Preparation And Applications Of Triphenylphosphine And Triphenylphosphine Oxide Functionalized Hybrid Porous Polymers Based On POSS

Porous materials have attracted much attention during the last few decades because they show great potential applications in the fields of gas storage and separation,heterogeneous catalysis,chemosensors,environment protection,et al.Because of the excellent properties and diversity developments of the synthesis methods,porous polymes based on POSS have been become one of the most attraction fields of porous materials in recent years.The topic of this dissertation was"preparation and applications of triphenylphosphine and triphenylphosphine oxide functionalized hybrid porous polymers based on POSS",which contained the following aspects:1.Triphenylphosphine(TPP)and triphenylphosphine oxide(TPPO)were chosen to react with cubic octavinylsilsesquioxane(OVS)to prepare two novel parallel series of phosphorus-containing hybrid porous polymers(denoted as HP-TPPs:HP-TPP-1?HP-TPP-4 and HP-TPPOs:HP-TPPO-1?HP-TPPO-4)via the Friedel-Crafts reaction,respectively.The results of FT-IR,NMR and element analysis showed HP-TPPs and HP-TPPOs were prepared successfully.N2 adsoption and desorption results showed that HP-TPPs and HP-TPPOs exhibited high porosity,with Brunauer-Emmett-Teller specific surface areas(SBET)of 581-1105 m2 g-1,and total pore volumes of 0.32-0.82 cm3 g-1,as well as bimodal pore-size distributions.And the porosities of the HP-TPPs and HP-TPPOs could be tuned by modulating the molar ratio of TPP or TPPO to OVS.The results of TGA,PXRD,FE-SEM and HR-TEM showed that HP-TPPs and HP-TPPOs exhibited high thermal stability and belonged to amorphous materials.For CO2 storage application,the CO2 capture capacities for HP-TPP-4 and HP-TPPO-4 were 3.97 wt%(0.90 mmol g-1)and 4.63 wt%(1.05 mmol g-1)at 273.0 K/101 kPa,respectively.2.HP-TPP-4 and HP-TPPO-4 possessed the same molar content of phosphorus and the highest SBET in HP-TPPs and HP-TPPOs;therefore,they were selected to compare their adsorption efficiency for three different kinds of dyes,rhodamine B(RB),methylene blue(MB),and methyl orange(MO).The adsorption capacities(Qe)for RB,MB and MO onto HP-TPP-4 were 675,154 and 26 mg g-1,respectively;for HP-TPPO-4 were 829,145 ? 65 mg g-1,respectively.Three well-known linear isotherm equations,Langmuir isotherm,Freundlich isotherm and Dubinin-Radushkevich isotherm,were applied to evaluate the data of RB adsorption.The results indicated that the adsorption behaviors of RB onto HP-TPP-4 could better fit to Langmuir model;however,the adsorption behaviors of RB onto HP-TPPO-4 followed Dubinin-Radushkevich isotherm.We further researched the adsorption rates of RB onto HP-TPP-4 and HP-TPPO-4 using pseudo-first-order,pseudo-second-order and intraparticle diffusion models.The results showed that both of them followed pseudo-second-order kinetic curve.And HP-TPP-4 and HP-TPPO-4 regenerated by soxhlet extraction with ethanol and colud use again.So,HP-TPP-4 and HP-TPPO-4 were very promising to be used in the field of dyes adsorption and wastewater treatment.3.HP-TPP-1 and HP-TPPO-1 possessed the highest molar content of phosphorus and moderate SBET in HP-TPPs and HP-TPPOs;therefore,they were selected as supports for Pd particles to make heterogeneous catalysts(denote as HP-TPP-1-Pd and HP-TPPO-1-Pd)for Suzuki-Miyaura cross-coupling reaction and Heck cross-coupling reaction.In Suzuki-Miyaura cross-coupling reaction,all the yields of target products could be>99%within 3 hours.In Heck reaction,the yields of target products for HP-TPP-1-Pd and HP-TPPO-1-Pd were 95%and 99%,respectively.So,HP-TPP-1 and HP-TPPO-1 were very promising to be use in the field of heterogeneous catalysis.