（2,3-Dimethylbutyl）（2,4,40-trimethylpentyl）phosphinic acid（INET-3） was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl（Pre-XAD-16） to prepare the solvent impregn...（2,3-Dimethylbutyl）（2,4,40-trimethylpentyl）phosphinic acid（INET-3） was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl（Pre-XAD-16） to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight（LMW） polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography（GPC）. The macroporous resins（XAD-16 ＆ Pre-XAD-16）, the corresponding solvent impregnated resins（SIRs-INET-3/XAD-16 ＆SIRs-INET-3/Pre-XAD-16） and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA. The effects of XAD-16 pretreatment and PVA coating technology on RE（III） adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics, selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time,less INET-3 loss and more Tm（III） adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm（III） adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE（III） on the SIRsINET-3/XAD-16 followed the pseudo-second-order kinetic model. The Tm（III） accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE（III） β（Er/Ho）, β（Tm/Er）, β（Yb/Tm） and β（Lu/Yb） values were 1.76, 2.59, 2.56 and 1.19,respectively. The adsorbed Lu（III） onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H2SO4.展开更多
The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The se...The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The separation operation of Th 4+ and Yb 3+ mixture was carried out by two successive extraction and stripping simultaneously. The concentration ratio of Th 4+ to Yb 3+ is 16 74 in the stripping solution. The recovery and purity of Th 4+ are 71 6% and 95 74% respectively.展开更多
Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for syn...Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10 times in Cu-catalyzed cross coupling.展开更多
The crystal structure of a (3-phenylureido)-a (2, 4-dichlorophenyl)methyl phenylphosphinic acid, C20H17Cl2N2O3P, Mr= 435. 25,which was obtained bydesulphurisation of cis-3, 4-dipheny1-5- (2, 4-dichlorophenyl ) -1, 3, ...The crystal structure of a (3-phenylureido)-a (2, 4-dichlorophenyl)methyl phenylphosphinic acid, C20H17Cl2N2O3P, Mr= 435. 25,which was obtained bydesulphurisation of cis-3, 4-dipheny1-5- (2, 4-dichlorophenyl ) -1, 3, 4-diazaphospholidin2-thione-4-oxide utilizing Ag+ -H2O system in a yield of 89%, is reported. It crystallizes in orthorhombic space group Pca21 with a= 11. 286(2), b= 20. 601 (4) f c=8. 695(2)A, V= 2021 (1) A3, Z= 4, D.= 1. 430 g/cm3, p=4. 21 cm-1, F(000) =896.The final R factor is 0. 040 and Rw is 0. 045 for 946 unique observed reflections[I>3a(I)]. The result of X-ray analysis indicates that the molecules in the crystal are linkedtogether by the O(3 ) ...H (2d) - N (2d ) intermolecular hydrogen-bondings.展开更多
A new extractant, [N,N-di（2-ethylhexyl）aminolmethylphenylphosphinic acid （DEAPP）, was synthesized to de- velop the mutual separation techniques of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ）. The extraction selectivity for I...A new extractant, [N,N-di（2-ethylhexyl）aminolmethylphenylphosphinic acid （DEAPP）, was synthesized to de- velop the mutual separation techniques of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ）. The extraction selectivity for In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP was higher than that of the commercial phosphorus acid extractants such as D2EHPA and PC-88A. The extraction selectivity for metal ions in 1 mob L 1 aqueous ammonium nitrate solution with DEAPP was in the following order： In（Ⅲ） 〉 Ga（Ⅲ） 〉 Zn（Ⅱ）. These selective extraction behaviors indicate that the amino moiety of DEAPP plays an important role in the mutual separation of ln（Ⅲ）, Ga（Ⅲ） and Zn（ll）. The extraction equilibria of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP （ = HR） were expressed by the following reactions： In3＋ ＋ 2（HR）2 InR3（HR） ＋ 3H＋, Ga3＋ ＋ 1.5（HR）2 ＋ N- = GaR2（HR）（NO3） ＋ 2H＋, and Zn2＋ 4- 2（HR）2 ZnR2 （HR） 2 determined 4- 2H＋. The extraction equilibrium constants of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP were to be Kex, M = 1.7 × 104 [dm3.mol 1], 4.17 [（dm3.mol-1）s], and 1.55 × 10 2 [-], respectively.展开更多
Strongly acidic cation exchange resin(1x1,H form)has been successfully used as a catalyst in synthesis of diphenyl N-benzyloxycarbonyl-1-aminobenzylphosphonate, N-benzyloxycarbonyl-1-aminobenzylphenylphosphinic acid a...Strongly acidic cation exchange resin(1x1,H form)has been successfully used as a catalyst in synthesis of diphenyl N-benzyloxycarbonyl-1-aminobenzylphosphonate, N-benzyloxycarbonyl-1-aminobenzylphenylphosphinic acid and N-p-tolylsulfonyl-1-aminobenzyl phenylphosphinic acid in high yields.展开更多
