Synthesis Of Calixarene Phosphorate Derivatives Of And Their Extraction Properties Of U(Ⅵ)

The calix[4],[6]arene are synthesized by using p-tert-butylphenol andformaldehyde as the starting material, then phosphorate derivatives ofcalix[4],[6]arene are synthesized through substitution by using calix[4],[6]arene anddiethyl chlorophosphate as the starting material. Infrared spectra,1HNMR and13CNMR were used to charaeterize the products; The complexing property ofcalix[4],[6]arene and its phosphorate derivatives to metal ions were studied,meanwhile, with chloroform as dissolvent, the extraction capacity of products to lowconcentration uranium were studied. The major research contents are listed as thefollowing:(1) Using p-tert-butylphenol, formaldehyde and ethyl acetate as raw material andsodium hydroxide (potassium hydroxide) as catalyst, the calix[4],[6]arene aresynthesized by a series prucedures including heating, reflux and recrystallization.After that, using calix[4],[6]arene and diethyl chlorophosphate as the starting material,dichloromethane and carbon tetrachloride as solvent, tetrabutylammonium iodide ascatalyst, the phosphorate derivatives of calix[4],[6]arene were obtained respectivelythrough substitution by a series steps including heating, reflux, recrystallization.(2) Infrared spectra,1HNMR,13CNMR were used to charaeterize thecalix[4],[6]arene and its phosphorate derivatives. Infrared spectra indicate that themain functional groups were successfully introduced to the products. Compared withthe infrared spectra of the calix[4],[6]arene, the absorption peaks of phosphoratederivatives of calixarene have obviously changed obout the functional group P-O andP=O,1HNMR and13CNMR show that the conformations have changed. Thesynthetics can be basically judged as the end products from the above spectra.（3） The complexing property of calix[4],[6]arene and its phosphoratederivatives to metal ions were studied by UV-vis. Analysis showed that the complexing property of phosphorate calixarenes to metal ions were better thancalixarenes to metal ions, UV spectrums of phosphorate derivatives of calix [6]areneto uranium had obviously removed. The complex ability of the products with UO22+is2:3by Job’s method.（4）The effect of pH value, extraction concentration, extraction time, extractiontemperature and interference ion on that calix[4],[6]arene and its phosphoratederivatives extracted low concentration uranium was studied respectively, theetraction property of calix[4],[6]arene and its phosphorate derivatives to uranium wasdiscussed. The results showed that the reaction of calix[4],[6]arene and itsphosphorate derivatives on uranium is exothermic reaction; The best pH ofcalix[4],[6]arene and calix[6]arene’s phosphorate derivatives to uranium were5,while the best pH of calix[4]arene’s phosphorate derivatives to uranium was4; Theequilibrium time of calix[4],[6]arene and its phosphorate derivatives on uranium wasabout60min; The extraction rate of calix[4],[6]arene and its phosphorate derivativeson uranium have more influence by metal ions (Na+，Mn2+，Cu2+，Ni2+，Mg2+and Pb2+)than anion（CO32-，SO42-，NO3-and C2O42-）. Under the same condition, extractioneffect of uranium by calix[6]arene is higher than calix[4]arene, meanwhile, theextraction rations of uranium by the calixarene phosphinoxide derivatives were higherthan the extraction rations of uranium by calixarenes. Compared with calixarenes, thecalixarene phosphinoxide derivatives’ extraction rations of uranium were improved36%~39%.(5) The ion coordination on calixarenes and metal ions was firstly confirmed byIR、1HNMR and13CNMR, which were mainly formed by phenolic hydroxyl bindinginteractions and hydrophobic benzene ring cavity, While the ion coordination oncalixarene’s phosphinoxide derivatives and metal ions were mainly by the group ofphosphorus oxygen, because the phosphorus oxygen has stronger affinity thanphenolic hydroxyl, which can improve the stability of calixarene’s phosphinoxidederivatives with uranium and other metal ions.