高品质桐油基PVC增塑剂的合成、分离及增塑机理研究

The development of deep processing of tung oil is shortage; technology of high quality plasticizer is lacks, which need to be solved urgently in our counry. The scientific and technical problems which are not yet solvedis include that the plasticizing mechanism is not clear, the microscopic research methods are missing, and the purification and separation of tung oil are difficulties because the heat sensitive of tung oil is high. Aiming at the problems, first, the modified products of tung oil with high plasticizing structure is designed and synthesized by applicants, while the heat sensitive of tung oli is reduced; then the high purity products wil be separated by the commonly used separation technology in industry; last, the high purity of tung oil based plasticizer will be obtained by a series of chemical steps. The purpose of this study is to solve the problem in the laboratory stage that the oil based plasticizer can not be used as the main plasticizer of PVC. The research methods of plasticizing mechanism from molecular level will be explored uisng of modern analytical methods, and the combine form and interaction between the molecular chain of the plasticizer and PVC resin are revealed. Improving plasticizing mechanism of plasticizer for PVC resin, which makes the theoretical guidance for designing a new type of high efficient plasticizer.

针对目前桐油深加工应用开发不足、国内高品质环保型增塑剂技术缺乏和环保型油脂基增塑剂的品质差等迫切需要解决的问题，以及PVC增塑剂的增塑机理不清晰，微观研究方法缺失，桐油的热敏性高难纯化分离等科学问题和技术问题。申请人首先设计合成出具有高效增塑结构的桐油改性产品，同时降低其热敏性；接着分别利用间歇减压蒸馏、精馏和分子蒸馏等分离技术分离得到较高纯度的产品；进一步合成出一系列的高纯度桐油基PVC增塑剂；和石油基PVC增塑剂对比应用研究，得到几种综合性能优良的桐油基PVC增塑剂；拟在实验室阶段解决油脂基增塑剂不能作为PVC主增塑剂的难题。利用现代的分析手段，探讨从分子层面上研究PVC增塑剂增塑机理的研究方法，揭示增塑剂分子与PVC树脂分子链结合形式和相互作用关系，完善增塑剂对PVC树脂的增塑机理，深入研究桐油基PVC增塑剂的增塑机理，为精确的设计新型高效的油脂基增塑剂做理论指导。

针对目前桐油等非食用油脂深加工应用开发不足、国内环保型油脂基增塑剂的品质差等迫切需要解决的问题，本项目以桐油等非食用油脂为主要原料通过环氧化、羧酸开环、乙酰化和点击等化学反应成功制备了几种油脂基增塑剂；分析了各类油脂基增塑剂的增塑性能、热稳定性能、耐迁移性能，利用交叉极化魔角自旋核磁共振（13C CP/MAS NMR）和红外光谱（在低波段600-700cm-1）建立增塑剂与PVC链段的微观结构关系。.1.所得ETM和TEP的环氧值分别为4.9%和5.2%。ETM和TEP增塑PVC薄膜的热稳定性和耐溶剂性均优于DOP。ETM和TEP的塑化率分别达到104.1%和101.5%。2.研究了在脂肪酸链上不同结构的引入对增塑性能的影响：①苯环和更多酯键的引入增加了增塑剂分子的极性，改善了与增塑剂和PVC树脂的相容性；②较高的分子量可以降低挥发分和萃取损失；③含链状烷基二酸改性所得油脂基增塑剂AC-FAME-AA和AC-FAME-SA的低温塑化效果优于其他化合物，但增塑剂效果不及含有苯环结构的油脂基增塑剂。用苯甲酸改性的油脂基增塑剂AC-FAME-BA分子结构相对较小，相对极性基团较多，增塑效率较高，耐迁移性能好。由于结构中含有长的脂肪链，使AC-FAME-PTA、AC-FAME-IPA和AC-FAME-BA作为PVC增塑剂制品在水中的耐析出性能都优于DOP。3. 13C CP/MAS NMR）分析表明，Cl-CH••••O=C-之间的氢键能量越大，脱屏蔽效应越强，即增塑PVC的-CH-Cl基团的向低场位移越大，增塑效果越好。红外光谱分析表明，增塑的PVC材料中C-Cl的TTTT吸收峰（635.75cm-1，PVC链的结晶区存在TTTT序列）向低频移动越多，表明增塑剂能达到PVC的晶区，与PVC的相容性更好增塑效果越好。如果只在TGTG的非晶区出现向低频移动表明该类增塑剂不能作为主增塑剂使用，只能作为辅助增塑剂。4.本项目得到了2种可完全替代邻苯类增塑剂（DOP）的油脂基增塑剂AC-FAME-BA 和SF-PE；3种在某些溶剂（如乙醇或水）中的耐析出性能优良油脂基增塑剂AC-FAME-PTA、AC-FAME-IPA和AC-FAME-CAE。本项目申请国家发明专利2件，其中授权1件；发表文章7篇，其中SCI收录文章3篇，EI收录文章1篇，CSCD收录文章2篇。