| Crystalline Porous Materials（CPMs）are a class of materials including metal organic frameworks（MOFs）,covalent organic frameworks（COFs）and hydrogen organic frameworks（HOFs）.CPMs show the characteristics of high specific surface areas,tunable structure,thermal stability and customized functions which have received considerable investigations from researchers over the past few decades.CPMs have a wide range of applications in catalysis,separation,energy storage,and other fields,while relatively few studies have been conducted in the fields of fluorescent probes and solid fluorescent materials.Therefore,we sought to develop new types of stimuli-responsive COF materials with aggregation induced emission（AIE）properties for detection of target analytes and optoelectronics applications in this work.However,CPMs process some intrinsic deficiencies,most of which are in powder form,unable to achieve self-standing,and lack of processability,which limit their practical applications in some fields.Introducing functional polymers to construct CPM-organic polymer hybrid membrane materials can overcome the above problems.CPM-organic polymer hybrid membrane materials inherit the advantages of traditional organic polymer materials（excellent mechanical properties,processability）and CPMs（regular structure,adjustable pore size）.In this paper,we designed and synthesized a new type of hyper-crosslinked metal-organic framework-hyperbranched polymer membrane and prepared a uniform and multifunctional membrane material with tunable mechanical strength.These excellent properties endow it with important application potential in the development of new multifunctional membranes.Based on the hot-topic of multi-functional CPMs and CPM-polymer hybrid materials,the main contents are as bellow:（1）Preparation of TFBE-TD COF and study of luminescence properties.In this paper,tetra-（4-aldehyde-（1,1-biphenyl））ethylene（TFBE）with aggregation-induced fluorescence properties and terephthalic acid hydrazide（TD）were prepared by grinding method to prepare aggregation-induced luminescence with excellent luminescence properties.Based on covalent organic framework material（TFBE-TD COF）,the TFBE-TD COF was characterized by infrared spectroscopy（FT-IR）,powder X-ray diffraction（PXRD）and solid-state NMR.the TFBE-TD COF belongs to the Kagome lattice.Thermogravimetric analysis showed that the temperature of TFBE-TD COF at 5%weight loss was 316℃,indicating that the material has good thermal stability.According to the nitrogen adsorption-desorption curve,the TFBE-TD COF has a mesoporous structure with a specific surface area of 12.51 m2/g.The fluorescence spectra of TFBE-TD COFs in water/tetrahydrofuran solutions with different water contents indicate that the weak aggregation-induced fluorescence（AIE）properties of COF materials are caused by the fact that the structural units of the benzene ring are locked in a two-dimensional framework.Fluorescence spectroscopy tests show that the TFBE-TD COF exhibits a rapid fluorescence color change in gaseous TFA/TEA,and the sensing process has good reversibility within four cycles.Scanning electron microscopy（SEM）,FT-IR and X-ray photoelectron spectroscopy（XPS）tests confirmed that the TFA response mechanism of TFBE-TD COF is the bi-protonation effect of imine bond and hydrazide amino group.The application of the luminescence properties of white LEDs prepared from TFBE-TD COF was studied by fluorescence spectroscopy.The luminescence color was cool white light with CIE color coordinates of（0.29,0.31）.（2）Preparation of hyper-crosslinked porous framework hyperbranched polymer film（HHMOP）and study of its multifunctional properties.A series of HHMOPs were prepared by polycondensation reaction using Ui O-66-NH2,amino-terminated hyperbranched polymer（HPMA）.Their chemical compositions,crystal structures and microscopic morphologies were analyzed by FT-IR,PXRD,SEM,and EDX characterization.The FT-IR results confirmed the formation of imine bonds in the cross-linked network,and PXRD confirmed that the structure of Ui O-66-NH2 was completely preserved in the HHMOP films.SEM and EDX analysis results show that the HHMOP film is a composite material with hyperbranched polymer material as the main body and Ui O-66-NH2 as the internal connection structure of the cross-linked network.In addition,the tensile test of the films with different histamines showed that the films with HPMA,Ui O-66-NH2,DETA,and terephthalaldehyde was added at the same time,which exhibited the most excellent mechanical properties.The mechanical properties of the HHMOP film and the intermolecular hydrogen bonding effect that affects the mechanical strength of the material were tested by different humidity conditions.With the increase of humidity,the tensile strength of the film gradually decreased,and the elongation at break first increased and then decreased with the increase of humidity,which indicated that the HHMOP film had tunable mechanical properties.The effects of temperature and humidity on the self-healing properties of the films were tested under a microscope.Under the conditions of 30%relative humidity and 80℃,the scratches of HHMOP-4 film can be completely repaired in 4 minutes;under the condition of 55%humidity at room temperature,the scratches can be completely repaired after20 minutes.The film was divided into two sections and repaired under the condition of 60%.After 24 h,the mechanical properties of the film before and after the repair were tested,and the repair efficiency of the film could reach 91.35%.The micro-and macroscopic self-healing test results of HHMOP films show that HHMOP films have excellent self-healing properties.We tested the radius of inhibition zone of HHMOP film against Bacillus and Staphylococcus aureus,which showed that HHMOP film had good antibacterial activity performance against both Bacillus and Staphylococcus aureus. |
