Design,Synthesis and the Catalytic Properties of Functionalized Porous Organic Materials

Author:Kong Sheng Nan

Supervisor:shu mou hai qian xue feng

Database:Doctor

Degree Year:2018

Download:56

Pages:255

Size:10722K

Keyword:

Porous organic materials include covalent organic frameworks(COFs)with crystalline structures,amorphous porous organic polymers(POPs)and organic cages.Considering the structural features,porous organic polymers are divided into hyper crosslinked polymers(HCPs),polymers of intrinsic microporosity(PIMs),covalent organic frameworks(COFs)and conjugated microporous polymers(CMPs).POPs is composed of elements C,H,N,O and B et al,and exhibit low density and high surface area.They could be resistant to high temperature and stable in acid and basic solutions.Due to their synthetic diversity and the flexiblely designed structures,they are widely used in gas storage and separation,energy storage,light absorption and emission and heterogeneous catalysis.In this thesis,various porous organic polymers(POPs)including three functionalized POPs were synthesized and characterized by several techniques including powder X-ray diffraction,SEM and TEM,solid state 13C&31P NMR spectra and nitrogen adsorption.After postsynthetic modification with metal ions such as Pd(II),Ru(II)and Ti(IV),these materials could be applied in the catalytic organic reactions such as Suzuki-Miyaura reaction and Sonogashira reaction in water medium,hydrogenation ofβ-keto esters,asymmetric diethylzinc addition to aldehydes,and exhit highly effective catalytic activity.Four chiral molecular containers based on resorcinarene cavitand have been synthesized,and characterized by using 1H and 13C NMR spectra,circular dichroism spectra,ESI-MS and single crystal X-ray diffraction analysis,the application of one molecular container has been investigated by using 1H NMR spectra and electrospray ionization mass spectra(ESI-MS).The main results of this thesis are listed as following.First,nine covalent organic polymers were synthesized by Sonogashira reaction and“Click”reaction.The materials were characterized by nitrogen adsorption.The influences of the reaction temperature,the amount of catalyst and the post-treatment of the materials on BET specific surface area are investigated.The BET specific surface area of the polymers decreases with the increase of the amount of the catalyst.The BET specific surface area of polymers got by temperature programming is much bigger than one-step temperature procedure.And the BET specific surface area of polymers washed by EDTA-2Na is much higher than those washed by acid solution or basic solution.Second,a porous organic polymer bearing 2,2’-bipyridine functional group,namely POP-bipy,has been synthesized.After treating with Pd(CH3CN)2Cl2,a composite material Pd/POP-bipy was obtained.The materials have been characterized by 13C CP/MAS NMR,FT-IR,p-XRD,nitrogen adsorption and thermogravimetric(TG)techniques.The content and valence of palladium in Pd/POP-bipy have been determined by ICP and XPS.The composite material Pd/POP-bipy exhibits excellent catalytic activity for Suzuki-Miyaura reaction in water and Sonogashira coupling reaction in methanol/water,the yield was as high as 99%.The catalyst could be recycled five times in Suzuki-Miyaura reaction,and could be recycled eight cycles in Sonogashira coupling reaction without significant loss of the activity.Third,a porous organic polymer(POP-BINAPO)with chiral BINAPO has been prepared by Copper-catalyzed alkynes-superimposed nitride reaction(CuAAC).After deoxidization and loading with Ruthenium(II)species via coordination,the composite material Ru/POP-BINAP could be used as one heterogeneous catalyst for the asymmetric hydrogenation ofβ-keto esters.The yield was as high as 99%,and the ee value is as high as 96%.The material could be resued for four times without significant loss of the activity and ee value.Fourth,an amorphous porous organic polymer CMP-BINOL has been synthesized.After being treated with Ti(OiPr)4,the CMP-BINOL could be used as highly effective and reusable heterogeneous catalyst for the asymmetric diethylzinc addition reaction to aldehydes.Fifth,chiral molecular containers(R)/(S)-CPT-OH and(R)/(S)-CPT-DC-OH were got by 2-methylbenzene diphenol and tripolyacetaldehyde using as the starting materials.The structure of the molecular containers was characterized by 1H&13C NMR,ESI-MS and X-ray single crystal diffraction,and the chirality of the molecular containers was proved by the circular dichroism(CD)spectra.Molecular containers could be used to recognize small molecules because of their cavity structures.The recognition effect of(R)-CPT-OH on(R)-1-phenyl ethanol was demonstrated by 1H NMR and ESI-MS.The further research is ongoing.