Study On Heterogeneous Catalytic Aldol Reaction In Molecularly Imprinted Microreactor With Photoregulated Properties

The application of molecularly imprinted materials in the field of catalytic field is very promising.Therefore,it is a hot research topic in the field of materials.The application of photoresponsive molecularly imprinted materials in catalysis is scarce.In this dissertation,modified hydroxyproline was synthesized and used as catalyst monomer,three photo-responsive azobenzene derivatives and used as the photorespnosive monomer.Based on such dual functional monomers and using product as the template,molecular imprinting materials were fabricated,and their catalytic performance and photoswitchable properties on aldol reaction were studied.The specific research contents are as follows:In Chapter One,the molecular imprinting is summarized and the development,characteristics,and potential applications of molecular imprinting are introduced.The development in photocontrolled reaction using azobenzene as a photoresponsive unit was summarized.The research status of Aldol reaction catalyzed by supported polymer was summarized.The preparation of photo-responsive molecularly imprinted microreactor using molecular imprinting technique for aldol reaction was proposed.In Chapter Two,3,5-dimethylaniline,phenol,methacrylic acid,and hydroxyproline were used as raw materials to synthesize a photoresponsive functional monomer DMAMA via diazo coupling and esterification.The catalytic monomer ProMA was synthesized via and esterification.The chemical structures of DMAMA and ProMA were confirmed by 1HNMR,13 CNMR,elemental analysis,and mass spectroscopy.The photo-isomerization of DMAMA was investigated.The molecularly imprinted materials were fabricated using the product as template molecule,DMAMA and ProMA as dual functional monomers,and EGDMA as crosslinker.The effect of the amount of crosslinker,the molar ratio of azobenzene monomer and catalyst monomer were discussed.The morphology and structure of the materials were characterized by SEM,TG,FT-IR,UV-Vis and nitrogen adsorption-desorption analysis.The experimental conditions including solvent,MIP amount,photoirradiation,reaction temperature and time were optimized.MIP catalytic aldol reaction conversion rate of 82%,light control difference of 20%.The catalyst has different catalytic properties for different substrates,which can be reused three times.In Chapter Three,three photoresponsive azobenzene monomers were synthesized by diazo coupling reaction and esterification reaction using three alcohols with different chain length.The chemical structure of the monomer was confirmed by 1HNMR,13 CNMR,and mass spectroscopy.The photo-isomerization of the monomer and MIP was investigated.The morphology and structure of the MIP materials were characterized by SEM,TG,FT-IR and nitrogen adsorption-desorption analysis.The experimental conditions were optimized.The effects of chain length of alcohols and photoirradiation on the catalytic activity of MIP were studied.Light isomerization rate is reduced with chain longer.MIP catalytic conversion rate of 66%,light control difference of 23%.In Chapter four,a photoresponsive azobenzene monomer DOAMA was synthesized by diazo coupling reaction and esterification reaction using 3,5-dimethoxyaniline and phenol as raw materials.The chemical structure of DOAMA was confirmed by 1HNMR,13 CNMR,and mass spectroscopy.The photo-isomerization of DOAMA was investigated.The molecular imprinting materials were synthesized using product as template molecule,DOAMA and ProMA as dual functional monomers,and EGDMA as crosslinker.The morphology and structure of the materials were characterized by SEM,TG,FT-IR and nitrogen adsorption-desorption analysis.The experimental conditions including solvent,reaction temperature,molar ratio of azobenzene monomer and catalyst monomer were discussed.Catalytic conversion rate of 83%,light control difference of 27%,which can be reused 3 times.In the last chapter,the contents of the whole paper were summarized,and some recommendations for future work were provided.