The random copolymer poly （1, 3-pentadiene-co-styrene） formed through cationic copolymerization using the ~ethylamine hydrochloride and hydrous aluminium chloride （Et3NHCl-AlCl3） room temperature ionic liquid as i...The random copolymer poly （1, 3-pentadiene-co-styrene） formed through cationic copolymerization using the ~ethylamine hydrochloride and hydrous aluminium chloride （Et3NHCl-AlCl3） room temperature ionic liquid as initiating agent in toluene was analyzed using IR spectra in conjunction with gel permeation chromatography （GPC）. The room temperature ionic liquid was found to have high initiatic activity for copolymerization.展开更多
Three multi-fluorous-carried anions-based ionic copolymers(ICs)including(fluorosulfonyl)imide(FSI-),(trifluorometha-nesulfonyl)imide(TFSI-)and hexafluorophosphate anions(PF6-)(IC[FSI-]),poly[1,1'-(butane-1,4-diyl)...Three multi-fluorous-carried anions-based ionic copolymers(ICs)including(fluorosulfonyl)imide(FSI-),(trifluorometha-nesulfonyl)imide(TFSI-)and hexafluorophosphate anions(PF6-)(IC[FSI-]),poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bis(fluorosulfonyl)amide](IC[TFSI-]),poly{1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bis[(trifluoromethyl)sulfonyl]-amide}(IC[PF6-]),poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bishexafluorophosphate]were synthesized with a simple ionic exchange method by using amphiphilic poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bisbromide](IC[Br-])as the intermediate ionic polymer.The chemical srutrcures of the target ICs were characterized by nuclear magnetic resonance(NMR)spectroscopy and Fourier-transform infrared spectroscopy(FTIR).It is shown that the target ICs could be spontaneously adsorbed on copper surface in N,N-dimethflormamide(DMF),and the tight adsorption films were formed on metal surface.The contacting angles suggest that the formed adsorption layers of target ICs on copper surface were characterized with hydrophobic nature.Furthermore,the target ICs-copper chemistry bonding was confirmed by various means.The electrochemistry analysis showed that the target ICs adsorption layers could prevent from copper corrosion in H2SO4solution efficiently,and the maximal anticorrosion efficiency was over 95%at 0.100 g/L.In particular,the target ICs showed 85%or above anticorrosion efficiency for copper at a low concentration of 0.025 g/L,which was greater than the intermediate polymer IC[Br-].In addition,an insight of mixed chemisorption and physisorption of the target ICs on metal surface was analyzed and discussed.展开更多
Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride （AmimCl） with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose ...Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride （AmimCl） with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose graft copolymers were characterized by FTIR, ^1 H-NMR and XRD spectroscopy. The results show that AmimCl dissolved cellulose directly by destroying intermolecular and intramolecular hydrogen bonds in cellulose and the crystalline form of cellulose was transformed from cellulose Ⅰ to cellulose Ⅱ after regeneration from AmimCl. The best synthetic condition of the cellulose-graft-P （2-hydroxyethyl methacrylate） was that cellulose 0.5 g, 2-hydroxyethyl methacrylate 3.00 g and initiator ammonium persulfate 0.05 g reacted for 180 min at 60℃; the rate of grafting reached 77.3%.展开更多
The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones(PK)was studied in the N-valeronitrile-N'-methylimidazolium hexafluorophosphate([C4CNmim]+PF-6) medium. The synthesized P...The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones(PK)was studied in the N-valeronitrile-N'-methylimidazolium hexafluorophosphate([C4CNmim]+PF-6) medium. The synthesized PK was characterized by Fourier transform infrared(FTIR), elemental analysis, 13C-nuclear magnetic resonance(13C-NMR), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and gel permeation chromatography(GPC). The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%(0.1 g ionic liquid / 1 g active carbon carrier) and the theoretical content of Pd2+ is 5wt%(0.05 g Pd2+/ 1 g active carbon carrier), the highest catalytic activity 2 963.64 gSTCO/(gPd·h) is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw /Mn=1.389.展开更多
Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a c...Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a consequence the introduction of MAn onto polymer chain retards crystallization of the ether pendants considerably, and improves the ion conductivity to a larger degree compared with other polar groups once investigated (σ_(max),25℃=8.5×10^(-5) S/cm). The structure-ion conduction relation in the polymer-salt matrix is also analyzed macroscopically through the correspondence between composition-dependences of polymerization conversion and isothermal ion conductivity, and microscopically through the measurements of cross polarized light and electron transmission.展开更多
