Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performa...Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.展开更多
A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applicatio...A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applications.In this work,a PEG was incorporated into block copolymer as a plasticizer by solvent casting.PLLA-PEG-PLLA/PEG blends with different blend ratios were prepared,and the plasticizing effect and miscibility of PEG in block copolymer were intensively investigated compared to PLLA/PEG blends.The results indicated that the PEG was an effective plasticizer for the block copolymer.The blending of PEG decreased glass-transition temperature and accelerated the crystallization of both the PLLA and PLLA-PEG-PLLA matrices.The PEG was completely miscible when blended with block copolymer and it improved thermal stability of the block copolymer matrix but not of the PLLA matrix.Film extensibility of PLLA-PEG-PLLA/PEG blends steadily increased as the PEG ratio increased.These non-toxic and highly flexible PLLA-PEG-PLLA/PEG bioplastics are promising candidates for several applications such as biomedical devices,tissue scaffolds and packaging materials.展开更多
Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylen...Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.展开更多
A new blend of poly(2-hydroxyethyl methacrylate) (PHEMA) with poly (ethylene glycol) (PEG) was prepared. The results from solid-state NMR indicate that the PHEMA/PEG(88:12, w/w) blend is miscible on a molecular level.
Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal proper...Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.展开更多
Hydrogels composed of poly(vinyl alcohol)(PVA) and poly(ethylene glycol)(PEG) were synthesized using glutaraldehyde as crosslinker and investigated for controlled delivery of the common anti-inflammatory drug, ibuprof...Hydrogels composed of poly(vinyl alcohol)(PVA) and poly(ethylene glycol)(PEG) were synthesized using glutaraldehyde as crosslinker and investigated for controlled delivery of the common anti-inflammatory drug, ibuprofen(IBF). To regulate the drug delivery, solid inclusion complexes(ICs) of IBF in β–cyclodextrin(β–CD) were prepared and added to the hydrogels. The ICs were prepared by the microwave irradiation method, which is more environmentally benign. The formation of IC was confirmed by various analytical techniques and the synthesized hydrogels were also characterized. Controlled release of drug was achieved from the hydrogels containing the ICs in comparison to the rapid release from hydrogels containing free IBF.The preliminary kinetic analysis emphasized the crucial role of β–CD in the drug release process that influences the polymer relaxation, thereby leading to prolonged release. The cytotoxicity assay validated the hydrogels as non-toxic in nature and hence can be utilized for controlled delivery of IBF.展开更多
In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were...In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were then modified by SO2 gas plasma treatment. ATR-FITR and XPS were used to analyze the chemical change which had occurred on the film's surface. When the content of sulfur on the surface of blend films surpasses 1.59%, the antithrombogenicity of plasma treated films increases remarkably due to surface sulfonation. This result implies that SF with blend of PEGM after SO2 plasma treatment have potential use for making blood-contacting biomaterials.展开更多
Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation (UHDP) technique have been proposed focusing on the effect of copper loading.The texture,structure a...Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation (UHDP) technique have been proposed focusing on the effect of copper loading.The texture,structure and composition are systematically characterized by ICP,FTIR,N 2-physisorption,N2O chemisorption,TPR,XRD and XPS.The formation of copper phyllosilicate is observed in Cu/SiO2 catalyst by adopting UHDP method,and the amount of copper phyllosilicate is related to copper loading.It is found the structure properties and catalytic performance is profoundly affected by the amount of copper phyllosilicate.The excellent catalytic activity is attributed to the synergetic effect between Cu0 and Cu +.DMO conversion and EG selectivity are determined by the amount of Cu0 and Cu+,respectively.The proper copper loading (30 wt%) provides with the highest ratio of Cu + /Cu0,giving rise to the highest EG yield of 95% under the reaction conditions of p=2.0 MPa,T=473 K,H2/DMO=80 and LHSV=1.0h-1.展开更多
The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. I...The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.展开更多
Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as ...Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.展开更多
The ternary hybrid films consisting of chitosan(CS),polyethylene glycol(PEG)and nano-sized silica which was surface-modified by amino groups(RNSA)were prepared.The structures of the blend membranes were characterized ...The ternary hybrid films consisting of chitosan(CS),polyethylene glycol(PEG)and nano-sized silica which was surface-modified by amino groups(RNSA)were prepared.The structures of the blend membranes were characterized by attenuation total reflection-infrared spectroscopy(ATR-IR),X-ray diffraction(XRD),optical microscopy(OM)and differential scanning calorimetry(DSC).The results showed that the addition of silica affected not only the distribution and crystallinity of PEG on the sample surface,but also the pha...展开更多
Novel Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide), PEG-b-(PNIPAM)2, were successfully synthesized through atom transfer radical polymerization (ATRP). A difunctional macr...Novel Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide), PEG-b-(PNIPAM)2, were successfully synthesized through atom transfer radical polymerization (ATRP). A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether (PEG). The copolymers were obtained via the ATRP ofN-isopropylacrylamide (NIPAM) at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O (v/v = 3:1) mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography (GPC) and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions (PDI 〈 1.15). Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry (DSC). As a result, the phase transition temperature of PEG45-b-(PNIPAM55)2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.展开更多
The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized b...The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized by ICP-AES, BET and TPR. The results demonstrated that the dehydrogenation was improved by addition of chromium promoter. The selectivity of 2-methylpyrazine reached 84.75%, while the conversions of reactants were also enhanced.展开更多
Highly active and selective Cu/SiO2 catalysts for hydrogenation of dimethyl oxalate(DMO) to ethylene glycol(EG) were successfully prepared by means of a convenient one-pot synthetic method with tetraethoxysi lane...Highly active and selective Cu/SiO2 catalysts for hydrogenation of dimethyl oxalate(DMO) to ethylene glycol(EG) were successfully prepared by means of a convenient one-pot synthetic method with tetraethoxysi lane(TEOS) as the source of silica. XRD, H2-TPR, SEM, TEM, XRF and N2 physisorption measurements were performed to characterize the texture and structure of Cu/SiO2 catalysts with different copper loadings. The active components were highly dispersed on SiO2 supports. Furthermore, the coexistence of Cu0 and Cu+ contributed a lot to the excellent performance of Cu-TEOS catalysts. The DMO conversion reached 100% and the EG selectivity reached 95% at 498 K and 2 MPa with a high liquid hourly space velocity over the 27-Cu-TEOS catalyst with an actual cop per loading of 19.0%(mass fraction).展开更多
Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein...Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.展开更多
The mechanism of dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO2 catalyst was investigated by in situ Fourier transform infrared (FTIR) spectroscopy. It was found that dimethyl oxalate and methyl glyc...The mechanism of dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO2 catalyst was investigated by in situ Fourier transform infrared (FTIR) spectroscopy. It was found that dimethyl oxalate and methyl glycolate proceeded via dissociative adsorption on Cu/SiO2 catalyst, and four main intermediates, CH3OC(O)(O)C-M (1655 cm-1), M-C(O)(O)C-M (1618 cm-1), HOCH2(O)C--M (1682 cm-1) and CH3O-M (2924-2926 cm-1), were identified during the reaction. It was concluded that dimethyl oxalate hydrogenation to ethylene glycol mainly proceeded along the route: dimethyl oxalate /rightarrow CH3OC(O)(O)C-M → methyl glycolate →HOCH2(O)C-M → ethylene glycol. Finally a schematic reaction network was proposed.展开更多
MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the...MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the roles of nickel, ZnO and MnOx were investigated. The results show that nickel provided a new pathway of glucose to sorbitol and played an important role in the hydrogenation of C3 intermediates to 1,2-propanediol(1,2-PDO). The high yield of 1, 2-PDO was attributed to effective C–C bond cleavage performance of ZnO support promoted by MnOx. ZnO and MnOx contribute to the conversion of glycerol to lactic acid(LA) and LA to 1, 2-PDO, respectively. A concise pathway for hydrogenation of glucose over Ni-based catalyst was proposed.展开更多
