子基团相连，侧链含有羟基、琉基等给电子基团的不饱和聚酯，利用羟基对缺电子双键的亲核加成反应实现自交联聚合。在树脂制备的基础上，系统研究分子结构因素对自交联固化活性的影响规律，确立自交联不饱和聚酯的分子结构特征与制备技术路线，研究自交联不饱和聚酯的自交联固化工艺、固化机理与固化后树脂的综合性能，为自交联不饱和聚酯的进一步应用开发奠定基础。预期本课题的研究，是对不饱和聚酯传统固化成型方法的一次变革与探索，对解决不饱和聚酯工业中，交联单体挥发份的空气污染问题，具有重要意义。

为了解决不饱和聚酯工业中交联单体对大气的污染问题，设计制备了两大类自交联不饱和聚酯。一类是侧链或链末端含有端基双键的新型不饱和聚酯，设计制备了五种不同结构特征不饱和聚酯：IPP-UP，TGG-UP， PGA-UP，P-4221-UP和PE-44-UP。另一类是侧链含羟基的不饱和聚酯。采用缩水甘油与马来酸酐为原料，分别按照摩尔比为2:1、12:7、3:2、1.1:1.0的比例，制备不同聚合度的侧链含羟基的不饱和聚酯MA-UP；以缩水甘油和衣康酸酐为原料，按照摩尔比为2: 1、3: 2和4: 3的比例，制备了一系列不同聚合度的侧链含羟基的不饱和聚酯IG-UP。确立了各自的合成技术路线，研究了树脂固化机理、固化工艺和固化活性,探索了不饱和聚酯的分子结构特征对固化活性的影响规律。其中，除IPP-UP的双键自由基聚合活性较低，无法自交联固化，其他六种不饱和聚酯均实现了自交联固化功能。对各种自交联不饱和聚酯的自交联固化性能进行了综合比较分析，总结了自交联型不饱和聚酯的分子结构设计规律。表征了固化后树脂的力学性能与热性能。对此类新型不饱和聚酯的应用前景进行了探索，利用其中部分不饱和聚酯为基体，以空心玻璃微珠为填料，结合各种助剂，成功制备了深海用高强轻质浮力材料。所得的浮力材料配方具有优异的综合性能，尤其是材料密度显著优于常见的环氧树脂基浮力材料和不饱和聚酯基浮力材料，发展潜力很大。