End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerizatio...End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.展开更多
Hydroxyl-epoxy phosphate （HEP） as a reactive corrosion inhibitor was innovatively synthe- sized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crossl...Hydroxyl-epoxy phosphate （HEP） as a reactive corrosion inhibitor was innovatively synthe- sized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crosslinked with waterborne isocyanate curing agent, which was used to form waterborne HEP/acrylic polyurethane composite （HEP-APU） coatings on Q235 steel surfaces. Electrochemical impedance spectroscopy and polarization curves were applied to analyze the corrosion behavior of the HEP-APU coatings in 3.5wt% NaCl solutions. The results indicated that the HEP-APU coatings show a superior passivation property and efficient corrosion protection of Q235 steel. The waterborne acrylic polyurethane coating containing 0.5wt% HEP exhibited the best corrosion performance among all the coating specimens. The improved flash-rust resistance can be attributed to the introduction of the phosphate group which could form phosphate film on the steel substrate.展开更多
The catalytic properties of KF/MgO for the synthesis of didodecyl carbonate (DDC) by transesterification from dimethyl carbonate (DMC) and dodecanol were studied.The effects of loading amount of KF and calcining tempe...The catalytic properties of KF/MgO for the synthesis of didodecyl carbonate (DDC) by transesterification from dimethyl carbonate (DMC) and dodecanol were studied.The effects of loading amount of KF and calcining temperature were systemically investigated.The phase structure was characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR).Interaction between KF and the carrier MgO occurred in the process of calcination,and a new phase K2MgF4 formed when calcining temperature was 673 K or above.FTIR results showed that K2CO3 was observed when catalysts calcined in air.When calcining temperature was 873 K and the loading mass amount of KF was 30%,the KF/MgO catalyst exhibited the optimal catalytic properties and the yield of DDC was maximized to 80%.The excellent catalytic properties of KF/MgO was ascribed to the formation of K2MgF4+K2CO3 during the calcination in air.展开更多
Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprol...Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprolactone modified hydroxyethyl acrylate （PCLA2）. The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy （FT-IR）, IH nuclear magnetic resonance （^H NMR）, gel permeation chromatography （GPC） and differential scanning calorimeter （DSC）, and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis （TGA） and dynamic mechanical analysis （DMA）, respectively. The viscosity of the oligomers and mechanical properties of the cured films were also studied. The results show that both oligomers have narrow molecular weight distribution. The viscosity of PUPA is 2.310 Pa.s at 25 ℃, while that of PUCA is： up to 3.980 Pa-s. The UV cured PUPA and PUCA films have homogeneous phase structure, and the PUCA film shows higher glass transition temperature and storage modulus. Furthermore, the PUCA film possesses better mechanical properties than PUPA, while the latter shows better alkali resistance.展开更多
The Fe-modi fied sepiolite-supported Mn–Cu mixed oxide(Cux Mny/Fe-Sep) catalysts were prepared using the co-precipitation method.These materials were characterized by means of the XRD,N_2 adsorption–desorption,XPS,H...The Fe-modi fied sepiolite-supported Mn–Cu mixed oxide(Cux Mny/Fe-Sep) catalysts were prepared using the co-precipitation method.These materials were characterized by means of the XRD,N_2 adsorption–desorption,XPS,H_2-TPR,and O_2-TPD techniques,and their catalytic activities for CO and ethyl acetate oxidation were evaluated.The results show that catalytic activities of the Cux Mny/Fe-Sep samples were higher than those of the Cu1/Fe-Sep and Mn2/Fe-Sep samples,and the Mn/Cu molar ratio had a distinct in fluence on catalytic activity of the sample.Among the Cux Mny/Fe-Sep and Cu1Mn2/Sep samples,Cu1Mn2/Fe-Sep performed the best for CO and ethyl acetate oxidation,showing the highest reaction rate and the lowest T50 and T90 of 4.4×10^(-6) mmol·g-1·s-1,110,and 140 °C for CO oxidation,and 1.9×10^(-6) mmol·g-1·s-1,170,and210 °C for ethyl acetate oxidation,respectively.Moreover,the Cu1Mn2/Fe-Sep sample possessed the best lowtemperature reducibility and the lowest temperature of oxygen desorption as well as the highest surface Mn^(4+)/Mn^(3+) and Cu^(2+)/CuO atomic ratios.It is concluded that factors,such as the strong interaction between the Cu or Mn and the Fe-Sep support,good low-temperature reducibility,and good mobility of chemisorbed oxygen species,might account for the excellent catalytic activity of Cu1Mn2/Fe-Sep.展开更多
