松节油基吡嗪系化合物的合成及其对聚氨酯预聚反应的催化作用  

Synthesis of turpentine based pyrazine and its catalytic effect on polyurethane pre-polymerization

作　　者：郭佳雯 王俊 陈莉晶 徐徐 GUO Jiawen;WANG Jun;CHEN Lijing;XU Xu(College of Chemical Engineering,Nanjing Forestry University;Jiangsu Key Laboratory of Biomass Green Materials and Chemicals,Nanjing 210037,China)

机构地区：[1]南京林业大学化学工程学院,江苏省生物质绿色燃料与化学品重点实验室,南京210037

出　　处：《林业工程学报》2018年第2期70-76,共7页Journal of Forestry Engineering

基　　金：十二五”农村领域国家科技计划课题(2015BAD15B04)；国家自然科学基金(31600462)。

摘　　要：以松节油为原料,分别经选择性氧化、环化、脱氢等反应,合成了新型吡嗪系化合物,并通过FT-IR、GCMS、1H NMR、13C NMR等分析手段对松节油基吡嗪系化合物的结构进行表征。将合成得到的松节油基吡嗪系化合物作为催化剂,采用化学滴定法研究其对六亚甲基二异氰酸酯(HDI)与异丁醇的预聚反应的催化性能,通过数学模型法对预聚反应的表观动力学进行分析,并计算不同松节油基胺类催化剂作用下的反应速率常数。研究结果表明,2-甲基-2,3-二氢樟脑并[2,3-e]吡嗪对聚氨酯的催化作用明显大于N,N-二甲基环己胺;樟脑并[2,3-b]吡嗪的催化作用与N,N-二甲基环己胺接近;2,3-二氢樟脑并[2,3-e]吡嗪、樟脑并[2,3-b]-5,6-二氢吡嗪并[e]环己烷、2-甲基樟脑并[2,3-b]吡嗪、樟脑并[2,3-b]吡嗪并[e]环己烷基本无催化效果。本研究结果表明结构中连接甲基等推电子基团时,可增强催化剂的碱性,从而使其达到较好的催化效果。Novel pyrazine compounds were synthesized from turpentine by a series of reactions including selective oxidation,cyclization,and dehydrogenation.The structures of the compounds were characterized by Fourier infrared spectroscopy(FTIR),gas chromatographymass spectrometry(GCMS),hydrogen1 nuclear magnetic resonance(1H NMR),carbon13 nuclear magnetic resonance(13C NMR)and other analytical methods.The catalytic effect of synthesized turpentine based pyrazine compounds on the prepolymerization reaction between hexamethylene diisocyanate(HDI)and isobutanol were studied by titration.Moreover,the apparent kinetics of the prepolymerization reaction was investigated by mathematical modeling approach,and the reaction rate constants with different turpentinebased pyrazine catalysts were calculated as well.The results showed that the catalytic activity of 2-methyl-2,3-dihydrocamphor[2,3-e]pyrazine was significantly better than that of N,Ndimethylcyclohexylamine.The catalytic activity of camphor[2,3-b]pyrazine was similar to that of N,Ndimethylcyclohexylamine.Meanwhile,no catalytic activity of 2,3-dihydrocamphor[2,3-e]pyrazine,camphor[2,3-b]5,6-dihydrocamphor[e]cyclohexane,2-methyl-camphor[2,3-b]pyrazine and camphor[2,3-b]pyrazino[e]cyclohexane were found on prepolymerization reaction.The results of this study indicated that the catalytic effect can be improved when the methyl isoelectric group is introduced in the structure because of the enhanced alkalinity.

关 键 词：松节油 吡嗪系化合物 聚氨酯 催化剂 

分 类 号：S789.2[农业科学—林学] TQ351[化学工程]