Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-sca...Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-scale production.However,most researches related with heterogeneous Z-N catalysts focused onα-olefin polymerizations like ethylene,propylene,etc.展开更多
?Ethene/norbornene copolymerization by the catalyst system [Me_2Si( 3- tertBuCp)(N tertBu)]TiCl_2/MAO was investigated in detail at 30 ℃, 60℃, and 90℃. A mass flow controller was used in this work to obtain kine ...?Ethene/norbornene copolymerization by the catalyst system [Me_2Si( 3- tertBuCp)(N tertBu)]TiCl_2/MAO was investigated in detail at 30 ℃, 60℃, and 90℃. A mass flow controller was used in this work to obtain kine tic data and investigate tempera ture's effects on activity, norbornene incorporation, copolymerization parameter , microstructure, glass transition temperature, and molar masses were described. H igh copolymerization values r_E and high alternation are determined. The n umber of isotactic alternating sequences is much higher than that of the syndiot actic alter nating sequences.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＆#39;-methylimidazolium hexafluorophosphate （[C4CNmim]＋PF6-） medium. The synth...The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones （PK）was studied in the N-valeronitrile-N＆#39;-methylimidazolium hexafluorophosphate （[C4CNmim]＋PF6-） medium. The synthe-sized 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 chro-matography （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 car-bon carrier）, the highest catalytic activity 2 963.64 gSTCO/（gPd＆#183;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
Chloromethyl-2-norbornene was synthesized via Diels-Alder reaction of cyclopentadiene and allyl chloride using a polymer supported boron trifluoride as the catalyst, and was then lithiated and used to initiate a livin...Chloromethyl-2-norbornene was synthesized via Diels-Alder reaction of cyclopentadiene and allyl chloride using a polymer supported boron trifluoride as the catalyst, and was then lithiated and used to initiate a living anionic polymerization of styrene to prepare a macromonome, 5-polystyryl-2-norbornene NBPS. Comb graft copolymer PNBgPS was synthesized via ring opening metathesis polymerization of the macromonomer under the catalysis of ruthenium carbene complex RuCl2(PPh3)2(=CCHtBu) and its polymer supported correspondent. Experimental results showed that the behavior of both the supported boron and supported ruthenium catalysts are superior to their unsupported counterparts. The possible promotion mechanism of the tailor-made supports is discussed.展开更多
In order to investigate the rules on formation of zeolite during crystallization of titanium silicalite zeolite (TS-1) the X-ray diffractometry and Foulier transform infra-red spectrometry were applied to track the pr...In order to investigate the rules on formation of zeolite during crystallization of titanium silicalite zeolite (TS-1) the X-ray diffractometry and Foulier transform infra-red spectrometry were applied to track the process of crystallization of titanium silicalite zeolite. The research results revealed that at the initial stage of crystallization the interactions between silica gel and titania gel in the polymer blend could gradually lead to the formation of tiny crystal nuclei with complicated structure that could slowly grow up to form molecular sieves. Quite different from the conventional zeolites that use the acid sites as the catalytically active centers, the oxidative reactivity of the titanium silicalite zeolite was not proportional to its crystallinity and is associated with the oxidative centers of titanium contained in the zeolite.展开更多
In this review, a recent development of cationic ?-diimine palladium(II) complexes for ethylene polymerization and copolymerization with polar functionalized comonomers was briefly described. First, the polymerization...In this review, a recent development of cationic ?-diimine palladium(II) complexes for ethylene polymerization and copolymerization with polar functionalized comonomers was briefly described. First, the polymerization mechanism for this type of catalysts was discussed. Next, recent advances in ligand design were provided with special focus on the influence of ligand structures on the catalytic polymerization properties. Last, the ethylene homopolymerization and copolymerization with various polar comonomers, especially acrylate and vinyl ethers were summarized.展开更多
