Synthesis And Application Of Triphenylamine Functionalized POSS-Based Hybrid Porous Polymers

Organic porous polymers have excellent potential applications in gas storage and separation,heterogeneous catalysis,chemosensors,environmental protection,etc.Generally,organic porous polymers are constructed by using the different rigid monomers as the building blocks and prepared by chemical bonding.Because of the diversity and high efficiency of their synthesis methods,it is a current research focus.The use of monomers with diverse topology structures favors to obtain porous polymers with novel structure and property.Polyhedral oligomeric silsesquioxanes(POSS),with rigid 3D nanometer-sized structures,multi-reaction sites and high thermal stability,are particularly suitable building blocks to construct inorganic-organic hybrid porous polymers.Triphenylamine(TPA)is a very important nitrogenous heterocyclic compound.Because of its high fluorescence,high light-emitting efficiencies and photoconductivity,has been applied extensively in the fields of optoelectronic devices.In addition,triphenylamineshows a prominent thermal and chemical stability.The above characteristics make triphenylamine and its derivatives suitable for preparing fluorescent organic porous polymers.Based on the above analysis,the rigid structure and multi-functionality of polyhedral oligomeric silsesquioxanes(POSS)and triphenylamine can enable them to prepare new organic-inorganic fluorescent hybrid porous polymers through covalent bonding.The topic of this paper is"Synthesis and Application of Triphenylamine Functionalized POSS-Based Hybrid Porous Polymers".The main contents are as followings1.A novel triphenylamine-functionalized silsesquioxane monomer(OTS)is synthesized by Heck reaction involving octavinylsilsesquioxane(OVS)and(4-Bromophenyl)diphenylamine as the substrates.The structure of OTS was characterized by FT-IR,1H NMR,solid NMR and elemental analysis,indicating the successful preparation of target product.TGA result shows that OTS has a good thermal stability.XRD results show that OTS has a certain crystallinity.2.OTS is used as single precursor to prepare a triphenylamine functionalized POSS-based fluorescent hybrid porous polymer(HLPP-OTS-1)via Scholl coupling in presence of AICl3.HLPP-OTS-1 exhibits a high surface area of 814 m2 g-1 and hierarchical microporous/lesoporous structure,high fluorescence intensity and good thermal stability.HLPP-OTS-1 shows CO2 adsorption capacity of 8.04 wt%(1.83 mmol g-,)at 273.0 K/101 kPa as well as high 12 uptake of 406 wt%in vapor and 468 mg g-1 in solution.It shows high sensitivity for Fe3+and Ru3+,especially for Fe3+with KSV=40k M-1.HLPP-OTS-1 also exhibits excellent luminescence property and acts as a sensitive chemo sensor to detect nitro-aromatics with high sensitivity towards 5-Nitrosalicylaldehyde(Ksv=36560 M-1).3.Triphenylamine functionalized POSS-based fluorescent hybrid porous polymer(HLPP-OTS-2)have been synthesized by the Friedel-Crafts reaction of octavinylsilsesquioxane(OVS)with OTS.The structure of HLPP-OTS-2 was characterized by FT-IR and elemental analysis.The specific surface area and pore properties of HLPP-OTS-2 were determined by N2 adsorption-desorption experiment.HLPP-OTS-2 exhibits a high surface area of 730 m2 g-1;TGA result shows that HLPP-OTS-2 has a good thermal stability.The order and morphology of the porous polymer were characterized,and the results showed that the polymer had an amorphous structure.The polymer exhibits excellent luminescence property and acts as a sensitive chemo sensor to detect nitro-aromatics with high sensitivity towards p-Nitrophenol(Ksv=81018 M-1).