Synthesis Strategies And Catalytic Properties Research Of Functional Porous Organic Polymers

Organic porous polymers(POPs)are a new kind of porous materials which are composed of organic molecules connected by covalent bonds.Compared with traditional inorganic porous materials and inorganic-organic hybrid porous materials,POPs have the advantages of stable structure,strong modifiability and other comprehensive advantages,which make them have broad application prospects in the fields of catalysis,gas storage,pollutant adsorption and energy.At present,the development of new POPs has appeared a lot of academic and applied problems in urgent need of further research,mainly including:(1)how to control the aperture and function of POPs at the molecular level,and develop more universal functional regulation method;(2)how to develop POPs with special structures and explore their intrinsic structure-activity relationship;(3)how to reasonably utilize the weak skeleton rigidity of organic porous materials to achieve special intelligent catalysis applications.Based on the above questions,this doctoral thesis attempts to conduct basic research from the following perspectives and obtain the corresponding research results:(A)Based on the knowledge background of polymer chemistry,new POPs were constructed from polymer.Taking advantage of the diversity of polymer synthesis methods,strong controllability and easy functional modification,the size of(mesoporous)pore and the diversity of functionalization in POPs are rationally regulated,so as to make them perform well in the basic research in the fields of catalysis and adsorption.(B)Based on the core-shell bottlebrush copolymers and block copolymers,the hollow microporous organic nanotube materials and spherical materials were constructed.A triphenylphosphine mediated hyper-cross-linking self-assembly strategy was proposed to construct a honeycomb-like bicontinuous organic porous polymer material.These honeycomb-like bicontinuous organic porous polymer materials synthesized after the loading of noble metals have better catalytic activity than pure microporous catalysts in different catalytic experiments,fully proving the important influence of their structure on catalytic performance.(C)A yolk-shell polymer nanoreactor was constructed with hollow porous polymer nanospheres as the main body.Since the polymer flexible skeleton has different swelling phenomenon in different solvents,we try to explore the selective catalytic performance of the polymer shell microporous pore diameter in different solvents by intelligent response fine-tuning to the reactant molecules of different sizes,so as to achieve the effective combination of size selectivity and efficient catalytic rate.