Conjugated polymer photocatalysts have received extensive attention in the field of photocatalytic hydrogen evolution owing to their tunable molecular structures and electronic properties.Herein,we developed three don...Conjugated polymer photocatalysts have received extensive attention in the field of photocatalytic hydrogen evolution owing to their tunable molecular structures and electronic properties.Herein,we developed three donoracceptor(D-A)type thiophene-containing narrow-band-gap conjugated polymers with pyrene as a donor and different fused-thiophene derivatives as acceptors via direct C-H arylation coupling polymerization.It was found that the band gap of the polymers can be tuned by adjusting the number of the fused-thiophene rings.The visible light absorption range can be extended by increasing the number of the thiophene rings,the planar molecular structure for both donor and acceptor units facilitates the charge transmission along the polymer skeleton,and the D-A type polymer structure promotes the dissociation of photo-induced electrons and holes.As a result,a high photocatalytic hydrogen evolution rate of 33.07 mmol h^(−1)g^(−1) was obtained by PyTP-2 with an optimized molecular structure under visible light irradiation(λ>420 nm)without the aid of Pt co-catalyst.In addition,PyTP-2 also shows a photocatalytic activity for oxygen evolution with an average oxygen evolution rate of 58.37µmol h^(−1)g^(−1).展开更多
In the present work, a novel porous, and chemically stable amine-based covalent organic polymer （POP-1） was designed and synthesized under solvothermal conditions. The porosity, crystallinity, chemical stability, el...In the present work, a novel porous, and chemically stable amine-based covalent organic polymer （POP-1） was designed and synthesized under solvothermal conditions. The porosity, crystallinity, chemical stability, electrochemical properties, and diffuse reflectance of POP-1 were investigated via N2 sorp- tion experiment, power X-ray diffraction, thermogravimetric analysis, cyclic voltammetry, and ultraviolet visible near infrared spectrometry, respectively. POP-I exhibits good chemical stability in both acidic and alkaline aqueous solutions, as well as in organic solvents. Undoped POP-1 can be directly used as a pho- tocatalyst for rhodamine B irradiation degradation under light-emitting diode and natural light. The Ea of POP-1 for RhB degradation is 82.37 kJ/mol. Furthermore, POP-1 can be reused as a catalyst in RhB degra- dation without degraded catalytic activity.展开更多
基金Supported by National Key Research and Development Program of China(2022 YFB 3704700(2022 YFB 3704702))Major Scientific and Technological Innovation Project of Shandong Province(2021 CXGC 010901)Taishan Scholar Program。
文摘Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-scale production.However,most researches related with heterogeneous Z-N catalysts focused onα-olefin polymerizations like ethylene,propylene,etc.
文摘?Ethene/norbornene copolymerization by the catalyst system [Me_2Si( 3- tertBuCp)(N tertBu)]TiCl_2/MAO was investigated in detail at 30 ℃, 60℃, and 90℃. A mass flow controller was used in this work to obtain kine tic data and investigate tempera ture's effects on activity, norbornene incorporation, copolymerization parameter , microstructure, glass transition temperature, and molar masses were described. H igh copolymerization values r_E and high alternation are determined. The n umber of isotactic alternating sequences is much higher than that of the syndiot actic alter nating sequences.
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＆#39;-methylimidazolium hexafluorophosphate （[C4CNmim]＋PF6-） medium. The synthe-sized 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 chro-matography （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 car-bon carrier）, the highest catalytic activity 2 963.64 gSTCO/（gPd＆#183;h） is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw/Mn=1.389.
基金National Natural Science Foundation of China (Project grant No.: 29874018)
文摘Chloromethyl-2-norbornene was synthesized via Diels-Alder reaction of cyclopentadiene and allyl chloride using a polymer supported boron trifluoride as the catalyst, and was then lithiated and used to initiate a living anionic polymerization of styrene to prepare a macromonome, 5-polystyryl-2-norbornene NBPS. Comb graft copolymer PNBgPS was synthesized via ring opening metathesis polymerization of the macromonomer under the catalysis of ruthenium carbene complex RuCl2(PPh3)2(=CCHtBu) and its polymer supported correspondent. Experimental results showed that the behavior of both the supported boron and supported ruthenium catalysts are superior to their unsupported counterparts. The possible promotion mechanism of the tailor-made supports is discussed.