The coal(syngas)-to-ethylene glycol(CTEG),is contaminated with the naughty impurity 2-Methoxyethanol(ME)generated during the hydrogenation stage,which affect the quality of EG for fiber-grade polyester production.Dist...The coal(syngas)-to-ethylene glycol(CTEG),is contaminated with the naughty impurity 2-Methoxyethanol(ME)generated during the hydrogenation stage,which affect the quality of EG for fiber-grade polyester production.Distillation,is the employed separation process in industrial,which makes production complicated because of the heat sensitivity of the impurities system.Melt crystallization has been regarded as an effective technology to obtain high-purity organic compounds based on the melting points difference,which could avoid the problems by heating.In this work,we have explored the feasibility of the static melt crystallization on the separation of EG/ME in a jacketed crystallization tube.The experimental parameters were investigated,which covers crystallization and sweating stage in each step.The results showed that the purity of EG could reach≥99.8%from the binary system studied via the quaternary separation process.展开更多
Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via...Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via ring-opening polymerization. The most appropriate technological conditions of synthesis of lactide were researched in the paper. The copolymers were measured by Infrared spectroscopy (IR) and <sup>1</sup>H nuclear magnetic resonance (<sup>1</sup>H NMR). The results proved that the lactide and PLA-PEG were synthesized successfully. Hydrophilic performance of the copolymer was measured by a water contact angle tester after prepared into a flat membrane. The water contact angle changed from 81.5? to 71.6?, which proved that the hydrophily of PLA-PEG was better than PLA.展开更多
基金support of the Fundamental Research Funds for the Central Universities(No.2022CDJQY-004)the Fund for Innovative Research Groups of Natural Science Foundation of Hebei Province(No.A2020202002).
文摘Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.
基金financially supported by Mahasarakham University。
文摘A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applications.In this work,a PEG was incorporated into block copolymer as a plasticizer by solvent casting.PLLA-PEG-PLLA/PEG blends with different blend ratios were prepared,and the plasticizing effect and miscibility of PEG in block copolymer were intensively investigated compared to PLLA/PEG blends.The results indicated that the PEG was an effective plasticizer for the block copolymer.The blending of PEG decreased glass-transition temperature and accelerated the crystallization of both the PLLA and PLLA-PEG-PLLA matrices.The PEG was completely miscible when blended with block copolymer and it improved thermal stability of the block copolymer matrix but not of the PLLA matrix.Film extensibility of PLLA-PEG-PLLA/PEG blends steadily increased as the PEG ratio increased.These non-toxic and highly flexible PLLA-PEG-PLLA/PEG bioplastics are promising candidates for several applications such as biomedical devices,tissue scaffolds and packaging materials.
基金Fujian External Cooperation project of Natural Science Foundation,China(No.2022I0042)。
文摘Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.
文摘A new blend of poly(2-hydroxyethyl methacrylate) (PHEMA) with poly (ethylene glycol) (PEG) was prepared. The results from solid-state NMR indicate that the PHEMA/PEG(88:12, w/w) blend is miscible on a molecular level.
基金Financial support from the National Science and Technology Planning Project (No. 2011BAC08B00)the National High Technology Research and Development Program of China (863 Program) (No.2012AA03A611)
文摘Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.
文摘Hydrogels composed of poly(vinyl alcohol)(PVA) and poly(ethylene glycol)(PEG) were synthesized using glutaraldehyde as crosslinker and investigated for controlled delivery of the common anti-inflammatory drug, ibuprofen(IBF). To regulate the drug delivery, solid inclusion complexes(ICs) of IBF in β–cyclodextrin(β–CD) were prepared and added to the hydrogels. The ICs were prepared by the microwave irradiation method, which is more environmentally benign. The formation of IC was confirmed by various analytical techniques and the synthesized hydrogels were also characterized. Controlled release of drug was achieved from the hydrogels containing the ICs in comparison to the rapid release from hydrogels containing free IBF.The preliminary kinetic analysis emphasized the crucial role of β–CD in the drug release process that influences the polymer relaxation, thereby leading to prolonged release. The cytotoxicity assay validated the hydrogels as non-toxic in nature and hence can be utilized for controlled delivery of IBF.