Hybrid materials were prepared using a silane coupling agent, tetraethoxysilane （ TEOS ） as the precursor, dilute hydrochloric acid as the catalyst, and epoxy as the matrices. The films coated with hybrid materials ...Hybrid materials were prepared using a silane coupling agent, tetraethoxysilane （ TEOS ） as the precursor, dilute hydrochloric acid as the catalyst, and epoxy as the matrices. The films coated with hybrid materials were expected to improve abrasion resistance and mechanical properties. The morphology, mechanical properties, adhesion, and abrasion resistance of the polyethylene terephthalate （PET） films were characterized using an atomic force microscope, a tensile testing machine, a bagger knife, and a reciprocating fabric abrasion tester. The result of research indicated that the modification significantly affected the abrasion resistance and roughness. The-tensile strength and abrasion resistance of the modified PET films increased by 40% and 50% respectively at 3 % TEOS mass fraction.展开更多
A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential therma...A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.展开更多
The purpose of this study was to investigate the suitability of palm diacylglycerol （PDAG）-enriched formulations for bakery shortening. Three types of palm diacylglycerol olein （PDAGOL） at different degree of unsa...The purpose of this study was to investigate the suitability of palm diacylglycerol （PDAG）-enriched formulations for bakery shortening. Three types of palm diacylglycerol olein （PDAGOL） at different degree of unsaturation （PDAGOL1V56, PDAGOLIV62 and PDAGOLIV64） were used as main raw materials blended with palm stearin （PS）. The blending compositions ranged from 30% to 70% of PDAGOLIV56/PS, PDAGOLIV62/PS and PDAGOLIV64/PS, respectively. The physicochemical properties of all binary blend systems were characterized for fatty acid composition （FAC）, slip melting point （SMP） and solid fat content （SFC）. The selected bakery shortening formulations were further characterised for polymorphic form of fat crystal and thermal behavior, using X-ray diffractometer （XRD） and differential scanning calorimetry （DSC）. Bakery shortening enriched with diacylglycerol that were produced from 40DS56 （40% PDAGOLIV56/60% PS）, 40DS62 （40% PDAGOL1V62/60% PS） and 40DS64 （40% PDAGOLIV64/60% PS） had 45%-50% unsaturated fatty acid and crystallized in β ＋ β polymorphs; thus they were suitable for shortening system. Based on product＇s baking performance, it could be found that all Madeira cakes prepared from bakery shortening enriched with diacylglycerol had higher specific cake volume as compared to commercial shortening （CS）. In customer acceptance test, Madeira cake made from 40DS56 shortening scored the highest rating for all sensory attributes, including overall customer acceptability. It had given an indication that 40DS56 shortening formulation was the most suitable fat blends to be used as bakery shortening.展开更多
基金Supported by PetroChina Company Limited(2020 B-2711)。
文摘End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.
文摘Hydroxyl-epoxy phosphate （HEP） as a reactive corrosion inhibitor was innovatively synthe- sized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crosslinked with waterborne isocyanate curing agent, which was used to form waterborne HEP/acrylic polyurethane composite （HEP-APU） coatings on Q235 steel surfaces. Electrochemical impedance spectroscopy and polarization curves were applied to analyze the corrosion behavior of the HEP-APU coatings in 3.5wt% NaCl solutions. The results indicated that the HEP-APU coatings show a superior passivation property and efficient corrosion protection of Q235 steel. The waterborne acrylic polyurethane coating containing 0.5wt% HEP exhibited the best corrosion performance among all the coating specimens. The improved flash-rust resistance can be attributed to the introduction of the phosphate group which could form phosphate film on the steel substrate.
文摘The catalytic properties of KF/MgO for the synthesis of didodecyl carbonate (DDC) by transesterification from dimethyl carbonate (DMC) and dodecanol were studied.The effects of loading amount of KF and calcining temperature were systemically investigated.The phase structure was characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR).Interaction between KF and the carrier MgO occurred in the process of calcination,and a new phase K2MgF4 formed when calcining temperature was 673 K or above.FTIR results showed that K2CO3 was observed when catalysts calcined in air.When calcining temperature was 873 K and the loading mass amount of KF was 30%,the KF/MgO catalyst exhibited the optimal catalytic properties and the yield of DDC was maximized to 80%.The excellent catalytic properties of KF/MgO was ascribed to the formation of K2MgF4+K2CO3 during the calcination in air.
