1,3,5-均三嗪三醇与二乙烯三胺的催化胺化反应
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摘要
CO2作为一种碳资源,对其进行化学利用以达到减排目的,已成为目前科学研究热点之一。1,3,5-均三嗪三醇是一种CO2封存产品,开发其下游产品具有广阔前景。以1,3,5-均三嗪三醇(sym-triazinetriol,CA)与二乙烯三胺(diethylenetriamine,DETA)为原料,合成6-二乙烯三胺基-1,3,5-三嗪-2,4(1H,3H)-二酮。采用单因素法探讨了反应物摩尔比、反应时间、反应温度以及催化剂对产率的影响,由FT-IR、1H NMR与13C NMR等表征产物。反应最佳条件:CA与DETA摩尔比为1∶4,反应温度210℃,反应时间为4 h,催化剂为5A分子筛,产率为70.9%。
As a carbon resource,it has become one of the hot spots at present through the chemical utilization of CO2 to achieve emission reduction purposes. Sym-triazinetriol is kind of CO2 sequestration products,and it has broad prospects to develop its downstream products. In this paper,synthesis of 6-divinyl three amine-1,3,5-triazine base-2,4(1 H,3 H)-diketone by diethylenetriamine(DETA) and Sym-triazinetriol(CA) was studied. The effects of molar ratio,reaction time,reaction temperature and catalyst on the yields were investigated by single-factor method. Then,the product was characterized by IR,1 H NMR and13 C NMR. The optimum conditions were as follows: the molar ratio of CA to DETA was 1∶ 4,the reaction temperature was 210 ℃,the reaction time was 4 h,the catalyst was 5 A molecular sieve. The yield of product can reach 70. 9%.
As a carbon resource,it has become one of the hot spots at present through the chemical utilization of CO2 to achieve emission reduction purposes. Sym-triazinetriol is kind of CO2 sequestration products,and it has broad prospects to develop its downstream products. In this paper,synthesis of 6-divinyl three amine-1,3,5-triazine base-2,4(1 H,3 H)-diketone by diethylenetriamine(DETA) and Sym-triazinetriol(CA) was studied. The effects of molar ratio,reaction time,reaction temperature and catalyst on the yields were investigated by single-factor method. Then,the product was characterized by IR,1 H NMR and13 C NMR. The optimum conditions were as follows: the molar ratio of CA to DETA was 1∶ 4,the reaction temperature was 210 ℃,the reaction time was 4 h,the catalyst was 5 A molecular sieve. The yield of product can reach 70. 9%.
引文
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[2]COMPSTON H,BAILEY I.Climate policy strength compared:China,the US,the EU,India,Russia,and Japan[J].Climate Policy,2016,16(2):145-164.
[3]PEARSON P N,FOSTER G L,WADE B S.Atmospheric carbon dioxide through the eocene-oligocene climate transition[J].Nature,2009,461(7267):1110-1113.
[4]OCHIAI B,ENDO T.Carbon dioxide and carbon disulfide as resources for functional polymers[J].Progress in Polymer Science,2005,30(2):183-215.
[5]PRENTICE I C,FARQUHAR G D,FASHAM M J R,et al.The carbon cycle and atmospheric carbon dioxide[J].Cambridge University Press,2001,41(3):159-165.
[6]朱维群,齐情情,王倩,等.化石燃料环境友好工业路线开发[J].山东大学学报(理学版),2017,52(5):25-30.ZHU Weiqun,QI Qingqing,WANG Qian,et al.The development of fossil fuel environment-friendly industrial route[J].Journal of Shandong University(Natural Science),2017,52(5):25-30.
[7]王付燕,孙洪志,宋名秀,等.二氧化碳的氨化反应研究进展[J].化工进展,2014,33(1):209-218.WANG Fuyan,SUN Hongzhi,SONG M ingxiu,et al.Research progress of ammonization reaction of carbon dioxide[J].Journal of Chemical Industry and Engineering Progress,2014,33(1):209-218.
[8]宋名秀,孙洪志,阿布都拉江·那斯尔,等.二氧化碳减排技术路线探讨[J].现代化工,2013,33(8):5-8.SONG M ingxiu,SUN Hongzhi,Abudoulajiang·Nasier,et al.Discussion on carbon dioxide emission reduction technologies[J].Journal of M odern Chemical Industry,2013,33(8):5-8.
[9]朱维群,王倩,阿不都拉江·那斯尔,等.利用氨气和二氧化碳合成三聚氰酸或三聚氰胺的方法:CN102633736A[P].2012-08-15.ZHU Weiqun,WANG Qian,Abudoulajiang·Nasier,et al.Process for synthesizing cyanuric acid or melamine by using ammonia gas and carbon dioxide:CN102633736A[P].2012-08-15.
[10]罗胜铁,孟丽军.氯代异氰脲酸类产品的制备和应用[J].化工进展,2002,21(9):693-696.LUO Shengtie,M ENG Lijun.Preparation and application of isocyanuric acid chloride products[J].Journal of Chemical Industry and Engineering Progress,2002,21(9):693-696.