基金This work was supported by the National Basic Science Research and Development Grants (973) of China (No.G1999064705) and the National High Technology Project (863) of China (No. 2002AA326030).
文摘In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were then modified by SO2 gas plasma treatment. ATR-FITR and XPS were used to analyze the chemical change which had occurred on the film's surface. When the content of sulfur on the surface of blend films surpasses 1.59%, the antithrombogenicity of plasma treated films increases remarkably due to surface sulfonation. This result implies that SF with blend of PEGM after SO2 plasma treatment have potential use for making blood-contacting biomaterials.
文摘Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation (UHDP) technique have been proposed focusing on the effect of copper loading.The texture,structure and composition are systematically characterized by ICP,FTIR,N 2-physisorption,N2O chemisorption,TPR,XRD and XPS.The formation of copper phyllosilicate is observed in Cu/SiO2 catalyst by adopting UHDP method,and the amount of copper phyllosilicate is related to copper loading.It is found the structure properties and catalytic performance is profoundly affected by the amount of copper phyllosilicate.The excellent catalytic activity is attributed to the synergetic effect between Cu0 and Cu +.DMO conversion and EG selectivity are determined by the amount of Cu0 and Cu+,respectively.The proper copper loading (30 wt%) provides with the highest ratio of Cu + /Cu0,giving rise to the highest EG yield of 95% under the reaction conditions of p=2.0 MPa,T=473 K,H2/DMO=80 and LHSV=1.0h-1.
文摘The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.
基金The authors are Indebted to the National Basic Science Rescarch and Development Grants(973)(No.1999054306).
文摘Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.
基金Henan Innovation Project for University Prominent Research Talents(“HAIPURT”)program.
文摘The ternary hybrid films consisting of chitosan(CS),polyethylene glycol(PEG)and nano-sized silica which was surface-modified by amino groups(RNSA)were prepared.The structures of the blend membranes were characterized by attenuation total reflection-infrared spectroscopy(ATR-IR),X-ray diffraction(XRD),optical microscopy(OM)and differential scanning calorimetry(DSC).The results showed that the addition of silica affected not only the distribution and crystallinity of PEG on the sample surface,but also the pha...
基金support from the National Natural Science Foundation of China(No. 20134020)the Visiting Scholar Project of Shandong Province of China(No.20081001)the Science Research Fund of Shandong Jiaotong University of China(No.Z200802)
文摘Novel Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide), PEG-b-(PNIPAM)2, were successfully synthesized through atom transfer radical polymerization (ATRP). A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether (PEG). The copolymers were obtained via the ATRP ofN-isopropylacrylamide (NIPAM) at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O (v/v = 3:1) mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography (GPC) and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions (PDI 〈 1.15). Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry (DSC). As a result, the phase transition temperature of PEG45-b-(PNIPAM55)2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.
文摘The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized by ICP-AES, BET and TPR. The results demonstrated that the dehydrogenation was improved by addition of chromium promoter. The selectivity of 2-methylpyrazine reached 84.75%, while the conversions of reactants were also enhanced.
基金Supported by the National Science and Technology Supporting Plan Through Contract, China(No.2011BAD22B06)the Zhejiang Provincial Natural Science Foundation, China(No. R1110089)+2 种基金the Fundamental Research Funds for the Central Univer-sities of China(No.2011FZA4012)the Research Fund for the Doctoral Program of Higher Education of China (No.20090101110034)the Zhejiang Provincial Key Science and Technology Innovation Team, China(No.2009R50012)
文摘Highly active and selective Cu/SiO2 catalysts for hydrogenation of dimethyl oxalate(DMO) to ethylene glycol(EG) were successfully prepared by means of a convenient one-pot synthetic method with tetraethoxysi lane(TEOS) as the source of silica. XRD, H2-TPR, SEM, TEM, XRF and N2 physisorption measurements were performed to characterize the texture and structure of Cu/SiO2 catalysts with different copper loadings. The active components were highly dispersed on SiO2 supports. Furthermore, the coexistence of Cu0 and Cu+ contributed a lot to the excellent performance of Cu-TEOS catalysts. The DMO conversion reached 100% and the EG selectivity reached 95% at 498 K and 2 MPa with a high liquid hourly space velocity over the 27-Cu-TEOS catalyst with an actual cop per loading of 19.0%(mass fraction).