A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of...A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.展开更多
基金Project supported by the National Natural Science Foundation of China(21301104)the State Key Laboratory of Chemical Engineering(SKLCh E-14A04)the Fundamental Research Funds for the Central Universities(FRFTP-16-019A3)
文摘（2,3-Dimethylbutyl）（2,4,40-trimethylpentyl）phosphinic acid（INET-3） was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl（Pre-XAD-16） to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight（LMW） polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography（GPC）. The macroporous resins（XAD-16 ＆ Pre-XAD-16）, the corresponding solvent impregnated resins（SIRs-INET-3/XAD-16 ＆SIRs-INET-3/Pre-XAD-16） and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA. The effects of XAD-16 pretreatment and PVA coating technology on RE（III） adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics, selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time,less INET-3 loss and more Tm（III） adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm（III） adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE（III） on the SIRsINET-3/XAD-16 followed the pseudo-second-order kinetic model. The Tm（III） accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE（III） β（Er/Ho）, β（Tm/Er）, β（Yb/Tm） and β（Lu/Yb） values were 1.76, 2.59, 2.56 and 1.19,respectively. The adsorbed Lu（III） onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H2SO4.
文摘The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The separation operation of Th 4+ and Yb 3+ mixture was carried out by two successive extraction and stripping simultaneously. The concentration ratio of Th 4+ to Yb 3+ is 16 74 in the stripping solution. The recovery and purity of Th 4+ are 71 6% and 95 74% respectively.
文摘Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10 times in Cu-catalyzed cross coupling.
文摘The crystal structure of a (3-phenylureido)-a (2, 4-dichlorophenyl)methyl phenylphosphinic acid, C20H17Cl2N2O3P, Mr= 435. 25,which was obtained bydesulphurisation of cis-3, 4-dipheny1-5- (2, 4-dichlorophenyl ) -1, 3, 4-diazaphospholidin2-thione-4-oxide utilizing Ag+ -H2O system in a yield of 89%, is reported. It crystallizes in orthorhombic space group Pca21 with a= 11. 286(2), b= 20. 601 (4) f c=8. 695(2)A, V= 2021 (1) A3, Z= 4, D.= 1. 430 g/cm3, p=4. 21 cm-1, F(000) =896.The final R factor is 0. 040 and Rw is 0. 045 for 946 unique observed reflections[I>3a(I)]. The result of X-ray analysis indicates that the molecules in the crystal are linkedtogether by the O(3 ) ...H (2d) - N (2d ) intermolecular hydrogen-bondings.
基金supported by The Environment Research and Technology Development Fund (3K133005)
文摘A new extractant, [N,N-di（2-ethylhexyl）aminolmethylphenylphosphinic acid （DEAPP）, was synthesized to de- velop the mutual separation techniques of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ）. The extraction selectivity for In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP was higher than that of the commercial phosphorus acid extractants such as D2EHPA and PC-88A. The extraction selectivity for metal ions in 1 mob L 1 aqueous ammonium nitrate solution with DEAPP was in the following order： In（Ⅲ） 〉 Ga（Ⅲ） 〉 Zn（Ⅱ）. These selective extraction behaviors indicate that the amino moiety of DEAPP plays an important role in the mutual separation of ln（Ⅲ）, Ga（Ⅲ） and Zn（ll）. The extraction equilibria of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP （ = HR） were expressed by the following reactions： In3＋ ＋ 2（HR）2 InR3（HR） ＋ 3H＋, Ga3＋ ＋ 1.5（HR）2 ＋ N- = GaR2（HR）（NO3） ＋ 2H＋, and Zn2＋ 4- 2（HR）2 ZnR2 （HR） 2 determined 4- 2H＋. The extraction equilibrium constants of In（Ⅲ）, Ga（Ⅲ） and Zn（Ⅱ） with DEAPP were to be Kex, M = 1.7 × 104 [dm3.mol 1], 4.17 [（dm3.mol-1）s], and 1.55 × 10 2 [-], respectively.
文摘Strongly acidic cation exchange resin(1x1,H form)has been successfully used as a catalyst in synthesis of diphenyl N-benzyloxycarbonyl-1-aminobenzylphosphonate, N-benzyloxycarbonyl-1-aminobenzylphenylphosphinic acid and N-p-tolylsulfonyl-1-aminobenzyl phenylphosphinic acid in high yields.
基金Project Supported by National Science Foundation of China.
文摘A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.
