Study On The Reaction Between Aliphatic Polyamines And Cyanuric Chloride And Synthesis Of Multi-arm Dendritic Initial Cores

In this thesis,the reaction between the primary amino groups and the secondary amino groups in diethylenetriamine(DETA),triethylenetetramine(TETA) and tetraethylenepentamine(TEPA) and the first chorine atom in cyanuric chloride(TCT) was studied.The kinetics of the reaction between the primary amino groups and the first chorine atom in cyanuric chloride was investigated.A series of four-arm,six-arm, eight-arm and ten-arm initial cores which can be used for synthesizing dendrimers were prepared through the above reactions.The structures of the target products were characterized and the solubility and thermostability of the products were examined.It can be summarized as follows:1.The reaction between the primary amino groups in DETA,TETA,TEPA and the first chorine atom in TCT:Using dichloromethane/water(volume 1:1) as solvent, NaOH as base,at 0～5℃,the primary amino groups in DETA,TETA,TEPA could react with the first chorine atom in TCT,with which a series of four-arm initial cores 2TDETA,2TTETA and 2TTEPA were prepared.The structures of the target products were characterized by FTIR,~1H-NMR,MS and elementary analysis,and the synthesis conditions were optimized.2.The kinetics of the reaction between the primary amino groups and the first chorine atom in cyanuric chloride:The reactions between 1 equivalent DETA,TETA, TEPA and 2 equivalent TCT at 0～5℃were studied.The kinetics of the reaction showed two grade characteristic,which suggested that the two primary amino groups in DETA, TETA,TEPA be reacted step by step.3.The reaction between the primary amino groups and the secondary amino groups in DETA,TETA,TEPA and the first chorine atom in TCT:Using anhydrous tetrahydrofuran as solvent,N,N-diisopropylethylamine as base,nitrogen as protection gas,the reactions were carried out at 0～5℃for some time,then,at room temperature for another period of time,both of the primary amino groups and the secondary amino groups in DETA,TETA,TEPA could react with the first chorine atom in TCT,with which a series of six-arm,eight-arm and ten-arm initial cores 3TDETA,4TTETA and 5TTEPA were prepared.The structures of the target products were characterized by FTIR,~1H-NMR,MS and elementary analysis,and the synthesis conditions were optimized.4.Study of the properties of the products:The solubility and thermostability of 2TDETA,2TTETA,2TTEPA,3TDETA,4TTETA and 5TTEPA were investigated. 2TTETA and 2TTEPA had poor solubility,2TTETA only could be dissolved a very small amount in dimethylsulfoxide(DMSO),while 2TTEPA could hardly be dissolved in DMSO.All other products were soluble in DMSO,partially soluble in DMF,THF and 1,4-dioxane.They also had small solubility in acetone and ethyl alcohol,and very small solubility in acetonitrile,methyl alcohol and ethyl acetate,however,all the products could not be dissolved in dichloromethane.Their melting points were above 320℃,and their thermogravimetric analysis(TGA) data indicated that all products had good thermostability.