基金Project(2007168303) supported by Guangdong-Hong Kong Technology Cooperation Funding
文摘Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprolactone modified hydroxyethyl acrylate （PCLA2）. The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy （FT-IR）, IH nuclear magnetic resonance （^H NMR）, gel permeation chromatography （GPC） and differential scanning calorimeter （DSC）, and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis （TGA） and dynamic mechanical analysis （DMA）, respectively. The viscosity of the oligomers and mechanical properties of the cured films were also studied. The results show that both oligomers have narrow molecular weight distribution. The viscosity of PUPA is 2.310 Pa.s at 25 ℃, while that of PUCA is： up to 3.980 Pa-s. The UV cured PUPA and PUCA films have homogeneous phase structure, and the PUCA film shows higher glass transition temperature and storage modulus. Furthermore, the PUCA film possesses better mechanical properties than PUPA, while the latter shows better alkali resistance.
基金Supported by the National Natural Science Foundation of China(21277008,20777005)the Natural Science Foundation of Beijing(8082008)
文摘The Fe-modi fied sepiolite-supported Mn–Cu mixed oxide(Cux Mny/Fe-Sep) catalysts were prepared using the co-precipitation method.These materials were characterized by means of the XRD,N_2 adsorption–desorption,XPS,H_2-TPR,and O_2-TPD techniques,and their catalytic activities for CO and ethyl acetate oxidation were evaluated.The results show that catalytic activities of the Cux Mny/Fe-Sep samples were higher than those of the Cu1/Fe-Sep and Mn2/Fe-Sep samples,and the Mn/Cu molar ratio had a distinct in fluence on catalytic activity of the sample.Among the Cux Mny/Fe-Sep and Cu1Mn2/Sep samples,Cu1Mn2/Fe-Sep performed the best for CO and ethyl acetate oxidation,showing the highest reaction rate and the lowest T50 and T90 of 4.4×10^(-6) mmol·g-1·s-1,110,and 140 °C for CO oxidation,and 1.9×10^(-6) mmol·g-1·s-1,170,and210 °C for ethyl acetate oxidation,respectively.Moreover,the Cu1Mn2/Fe-Sep sample possessed the best lowtemperature reducibility and the lowest temperature of oxygen desorption as well as the highest surface Mn^(4+)/Mn^(3+) and Cu^(2+)/CuO atomic ratios.It is concluded that factors,such as the strong interaction between the Cu or Mn and the Fe-Sep support,good low-temperature reducibility,and good mobility of chemisorbed oxygen species,might account for the excellent catalytic activity of Cu1Mn2/Fe-Sep.
基金Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education of China(No.2005-383)
文摘Hybrid materials were prepared using a silane coupling agent, tetraethoxysilane （ TEOS ） as the precursor, dilute hydrochloric acid as the catalyst, and epoxy as the matrices. The films coated with hybrid materials were expected to improve abrasion resistance and mechanical properties. The morphology, mechanical properties, adhesion, and abrasion resistance of the polyethylene terephthalate （PET） films were characterized using an atomic force microscope, a tensile testing machine, a bagger knife, and a reciprocating fabric abrasion tester. The result of research indicated that the modification significantly affected the abrasion resistance and roughness. The-tensile strength and abrasion resistance of the modified PET films increased by 40% and 50% respectively at 3 % TEOS mass fraction.
基金Supported by the National Natural Science Foundation of China（21161009）the Natural Science Foundation of Jiangxi Province（20122BAB213001,20114BAB213002）the Science and Technology Foundation of Jiangxi Province（GJJ11613）
文摘A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.
文摘The purpose of this study was to investigate the suitability of palm diacylglycerol （PDAG）-enriched formulations for bakery shortening. Three types of palm diacylglycerol olein （PDAGOL） at different degree of unsaturation （PDAGOL1V56, PDAGOLIV62 and PDAGOLIV64） were used as main raw materials blended with palm stearin （PS）. The blending compositions ranged from 30% to 70% of PDAGOLIV56/PS, PDAGOLIV62/PS and PDAGOLIV64/PS, respectively. The physicochemical properties of all binary blend systems were characterized for fatty acid composition （FAC）, slip melting point （SMP） and solid fat content （SFC）. The selected bakery shortening formulations were further characterised for polymorphic form of fat crystal and thermal behavior, using X-ray diffractometer （XRD） and differential scanning calorimetry （DSC）. Bakery shortening enriched with diacylglycerol that were produced from 40DS56 （40% PDAGOLIV56/60% PS）, 40DS62 （40% PDAGOL1V62/60% PS） and 40DS64 （40% PDAGOLIV64/60% PS） had 45%-50% unsaturated fatty acid and crystallized in β ＋ β polymorphs; thus they were suitable for shortening system. Based on product＇s baking performance, it could be found that all Madeira cakes prepared from bakery shortening enriched with diacylglycerol had higher specific cake volume as compared to commercial shortening （CS）. In customer acceptance test, Madeira cake made from 40DS56 shortening scored the highest rating for all sensory attributes, including overall customer acceptability. It had given an indication that 40DS56 shortening formulation was the most suitable fat blends to be used as bakery shortening.
