Preparation Of Highly Crystalline Porous Polymers Based On Cyclobutane And Imine Bonds And Their Catalytic Applications

Crystalline porous polymers have highly ordered crystalline structures,long range ordered atomic arrangement,clear structure,regular pore structure and clear pore properties.In addition,its open pore structure is easy to modify,and through the post-modification method,the functional groups can be more accurately introduced into the defined position of the polymer framework to obtain specific functions.Crystalline porous polymers have great application value in many fields such as gas storage and separation,catalysis,photoelectric devices and energy storage,etc.Therefore,highly crystalline porous polymer materials have been widely concerned by scientists.According to the different dimensions of the structure,crystalline porous polymer materials can be divided into two-dimensional porous polymer materials and three-dimensional porous polymer materials.In this paper,two-dimensional porous polymer and three-dimensional porous polymer materials were prepared by different design and synthesis strategies,and the related catalytic applications were explored.1)In the second chapter,crystalline ultrathin 2D polymer films based on cyclobutane bonding was obtained by gas/water interface synthesis strategy,and verified the polymerization success and chemical composition using tip enhanced Raman spectroscopy.By combining TEM selected electron diffraction technique and molecular mechanics simulation,it is proved that the two-dimensional polymer film has a definite molecular structure.This kind of two-dimensional polymer with highly ordered crystalline structure and regular pore size will show great application potential as membrane material in gas and ion separation.2)In the third chapter,a new covalent organic framework porous polymer material(TPM-3D-COF-BPY)based on imine bonding was constructed with tetraphenylmethane as the core and bipyridine as the connecting functional unit.Combined with computer simulation and experimental PXRD analysis,the 7-fold interpenetrating structure was proved.Then,using the strong coordination between Pd metal ions and the bipyridine unit in the material,Pd@TPM-3DCOF-BPY was prepared.Pd@TPM-3D-COF-BPY showed excellent catalytic effect and stability in the Suzuki-Miyaura coupling reaction.This work further proves that the highly crystalline porous three-dimensional covalent organic frame material as a catalytic metal carrier has a very high application value in heterogeneous catalysis.