尿素法合成甲苯-2,4-二氨基甲酸正丙酯反应.pdf

石油学报(石油加工
2013年6月
ACTA PETROLEI SINICA (PETROLEUM PROCESSING SECTION)
第29卷第3期
文章编号:1001-8719(2013)03-0494-07
尿素法合成甲苯-2,4-二氨基甲酸正丙酯反应
耿艳楼,方鸿刚,安华良,王桂荣,赵新强,王延吉
(河北工业大学化工学院绿色化工与高效节能河北省重点实验室,天津300130)
摘要:以2,4二氨基甲苯(TDA)、尿素和正丙醇( Proh)为原料,非催化合成了甲苯-2,4-ニ氨基甲酸正丙酯(TDC-P)
考察了反应条件对该合成反应的影响,并基于反应产物的液相色谱一质谱分析结果,推测了可能的反应路径。结果
表明,该反应适宜的反应条件为n(TDA)/n(Urea)ー1/3、n(TDA)/n(PrOH)=1/84、反应温度170℃、反应压力
0.6MPa、反应时间4h。此时,TDA转化率95.3%,TDCP产率66.1%、选择性69.4%。合成TDC-P可能的反
应路径有3条,(1)经过氨基甲酸正内酯和3-氨基-4-甲基苯氨基甲酸正丙酯或2-甲基-5-氨基苯氨基甲酸正丙酯生成
TDC-P的反应路径;(2)以2,4-甲莱二脲为中间产物的反应路径;(3)以3-脲基-4-甲基苯氨基甲酸正丙酯或2-甲基
5-脲基苯氨基甲酸正丙酯为中间产物的反应路径。
关键词:2,4-二氨基甲苯;尿素;正丙醇;甲翠-2,4-二氨基甲酸正丙酯;反应路径
中图分类号:TQ246.3文献标识码:Adoi:10.3969/j.issn,1001-8719.2013.03.021
Synthesis of Dipropyl Toluene-2, 4-dicarbamate via Urea Route
GENG Yanlou, FANG Honggang, AN Hualiang, WANG Guirong, ZHAO Xingiang, WANG Yanji
Ebei Provincial Key Lab of Green Chemical Technology &High Efficient Energy Saving, School of
Chemical Engineering &Technology, Hebei University of Technology, Tianjin 00130, China)
Abstract: Dipropyl toluene-2, 4-dicarbamate (TDC-P)was synthesized successfully by using 2, 4
diamino toluene (TDA), urea and propanol(PROH) as raw materials in the absence of catalyst.
The effects of reaction conditions on the synthesis of TDC-P were studied. The plausible reaction
paths existed in this synthesis were speculated based on the result of HPLC-MS analyses. The
results showed that the suitable reaction conditions for this synthesis were TDA/urea molar ratio of
1/3, TDA/PROH molar ratio of 1/84, reaction temperature of 170C, reaction pressure of 0.6 Mpa
and reaction time of 4 h, under which TDA conversion, TDC-P yield and selectivity were 95.3%
66.1% and 69.4%, respectively. There existed three possible reaction paths in the TDC-P
synthesis, which were (1 through propyl carbamate and propyl 2-methyi-5-amino-n-
henylcarbamate or propyl 3-amino-4-mcthyl-n phenylcarbamate, (2 )via toluene-2, 4-bisurea as an
intermediate, (3 via propyl 3-ureido-4-methyl-n-phenylcarbamate or propyl 2-methyl-5-ureido-n
henylcarbamate as an intermediate.
Key words: 2, 4-diamino toluene; urea; propanol; dipropyl toluene-2, 4-dicarbamate; reaction path
甲苯二异氰酸酯(TDI)是生产聚氨酯的重要原原料剧毒、副产物腐蚀性强等缺点,寻求环境友好
料之一,工业上主要通过光气法生产,该方法存在的光气替代品以及开发洁净的非光气法合成TDI路
收稿日期:20120725
基金项目:国家自然科学基金项目(20976035)、河北省自然科学基金项目(B201000019)、天津市自然科学基金项目(12 ICYBIC12800)资助
第一作者:耿艳楼,男,教授,从事绿色过程工程与工艺的研究
通讯联系人:赵新强,男,教授,从事绿色过程工程与工艺的研究;Tel:022-60202427;E-mail:zhaoxu@hebut.edu.cn