To prepare polymer supported ionic liquids(PSILs)as effective catalysts for esterification,the free radical suspension copolymerization of vinylbenzyl chloride(VBC,monomer),styrene(St,monomer)and divinylbenzene(DVB,cr...To prepare polymer supported ionic liquids(PSILs)as effective catalysts for esterification,the free radical suspension copolymerization of vinylbenzyl chloride(VBC,monomer),styrene(St,monomer)and divinylbenzene(DVB,crosslinker)with the addition of n-heptane(porogen)was carried out for the fabrication of the porous polymer(PVD)microsphere as support,followed by the immobilization of sulfonic acid-functionalized ionic liquids by the successive treatment of benzimidazole(BIm),1,3-propane sultone and sulfuric acid(H2SO4)or trifluoromethanesulfonic acid(CF3SO3H).The effects of the compositions of DVB and n-heptane on the internal structure of the polymer supports were investigated,and it was found that the support with 40 wt%DVB and 60 wt%n-heptane(with relative to the monomer)could endow the final PSILs with the relatively optimal catalytic performance.The preliminary experiment in the batch reactor indicated that PSILs herein exhibited higher catalytic activities than commercial Amberlyst 46 resin for the esterification of propanoic acid(PROAc)with n-propanol(PROOH).Consequently,the optimal PSILs catalyst,PVD-[Bim-SO3H]HSO4,was selected for further study in the batch reactive distillation column because of low cost and its ease of preparation.The yield of propyl ropionate(PROPRO)could reach up to 97.78%at the optimized conditions of PROOH/PROAc molar ratio(2:1)and catalyst dosage(2.0 wt%).The investigation of the reaction kinetic manifested that the calculated results of second order pseudo-homogeneous kinetic model were in good agreement with experimental values.The pre-exponential factor and activation energy were 4.12×107 L·mol-1·min-1 and 60.57 k J·mol-1,respectively.It is worth noting that the PSILs catalyst could be simply recovered and reused with relatively satisfactory decrease in the catalytic activity,which made it an environmental friendly and promising catalyst in the industrial application.展开更多
文摘The random copolymer poly （1, 3-pentadiene-co-styrene） formed through cationic copolymerization using the ~ethylamine hydrochloride and hydrous aluminium chloride （Et3NHCl-AlCl3） room temperature ionic liquid as initiating agent in toluene was analyzed using IR spectra in conjunction with gel permeation chromatography （GPC）. The room temperature ionic liquid was found to have high initiatic activity for copolymerization.
基金This work was supported by the National Natural Science Foundation of China(Nos.21376282,21676035,21878029)the Project of the Chongqing Science and Technology Commission,China(No.2022NSCQ-MSX1298)+4 种基金the Graduate Student Research Innovation Project,Chongqing University,China(No.CYB18046)the Natural Science Foundation of Chongqing,China(No.cstc2019jcyj-msxmX0663)the Science and Technology Research Program of Chongqing Municipal Education Commission,China(Nos.KJQN201904102,KJQN202004104)the Beibei Scientific and Technological Program Project of China(No.2019-2)the Scientific Research Program of Chongqing Youth Vocational&Technical College,China(No.CQY2019KYY04).
文摘Three multi-fluorous-carried anions-based ionic copolymers(ICs)including(fluorosulfonyl)imide(FSI-),(trifluorometha-nesulfonyl)imide(TFSI-)and hexafluorophosphate anions(PF6-)(IC[FSI-]),poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bis(fluorosulfonyl)amide](IC[TFSI-]),poly{1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bis[(trifluoromethyl)sulfonyl]-amide}(IC[PF6-]),poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bishexafluorophosphate]were synthesized with a simple ionic exchange method by using amphiphilic poly[1,1'-(butane-1,4-diyl)bis(3-pentyl-1H-imidazol-3-ium)bisbromide](IC[Br-])as the intermediate ionic polymer.The chemical srutrcures of the target ICs were characterized by nuclear magnetic resonance(NMR)spectroscopy and Fourier-transform infrared spectroscopy(FTIR).It is shown that the target ICs could be spontaneously adsorbed on copper surface in N,N-dimethflormamide(DMF),and the tight adsorption films were formed on metal surface.The contacting angles suggest that the formed adsorption layers of target ICs on copper surface were characterized with hydrophobic nature.Furthermore,the target ICs-copper chemistry bonding was confirmed by various means.The electrochemistry analysis showed that the target ICs adsorption layers could prevent from copper corrosion in H2SO4solution efficiently,and the maximal anticorrosion efficiency was over 95%at 0.100 g/L.In particular,the target ICs showed 85%or above anticorrosion efficiency for copper at a low concentration of 0.025 g/L,which was greater than the intermediate polymer IC[Br-].In addition,an insight of mixed chemisorption and physisorption of the target ICs on metal surface was analyzed and discussed.
