On-line ATR-IR Spectroscopy Technology Combined With Chemometrics For Study The Synthesis Mechanism Of Triazole Heterocyclic Compounds

The triazole heterocyclic compounds have the advantages of high positive formation enthalpy,achieving oxygen balance easily,introduction of various groups conveniently,green and so on.Studying of synthesis mechanism not only optimize the reaction conditions and improve yield,but also help to investigate new types of energetic materials.On-line Attenuated Total reflection Infrared(ATR-IR)spectroscopy is simple,flexible,fast and non-destructive,without sample pretreatment,and can be used to real-time monitor the synthesis process.The chemometrics methods were uesd to analyze the hidden chemical information in spectra data.Thus,in this paper,the synthesis mechanism of energetic materials was studied,and the the accuracy of results were verified by the quantum chemical calculations.The study not only enrich the studying method of synthesis mechanism,but also provide new ideas,methods and technical support for the development and innovation of proceses analytical technology(PAT).The full text is divided into four chapters,the main research contents are shown as follows:1.On-line ATR-IR spectroscopy combined with Mutual Information Least Dependent Component Analysis(MILCA)was used to study the synthesis mechanism of 3,5-diamino-1,2,4-triazole(DAT).The Principal Component Analysis(PCA)and Subspace Compare Method(SCM)were used to analyze the IR spectroscopic matrix where 5 principal components were acquired,the effective spectral information of the principal components was extracted by the MILCA algorithm,and then the possible synthesis mechanism of DAT was deduced through the changes of functional groups,finally,the reliability of synthesis mechanism was verified by the quantum chemical calculations.Compared to other Independent Components Analysis(ICA)methods,MILCA has the advantages of convenient,fast and accurate.The study contributes to the optimization of chemical synthesis processes and provides strong technical support for the research and development of process analysis techniques.2.On-line ATR-IR.spectroscopy combined with Hard-and Soft-modelling Multivariate Curve Resolution-Alternating Least Squares(HS-MCR)was used to study the synthesis mechanism of DAT.The SCM was used to analyze the IR spectroscopic matrix where 5 principal components were acquired,the effective spectral information of the principal components were extracted by HS-MCR and ICA algorithm,the results obtained by HS-MCR method agreed well with actual measurement results,and then the accurate of spectra was verified by MCR-BANDS,finally,the possible synthesis mechanism of DAT was deduced.Compared with the traditional Multivariate Curve Resolution-Alternating Least Squares(MCR-ALS)method,this method can reduce rotation ambiguity and obtain the reaction rate constant.3.On-line ATR-IR spectroscopy combined with HS-MCR was used to study the synthesis mechanism of 4,4'-azo(1,2,4-triazole).The SCM was used to analyze the IR spectroscopic matrix where 4 principal components were acquired,the effective spectral information of the principal components was extracted by HS-MCR algorithm,the accurate of spectra was verified by MCR-BANDS,and then the possible synthesis mechanism of DAT was deduced,finally,the reliability of synthesis mechanism was verified by the quantum chemical calculations.Compared to other methods,the HS-MCR method can obtain a unique solution and reduce the peaks flip.This method is a promising method in proceses analytical technology and is particularly useful for studying the synthesis mechanism.