基金supported by the NationalScience Foundation of China(2006CB202508)wewould like to extend our heartfelt thanks to the RIPP’s labo-ratories engaging in XRD and FT-IR analyses for theirenergetical support and warm assistance provided to thisresearch work.
文摘In order to investigate the rules on formation of zeolite during crystallization of titanium silicalite zeolite (TS-1) the X-ray diffractometry and Foulier transform infra-red spectrometry were applied to track the process of crystallization of titanium silicalite zeolite. The research results revealed that at the initial stage of crystallization the interactions between silica gel and titania gel in the polymer blend could gradually lead to the formation of tiny crystal nuclei with complicated structure that could slowly grow up to form molecular sieves. Quite different from the conventional zeolites that use the acid sites as the catalytically active centers, the oxidative reactivity of the titanium silicalite zeolite was not proportional to its crystallinity and is associated with the oxidative centers of titanium contained in the zeolite.
基金supported by the National Natural Science Foundation of China(21374108,21304054)the Promotive Research Fund for the Young and Middle-aged Scientists of Shandong Province(BS2012CL018)+2 种基金the Foundation of Qufu Normal University(XJ201212)the Fundamental Research Funds for the Central Universities(WK3450000001)the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,Donghua University(LK1424)
文摘In this review, a recent development of cationic ?-diimine palladium(II) complexes for ethylene polymerization and copolymerization with polar functionalized comonomers was briefly described. First, the polymerization mechanism for this type of catalysts was discussed. Next, recent advances in ligand design were provided with special focus on the influence of ligand structures on the catalytic polymerization properties. Last, the ethylene homopolymerization and copolymerization with various polar comonomers, especially acrylate and vinyl ethers were summarized.
基金financially supported by the National Natural Science Foundation of China(21574077 and 21304055)the Fundamental Research Funds for the Central Universities(GK202102005)。
文摘Conjugated polymer photocatalysts have received extensive attention in the field of photocatalytic hydrogen evolution owing to their tunable molecular structures and electronic properties.Herein,we developed three donoracceptor(D-A)type thiophene-containing narrow-band-gap conjugated polymers with pyrene as a donor and different fused-thiophene derivatives as acceptors via direct C-H arylation coupling polymerization.It was found that the band gap of the polymers can be tuned by adjusting the number of the fused-thiophene rings.The visible light absorption range can be extended by increasing the number of the thiophene rings,the planar molecular structure for both donor and acceptor units facilitates the charge transmission along the polymer skeleton,and the D-A type polymer structure promotes the dissociation of photo-induced electrons and holes.As a result,a high photocatalytic hydrogen evolution rate of 33.07 mmol h^(−1)g^(−1) was obtained by PyTP-2 with an optimized molecular structure under visible light irradiation(λ>420 nm)without the aid of Pt co-catalyst.In addition,PyTP-2 also shows a photocatalytic activity for oxygen evolution with an average oxygen evolution rate of 58.37µmol h^(−1)g^(−1).
基金supported by the National Natural Science Foundation of China(21601109 and 21403130)the Natural Science Foundation of Shandong Province(ZR2014BQ028)
文摘In the present work, a novel porous, and chemically stable amine-based covalent organic polymer （POP-1） was designed and synthesized under solvothermal conditions. The porosity, crystallinity, chemical stability, electrochemical properties, and diffuse reflectance of POP-1 were investigated via N2 sorp- tion experiment, power X-ray diffraction, thermogravimetric analysis, cyclic voltammetry, and ultraviolet visible near infrared spectrometry, respectively. POP-I exhibits good chemical stability in both acidic and alkaline aqueous solutions, as well as in organic solvents. Undoped POP-1 can be directly used as a pho- tocatalyst for rhodamine B irradiation degradation under light-emitting diode and natural light. The Ea of POP-1 for RhB degradation is 82.37 kJ/mol. Furthermore, POP-1 can be reused as a catalyst in RhB degra- dation without degraded catalytic activity.
