Highly active calcium chloride（CaCl2） doped Zn-Co^Ⅲdouble metal-cyanide（Ca-DMC） catalysts were firstly reported.Ca-DMCs presented a very higher polymer yield（54 kg polymer/g catalyst） at relative low temperatur...Highly active calcium chloride（CaCl2） doped Zn-Co^Ⅲdouble metal-cyanide（Ca-DMC） catalysts were firstly reported.Ca-DMCs presented a very higher polymer yield（54 kg polymer/g catalyst） at relative low temperature（80-115℃） toward ringopening polymerization（ROP） of propylene oxide（PO） than did DMC catalysts without modification.展开更多
In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD...In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.展开更多
Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) ...Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.展开更多
Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact...Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact on the catalytic efficiency as well as the polymer selectivity for the reaction of PO/CO2. Zn-Ni（Ⅱ） DMC is a potential catalyst for alternating copolymerization of PO/CO2,and DMC catalysts based on Zn3[Co（CN）5X]2 （X = Br^- and N3^-） exhibit moderate efficiency for the production of polycarbonates.This research presents the preliminary exploration of novel DMC complex via chemical modification of its central metal and ligand.展开更多
Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownethe...Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.展开更多
The syntheses and structures of eleven novel polymeric transition metal complexes having one dimensional chain structures or three dimensional networks are summarized. They are prepared from the controlled assemblin...The syntheses and structures of eleven novel polymeric transition metal complexes having one dimensional chain structures or three dimensional networks are summarized. They are prepared from the controlled assembling reactions in organic solvents and characterized by X ray diffraction analyses. The spectroscopic or magnetic properties of some complexes are studied.展开更多
The design and synthesis of transition metal complexes with high thermal stability in olefin polymerization have become more and more important in order to meet the need of industrial application.This review focuses o...The design and synthesis of transition metal complexes with high thermal stability in olefin polymerization have become more and more important in order to meet the need of industrial application.This review focuses on the transition metal complex catalyst with high thermal stability containing different structures,including the backbone of bis（imino）pyridine,a-diimine and other types of ligands.Besides the catalytic activity,the influence of reaction temperature on the molecular weight and molecular weight distribution of the obtained polymer was also described.The plausible mechanism on the stability of catalysts at high temperature was proposed,which may give guidance to design catalyst with good thermal stability.展开更多
Late-transition-metal(LTM) catalysts are a family of very flexible ethylene polymerization catalysts because their catalytic performance can be easily adjusted by modifying the ligand structure.Their less oxyphilicity...Late-transition-metal(LTM) catalysts are a family of very flexible ethylene polymerization catalysts because their catalytic performance can be easily adjusted by modifying the ligand structure.Their less oxyphilicity character,which may promote the production of copolymers from ethylene and polar comonomers,is another aspect that attracts much attention in both academic and industrial fields.The immobilization of LTM catalysts on spherical supports is a crucial step prior to their use in the industrial processes of gas-phase or slurry polymerizations.This paper reviews recent developments in supported LTM catalysts for olefin polymerization,and summarizes loading methods and mechanisms of the immobilization of LTM catalysts on inorganic,organic,and inorganic-organic materials,and the effects of immobilization on catalytic activity,polymerization mechanism,and polymer morphology.展开更多
A series of new complexes {2,6-bis[1-((2-methyl-4-methoxyphenyl)imino)ethyl]pyri-dine}MCI2 [M=Fe(Ⅱ) (2), Co(Ⅱ) (3), Ni(Ⅱ) (4), Cu(Ⅱ) (5), Zn(Ⅱ) (6)] have been synthesized. At 25℃, using 500 equiv of methylalumin...A series of new complexes {2,6-bis[1-((2-methyl-4-methoxyphenyl)imino)ethyl]pyri-dine}MCI2 [M=Fe(Ⅱ) (2), Co(Ⅱ) (3), Ni(Ⅱ) (4), Cu(Ⅱ) (5), Zn(Ⅱ) (6)] have been synthesized. At 25℃, using 500 equiv of methylaluminoxane (MAO), the activities of Fe(Ⅱ), Co(Ⅱ) catalysts can reach 4.02×106 g/mol-Fehatm for ethylene polymerization and 3.98×105 g/mol-Cohatm for ethylene oligomerization. The effects of polymerization conditions such as reaction temperature, Al/M molar ratio and time on the activity of catalyst have been explored.展开更多