基金supported by the 11th Five-Year Plan of the National Scientific and Technological Support Projects of China (Grant No. 2006BAD18B10)the Major Project of Chinese National Programs for Fundamental Research and Development (973 Program) (Grant No. 2010CB732204)
文摘Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride （AmimCl） with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose graft copolymers were characterized by FTIR, ^1 H-NMR and XRD spectroscopy. The results show that AmimCl dissolved cellulose directly by destroying intermolecular and intramolecular hydrogen bonds in cellulose and the crystalline form of cellulose was transformed from cellulose Ⅰ to cellulose Ⅱ after regeneration from AmimCl. The best synthetic condition of the cellulose-graft-P （2-hydroxyethyl methacrylate） was that cellulose 0.5 g, 2-hydroxyethyl methacrylate 3.00 g and initiator ammonium persulfate 0.05 g reacted for 180 min at 60℃; the rate of grafting reached 77.3%.
基金Supported by the Tianjin Natural Science Foundation(No.07JCYBJC00600)
文摘The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones(PK)was studied in the N-valeronitrile-N'-methylimidazolium hexafluorophosphate([C4CNmim]+PF-6) medium. The synthesized PK was characterized by Fourier transform infrared(FTIR), elemental analysis, 13C-nuclear magnetic resonance(13C-NMR), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and gel permeation chromatography(GPC). The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%(0.1 g ionic liquid / 1 g active carbon carrier) and the theoretical content of Pd2+ is 5wt%(0.05 g Pd2+/ 1 g active carbon carrier), the highest catalytic activity 2 963.64 gSTCO/(gPd·h) is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw /Mn=1.389.
文摘Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a consequence the introduction of MAn onto polymer chain retards crystallization of the ether pendants considerably, and improves the ion conductivity to a larger degree compared with other polar groups once investigated (σ_(max),25℃=8.5×10^(-5) S/cm). The structure-ion conduction relation in the polymer-salt matrix is also analyzed macroscopically through the correspondence between composition-dependences of polymerization conversion and isothermal ion conductivity, and microscopically through the measurements of cross polarized light and electron transmission.
基金The National Natural Science Foundation of China(21576053,91534106)the Natural Science Foundation of Fujian Province(2016J01689).
文摘To prepare polymer supported ionic liquids(PSILs)as effective catalysts for esterification,the free radical suspension copolymerization of vinylbenzyl chloride(VBC,monomer),styrene(St,monomer)and divinylbenzene(DVB,crosslinker)with the addition of n-heptane(porogen)was carried out for the fabrication of the porous polymer(PVD)microsphere as support,followed by the immobilization of sulfonic acid-functionalized ionic liquids by the successive treatment of benzimidazole(BIm),1,3-propane sultone and sulfuric acid(H2SO4)or trifluoromethanesulfonic acid(CF3SO3H).The effects of the compositions of DVB and n-heptane on the internal structure of the polymer supports were investigated,and it was found that the support with 40 wt%DVB and 60 wt%n-heptane(with relative to the monomer)could endow the final PSILs with the relatively optimal catalytic performance.The preliminary experiment in the batch reactor indicated that PSILs herein exhibited higher catalytic activities than commercial Amberlyst 46 resin for the esterification of propanoic acid(PROAc)with n-propanol(PROOH).Consequently,the optimal PSILs catalyst,PVD-[Bim-SO3H]HSO4,was selected for further study in the batch reactive distillation column because of low cost and its ease of preparation.The yield of propyl ropionate(PROPRO)could reach up to 97.78%at the optimized conditions of PROOH/PROAc molar ratio(2:1)and catalyst dosage(2.0 wt%).The investigation of the reaction kinetic manifested that the calculated results of second order pseudo-homogeneous kinetic model were in good agreement with experimental values.The pre-exponential factor and activation energy were 4.12×107 L·mol-1·min-1 and 60.57 k J·mol-1,respectively.It is worth noting that the PSILs catalyst could be simply recovered and reused with relatively satisfactory decrease in the catalytic activity,which made it an environmental friendly and promising catalyst in the industrial application.