[11]KLUGE R,SCHULZ M,LIEBSCH S.Diastereoselective epoxidation of olefins by organo sulfonic peracids,II[J].Tetrahedron,1996,52(8):2957-2976.
[12]ERMAKOV A S,BULATOV P V,VINOGRADOV D B,et al.Synthesis of nitroesters based on methylol derivatives of parabanic and isocyanuric acids[J].Russian Journal of Organic Chemistry,2005,41(2):255-256.
[13]彭敏,单文伟,曾光明,等.三(环氧丙基)异氰尿酸酯的合成[J].热固性树脂,2004,19(6):12-14.PENG M in,SHAN Wenw ei,ZENG Guangming,et al.Synthesis of triglycidyl isocyanurate[J].Thermosetting Resin,2004,19(6):12-14.
[14]朱维群.一种低温合成三聚氰胺的新方法[C]//全国化工合成氨设计技术中心站2011年技术交流会论文集.长沙:全国化工合成氨设计技术中心站2011年技术交流会.2011.ZHU Weiqun.A new method for synthesis of melamine at low temperature[C]//Proceedings of National Chemical Ammonia Synthesis Design Technology Center Station 2011 Technical Exchange M eeting.Changsha:National Chemical Ammonia Synthesis Design Technology Center Station 2011 Technical Exchange M eeting,2011.
[15]林休休,刘小红,徐冬梅,等.一种含三嗪环的四臂引发核的合成与表征[J].精细化工,2007,24(2):194-198.LIN Xiuxiu,LIU Xiaohong,XU Dongmei,et al.Synthesis and characterization of a four-arm initiating core containing 1,3,5-triazine[J].Fine Chemicals,2007,24(2):194-198.
[16]杨贵宝.三聚氯氰与脂肪族多胺的反应研究及树枝状多臂引发核的制备[D].苏州:苏州大学,2009.YANG Guibao.Study on the reaction betw een aliphatic polyamines and cyanuric chloride and synthesis of multiarm dendritic initial cores[D].Suzhou:Soochow University,2009.
[17]王婉秦,张秀成,陈立宇,等.氨化法合成3,5-二甲基苯胺的工艺研究[J].染料与染色,2001,38(3):35-36.WANG Wanqin,ZHANG Xiucheng,CHEN Liyu,et al.A study on the synthesis of 3,5-dimethylaniline by amination[J].Dyestuff Industry,2001,38(3):35-36.
[18]文明.高活性负载金属镍催化剂上醇的催化胺化研究[D].南京:南京大学,2016.WEN M ing.A study of amination of alcohols to amines over supported nickel cahlysts[D].Nanjing:Nanjing University,2016.
[19]MANOHAR B,GANESH I,REDDY B M.Aniline synthesis from cyclohexanol and ammonia over mixed oxide catalysts[J].Journal of M olecular Catalysis A Chemical,1998,129(1):L5-L8.
[20]封超,陈立宇,应晓有,等.2,6-二甲基苯酚在超临界氨中的催化氨化工艺研究[J].高校化学工程学报,2012,26(6):977-982.FENG Chao,CHEN Liyu,YING Xiaoyou,et al.Catalytic amination of 2,6-dimethylphenol in supercritical ammonia[J].Journal of Chemical Engineering of Chinese Universities,2012,26(6):977-982.
[21]钱超.醇羟基及酚羟基化合物的催化胺化[D].杭州:浙江大学,2004.QIAN Chao.Study on catalytic amination of alcohols and phenols[D].Hangzhou:Zhejiang University,2016.
[22]LIAO Y W,ZHOU Q J,CHEN M J,et al.Standard test methods of amine value and preliminary investigation of spraying pure polyurea used in beijing-shanghai highspeed railw ay[J].Shanghai Coatings,2010,48(5):38-40.
[23]孙曼灵,郑高锋.胺类环氧固化剂胺值测定方法的探讨[J].热固性树脂,2006,21(2):30-32.SUN M anling,ZHENG Gaofeng.Study on measurement method of amine value of amine epoxy hardener[J].Thermosetting Resin,2006,21(2):30-32.
[24]余秦伟,李亚妮,梅苏宁,等.改性HZSM-5催化胺化异丙醇胺合成1,2-丙二胺[J].化工进展,2014,33(8):2060-2065.YU Qinw ei,LI Yani,M EI Suning,et al.Synthesis of1,2-propanediamine by amination of isopropanolamine on modified HZSM-5[J].Journal of Chemical Industry and Engineering Progress,2014,33(8):2060-2065.
[25]化工百科全书编委会.化工百科全书[M].北京:化学工业出版社,1990:150.Encyclopedia of chemical technology editorial society.Encyclopedia of chemical technology[M].Beijing:Chemical Industry Press,1990:150.
[26]KEN Motokura,NOBUAKI Nakagiri,TOMOO Mizugaki,et al.Nucleophilic substitution reactions of alcohols w ith use of montmorillonite catalysts as solid brnsted acids[J].Journal of Organic Chemistry,2007,72(16):6006-6015.