Researches of late-transition metal complexes for ethylene polymerization and oligomerization have attracted a lot of attention in the last two decades.A large number of late-transition metal complexes with symmetric ...Researches of late-transition metal complexes for ethylene polymerization and oligomerization have attracted a lot of attention in the last two decades.A large number of late-transition metal complexes with symmetric diimine ligands have been extensively studied.Although the research of unsymmetric diimine late-transition metal complexes was still in the initial stage,some superior performances were observed in olefin polymerization.Recent developments in the research of ethylene polymerization and oligomerization catalyzed by late-transition metal complexes with unsymmetric diimine ligands were summarized in this review,with the influence of complex structure on the catalytic performance of the catalyst analyzed.展开更多
Polymers grafted from solid surface are being extensively studied with a range of objectives.The most popular living/controlled polymerization used in polymers grafted from solid surfaces is the surface-initiated atom...Polymers grafted from solid surface are being extensively studied with a range of objectives.The most popular living/controlled polymerization used in polymers grafted from solid surfaces is the surface-initiated atom transfer radical polymerization（SI-ATRP）[1,2].An attractive feature of atom transfer radical polymerization（ATRP） is to simultaneously grow chains from multifunctional surface.Thus the grafted polymer with well-defined structures could be designed and controlled.ATRP has proven to be a powerful tool to synthesize homopolymers and copolymers,under easily accessible experimental conditions[3-7].Furthermore it is useful for the functionalization of material surfaces by grafting certain polymers.展开更多
基金the financial supports of the National Science Foundation of the People's Republic of China(No.20704034)Provincial Natural Science Foundation of Zhejiang(No.Y4090047)
文摘Highly active calcium chloride（CaCl2） doped Zn-Co^Ⅲdouble metal-cyanide（Ca-DMC） catalysts were firstly reported.Ca-DMCs presented a very higher polymer yield（54 kg polymer/g catalyst） at relative low temperature（80-115℃） toward ringopening polymerization（ROP） of propylene oxide（PO） than did DMC catalysts without modification.
基金Scientific Research Fund of Kahramanmaras Sutcu Imam University,Turkey(2012/3-7YLS)
文摘In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.
文摘Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.
基金the National Natural Science Foundation of China(No.50273031)China Postdoctoral Science Foundation(No.20060400339).
文摘Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact on the catalytic efficiency as well as the polymer selectivity for the reaction of PO/CO2. Zn-Ni（Ⅱ） DMC is a potential catalyst for alternating copolymerization of PO/CO2,and DMC catalysts based on Zn3[Co（CN）5X]2 （X = Br^- and N3^-） exhibit moderate efficiency for the production of polycarbonates.This research presents the preliminary exploration of novel DMC complex via chemical modification of its central metal and ligand.
文摘Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.
文摘The syntheses and structures of eleven novel polymeric transition metal complexes having one dimensional chain structures or three dimensional networks are summarized. They are prepared from the controlled assembling reactions in organic solvents and characterized by X ray diffraction analyses. The spectroscopic or magnetic properties of some complexes are studied.
文摘The design and synthesis of transition metal complexes with high thermal stability in olefin polymerization have become more and more important in order to meet the need of industrial application.This review focuses on the transition metal complex catalyst with high thermal stability containing different structures,including the backbone of bis（imino）pyridine,a-diimine and other types of ligands.Besides the catalytic activity,the influence of reaction temperature on the molecular weight and molecular weight distribution of the obtained polymer was also described.The plausible mechanism on the stability of catalysts at high temperature was proposed,which may give guidance to design catalyst with good thermal stability.