基金Supported by the National Natural Science Foundation of China(21776126)the National Basic Research Program of China(2015CB655301)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20150063)partially supported by the Open Fund of State Key Laboratory of Separation Membranes and Membrane Processes(M1-201702).
文摘Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.
文摘The mechanism of dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO2 catalyst was investigated by in situ Fourier transform infrared (FTIR) spectroscopy. It was found that dimethyl oxalate and methyl glycolate proceeded via dissociative adsorption on Cu/SiO2 catalyst, and four main intermediates, CH3OC(O)(O)C-M (1655 cm-1), M-C(O)(O)C-M (1618 cm-1), HOCH2(O)C--M (1682 cm-1) and CH3O-M (2924-2926 cm-1), were identified during the reaction. It was concluded that dimethyl oxalate hydrogenation to ethylene glycol mainly proceeded along the route: dimethyl oxalate /rightarrow CH3OC(O)(O)C-M → methyl glycolate →HOCH2(O)C-M → ethylene glycol. Finally a schematic reaction network was proposed.
基金financially supported by the National Science Foundation of China (21671132)Shanghai Science and Technology Committee(16dz1207200)the Youth Innovation Promotion Association CAS(2015231)
文摘MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the roles of nickel, ZnO and MnOx were investigated. The results show that nickel provided a new pathway of glucose to sorbitol and played an important role in the hydrogenation of C3 intermediates to 1,2-propanediol(1,2-PDO). The high yield of 1, 2-PDO was attributed to effective C–C bond cleavage performance of ZnO support promoted by MnOx. ZnO and MnOx contribute to the conversion of glycerol to lactic acid(LA) and LA to 1, 2-PDO, respectively. A concise pathway for hydrogenation of glucose over Ni-based catalyst was proposed.
基金financially supported by the Program for Sanjin Scholars of Shanxi Province of ChinaTen Thousand Talents Program:Millions of Leading Engineering Talents。
文摘The coal(syngas)-to-ethylene glycol(CTEG),is contaminated with the naughty impurity 2-Methoxyethanol(ME)generated during the hydrogenation stage,which affect the quality of EG for fiber-grade polyester production.Distillation,is the employed separation process in industrial,which makes production complicated because of the heat sensitivity of the impurities system.Melt crystallization has been regarded as an effective technology to obtain high-purity organic compounds based on the melting points difference,which could avoid the problems by heating.In this work,we have explored the feasibility of the static melt crystallization on the separation of EG/ME in a jacketed crystallization tube.The experimental parameters were investigated,which covers crystallization and sweating stage in each step.The results showed that the purity of EG could reach≥99.8%from the binary system studied via the quaternary separation process.
文摘Lactide was synthesized using lactic acid and stannous octoate as raw material and catalyst, respectively. Poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) was prepared by lactide and poly (ethylene glycol) (PEG) via ring-opening polymerization. The most appropriate technological conditions of synthesis of lactide were researched in the paper. The copolymers were measured by Infrared spectroscopy (IR) and <sup>1</sup>H nuclear magnetic resonance (<sup>1</sup>H NMR). The results proved that the lactide and PLA-PEG were synthesized successfully. Hydrophilic performance of the copolymer was measured by a water contact angle tester after prepared into a flat membrane. The water contact angle changed from 81.5? to 71.6?, which proved that the hydrophily of PLA-PEG was better than PLA.