Study Of The Morphology-Controlled Hyper-Crosslinking Polymers For Cascade Catalysis Reaction

Porous organic polymers as one of the most popular noble material in the recent years have aroused more and more interests from researchers from different fields for their unique structures and excellent properties including outstanding chemical modification and superior machinability.These properties make them have great application value in varieties of fields such as adsorption,separation,catalysis,energy storage and so on.Besides,POPs can also be used as the solid supports for other catalysts because of their huge specific surface area and excellent stability.On this basis,acid-base bifunctional and metal nanoparticles doped POPs catalysts were prepared and used for the one-pot catalysis and POPs different kinds of cascade reactions.This article was divided into three sections.The first section is the introduction which contains the preparation of POPs and palladium nanoparticles loaded POPs catalysts and their application in cascade catalysis reactions.The second section reports the synthesis of the acid-base bifunctional catalyst（NH₂-SO₃H-H-ONTFs）with special hollow microporous nanotube structure by Friedel-Crafts alkylation reaction using the core-shell bottlebrush copolymer（P（GM-g-PLA-g-PBOCa-g-PPVBs/PS））as precursors.In the process of synthesis,the acid groups were anchored into the wall of nanotubes and basic sites were introduced on the inner layer wall of nanotubes.by simple and rational molecular design.This can prevent the acid and base functionalized groups from neutralization reaction and mutual deactivation based on the effective isolation.The structures and properties of NH₂-SO₃H-H-ONTFs were tested by varieties of methods like FT-IR,TEM,¹H NMR and Nitrogen adsorption-desorption isotherms,which proved the morphology of hollow nanotube and micropore,mesopore,macropore structure.The BET surface area is 845m²/g and total volume of pores is 1.39cm³/g.The catalysts showed great catalytic performance in acid-base one-pot deacetalization-Knoevenagel cascade reaction and good recoverability after eight circles.Thethird sectioncontainstheintroduction ofpreparationof amino-functionalized hollow microporous organic nanospheres supported palladium catalysts（Pd@NH₂-H-MONs）and its application in the catalysis.At first,NH₂-H-MONs were prepared by using tri-block polymer as precursor（PLA-b-PBOCa-b-PS）via the hyper-crosslinking mediated self-assembly process.Then,the catalyst（Pd@NH₂-H-MONs）was produced through the coordination interaction between amino-groups and Pd.The structure and properties of catalysts were tested by TEM,ICP,XPS,XRD and so on.The surface area and total pore volume of the resulting Pd@NH₂-H-MONs are very large,values of which are468m²/g and 0.61cm³/g,respectively.Owing to high loading capacity,moderate particle size and dispersity of Pd nanoparticles,the catalysts can be used to cascade reactions.The cascade reactions of oxidation of alcohol-Knoevenagel condensation reaction and Knoevenagel condensation coupling with selective hydrogenation reaction were chosen as the model reactions.The study found that Pd@NH₂-H-MONs showed excellent catalytic performance,universality and chemo-selectivity in these reactions.This work can not only enrich the application fields of noble metal nanoparticles supported POPs,but also provide research basis for the usage of catalysts in varieties of cascade reactions research.