基金supported by the National Natural Science Foundation of China (20972025)the China National Petroleum Corporation (CNPC)Innovation Foundation (2010D-5006-0504)+1 种基金Scientific Research Foundation for the Returned Overseas Chinese Scholars,Heilongjiang Province(41417837-8-08016)Scientific Research Foundation for Overseas Chinese Scholars,Department of education of Heilongjiang Province(1154H14)
文摘Late-transition-metal(LTM) catalysts are a family of very flexible ethylene polymerization catalysts because their catalytic performance can be easily adjusted by modifying the ligand structure.Their less oxyphilicity character,which may promote the production of copolymers from ethylene and polar comonomers,is another aspect that attracts much attention in both academic and industrial fields.The immobilization of LTM catalysts on spherical supports is a crucial step prior to their use in the industrial processes of gas-phase or slurry polymerizations.This paper reviews recent developments in supported LTM catalysts for olefin polymerization,and summarizes loading methods and mechanisms of the immobilization of LTM catalysts on inorganic,organic,and inorganic-organic materials,and the effects of immobilization on catalytic activity,polymerization mechanism,and polymer morphology.
基金supported by the Chinese Academy of Sciences,the National Natural Science Foundation of China(Grant No.20371039)National Basic Research Program(the 973 Program,No.2003CB214600)+1 种基金the Key Laboratory Research and Establishment Program of Shaanxi Education Section(No.03JS006)the Natural Science Foundation of Shaanxi Province(Grant No.04JK143).
文摘A series of new complexes {2,6-bis[1-((2-methyl-4-methoxyphenyl)imino)ethyl]pyri-dine}MCI2 [M=Fe(Ⅱ) (2), Co(Ⅱ) (3), Ni(Ⅱ) (4), Cu(Ⅱ) (5), Zn(Ⅱ) (6)] have been synthesized. At 25℃, using 500 equiv of methylaluminoxane (MAO), the activities of Fe(Ⅱ), Co(Ⅱ) catalysts can reach 4.02×106 g/mol-Fehatm for ethylene polymerization and 3.98×105 g/mol-Cohatm for ethylene oligomerization. The effects of polymerization conditions such as reaction temperature, Al/M molar ratio and time on the activity of catalyst have been explored.
基金supported by the National Natural Science Foundation of China (20972025,U1362110)the China National Petroleum Corporation (CNPC) Innovation Foundation (2013D-5006-0503)+1 种基金the Scientific Research Foundation for the Returned Overseas Chinese Scholars,Heilongjiang Province (41417837-8-08016)the Scientific Research Foundation for Overseas Chinese Scholars,Department of Education of Heilongjiang Province (1154H14)
文摘Researches of late-transition metal complexes for ethylene polymerization and oligomerization have attracted a lot of attention in the last two decades.A large number of late-transition metal complexes with symmetric diimine ligands have been extensively studied.Although the research of unsymmetric diimine late-transition metal complexes was still in the initial stage,some superior performances were observed in olefin polymerization.Recent developments in the research of ethylene polymerization and oligomerization catalyzed by late-transition metal complexes with unsymmetric diimine ligands were summarized in this review,with the influence of complex structure on the catalytic performance of the catalyst analyzed.
基金Supported by the National Natural Science Foundation of China（Nos.51203015, 51243003）.
文摘Polymers grafted from solid surface are being extensively studied with a range of objectives.The most popular living/controlled polymerization used in polymers grafted from solid surfaces is the surface-initiated atom transfer radical polymerization（SI-ATRP）[1,2].An attractive feature of atom transfer radical polymerization（ATRP） is to simultaneously grow chains from multifunctional surface.Thus the grafted polymer with well-defined structures could be designed and controlled.ATRP has proven to be a powerful tool to synthesize homopolymers and copolymers,under easily accessible experimental conditions[3-7].Furthermore it is useful for the functionalization of material surfaces by grafting certain polymers.
