A series of imido-vanadium(Ⅴ)complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR,elemental analysis,and single-crystal X-ray diffraction.These complexes demonstrated excell...A series of imido-vanadium(Ⅴ)complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR,elemental analysis,and single-crystal X-ray diffraction.These complexes demonstrated excellent catalytic performance in ethylene/1-hexene copolymerization,achieving high activities of 12.0×10~6–49.0×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1)and affording random copolymers with tunable 1-hexene incorporations.These catalysts also exhibited ultrahigh activity,up to 112.2×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1),in ethylene/norbornene(NB)copolymerization,yielding cyclic olefin copolymers with adjustable NB incorporations.Remarkably,these catalysts demonstrated exceptional tolerance toward polar functional groups,enabling efficient copolymerization of ethylene with both 10-undecen-1-ol(U-OH)and 5-norbornene-2-methanol(NB-OH),incorporating about 2 mol%polar comonomers with high efficiency.Different with the catalytic behaviors in copolymerization of ethylene with nonpolar comonomers,the catalytic activities in E/U-OH copolymerization(25.7×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1))were much higher than those in E/NB-OH copolymerization(8.6×10^(6) g_(polymer)·(mol_(V))^(-1)·h^(-1)).DFT calculations revealed that the catalytic performance is governed by synergistic electronic and steric effects.For E/NB copolymerization,strong preference for cyclic olefins was attributed to favorable transition state stabilization.In polar comonomer systems,steric effects were predominant,with NB-OH exhibiting a larger buried volume around vanadium center upon coordination compared to U-OH.Overall,this work provides fundamental insights into vanadium-catalyzed(co)polymerization and offers new strategies for tailored polyolefin design.展开更多
The XYA-5 catalyst was first applied in commercial scale on an 80-kt/a acrylonitrile unit at the Daqing Refining and Chemical Company. Test results had shown that the once-through yield of acrylonitrile exceeded 80% w...The XYA-5 catalyst was first applied in commercial scale on an 80-kt/a acrylonitrile unit at the Daqing Refining and Chemical Company. Test results had shown that the once-through yield of acrylonitrile exceeded 80% with the unit consumption ofpropylene reaching 1032 kg on each ton of acrylonitrile. The product quality could be easily put under control and the distribution of reaction products was reasonable with good cleaning performance and stability of the catalyst that was suitable for use on this commercial unit.展开更多
This paper creates a LM (Levenberg-Marquardt) algorithm model which is appropriate to solve the problem about weights value of feedforward neural network. On the base of this model, we provide two applications in the ...This paper creates a LM (Levenberg-Marquardt) algorithm model which is appropriate to solve the problem about weights value of feedforward neural network. On the base of this model, we provide two applications in the oilfield production. Firstly, we simulated the functional relationships between the petrophysical and electrical properties of the rock by neural networks model, and studied oil saturation. Under the precision of data is confirmed, this method can reduce the number of experiments. Secondly, we simulated the relationships between investment and income by the neural networks model, and studied invest saturation point and income growth rate. It is very significant to guide the investment decision. The research result shows that the model is suitable for the modeling and identification of nonlinear systems due to the great fit characteristic of neural network and very fast convergence speed of LM algorithm.展开更多
基金financially supported by the National Natural Science Foundation of China(No.52130307)。
文摘A series of imido-vanadium(Ⅴ)complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized by NMR,elemental analysis,and single-crystal X-ray diffraction.These complexes demonstrated excellent catalytic performance in ethylene/1-hexene copolymerization,achieving high activities of 12.0×10~6–49.0×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1)and affording random copolymers with tunable 1-hexene incorporations.These catalysts also exhibited ultrahigh activity,up to 112.2×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1),in ethylene/norbornene(NB)copolymerization,yielding cyclic olefin copolymers with adjustable NB incorporations.Remarkably,these catalysts demonstrated exceptional tolerance toward polar functional groups,enabling efficient copolymerization of ethylene with both 10-undecen-1-ol(U-OH)and 5-norbornene-2-methanol(NB-OH),incorporating about 2 mol%polar comonomers with high efficiency.Different with the catalytic behaviors in copolymerization of ethylene with nonpolar comonomers,the catalytic activities in E/U-OH copolymerization(25.7×10~6 g_(polymer)·(mol_(V))^(-1)·h^(-1))were much higher than those in E/NB-OH copolymerization(8.6×10^(6) g_(polymer)·(mol_(V))^(-1)·h^(-1)).DFT calculations revealed that the catalytic performance is governed by synergistic electronic and steric effects.For E/NB copolymerization,strong preference for cyclic olefins was attributed to favorable transition state stabilization.In polar comonomer systems,steric effects were predominant,with NB-OH exhibiting a larger buried volume around vanadium center upon coordination compared to U-OH.Overall,this work provides fundamental insights into vanadium-catalyzed(co)polymerization and offers new strategies for tailored polyolefin design.
文摘The XYA-5 catalyst was first applied in commercial scale on an 80-kt/a acrylonitrile unit at the Daqing Refining and Chemical Company. Test results had shown that the once-through yield of acrylonitrile exceeded 80% with the unit consumption ofpropylene reaching 1032 kg on each ton of acrylonitrile. The product quality could be easily put under control and the distribution of reaction products was reasonable with good cleaning performance and stability of the catalyst that was suitable for use on this commercial unit.
文摘This paper creates a LM (Levenberg-Marquardt) algorithm model which is appropriate to solve the problem about weights value of feedforward neural network. On the base of this model, we provide two applications in the oilfield production. Firstly, we simulated the functional relationships between the petrophysical and electrical properties of the rock by neural networks model, and studied oil saturation. Under the precision of data is confirmed, this method can reduce the number of experiments. Secondly, we simulated the relationships between investment and income by the neural networks model, and studied invest saturation point and income growth rate. It is very significant to guide the investment decision. The research result shows that the model is suitable for the modeling and identification of nonlinear systems due to the great fit characteristic of neural network and very fast convergence speed of LM algorithm.
