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RATE－DETERMINING　STEP　IN　olefin　HYDROFORMYLATION　OVER　SUPPORTED　AQUEOUS－PHASE　CATALYSTS

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Chinese Chemical Letters 1994年第4期5卷 291-294页

作者： You Zhu YUAN Yi Quan YANG Jin Lai XU Hong Bin ZHANG and Khi Rui TSAI(Deportment of Chemistry Institute of Physical Chemistry Xiamen University Xiamen 361005)

A series of olefin hydroformylations over supported aqueous-phase rhodium catalyst with the substitUtion of CO/D2 for CO/H2 were cAned out to study the isotope effects of deuterium. The rate of aldehyde formation in CO/D2 was about 1.3 times faster than that in COns2, indicating that the aldehyde formation shows noticeable inverse deuterium isotope effect over SAP catalyst. The results of in-situIR stUdy of ethylene hydroformylation suggest that the reaction rate of acylhydrogenolysis forming aldehyde is the slowest one. It may be inferred from these results that the rate-determining step involved\in aldehyde formation is very probably astep ofhydrogenation.

关键词： STEP DETERMINING olefin HYDROFORMYLATION CATALYSTS AQUEOUS

Site-Selective Polyolefin Hydrogenolysis on Atomic Ru for Methanation Suppression and Liquid Fuel Production

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Research 2023年第3期6卷 423-432页

作者： Mingyu Chu Xianpeng Wang Xuchun Wang Xiangxi Lou Congyang Zhang Muhan Cao Lu Wang Youyong Li Sibao Liu Tsun-Kong Sham Qiao Zhang Jinxing Chen Institute of Functional Nano&Soft Materials(FUNSOM) Jiangsu Key Laboratory of Advanced Negative Carbon TechnologiesJoint International Research Laboratory of Carbon-Based Functional Materials and DevicesSoochow UniversitySuzhou 215123P.R.China Department of Chemistry University of Western OntarioLondonOntario N6A 5B7Canada Key Laboratory of Superlight Materials and Surface Technology Ministry of EducationCollege of Material Science and Chemical EngineeringHarbin Engineering UniversityHarbin 150001China Key Laboratory for Green Chemical Technology of Ministry of Education School of Chemical Engineering and TechnologyTianjin UniversityTianjin 300072China

Catalytic hydrogenolysis of end-of-life polyolefins can produce value-added liquid fuels and therefore holds great promises in plastic waste reuse and environmental remediation.The major challenge limiting the recycling economic benefit is the severe methanation(usually>20%)induced by terminal C–C cleavage and fragmentation in polyolefin chains.Here,we overcome this challenge by demonstrating that Ru single-atom catalyst can effectively suppress methanation by inhibiting terminal C–C cleavage and preventing chain fragmentation that typically occurs on multi-Ru sites.The Ru single-atom catalyst supported on CeO_(2)shows an ultralow CH_(4)yield of 2.2%and a liquid fuel yield of over 94.5%with a production rate of 314.93 gfuels gRu^(−1)h^(−1)at 250℃for 6 h.Such remarkable catalytic activity and selectivity of Ru single-atom catalyst in polyolefin hydrogenolysis offer immense opportunities for plastic upcycling.

关键词： catalyst olefin fragmentation

Low Sulfur Low olefin Gasoline Production by RIDOS Technology

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维普期刊数据库

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工程科学（英文版） 2003年第2期1卷 40-46,95页

作者： Li Dadong 1, Shi Yahua 1, Yang Qingyu 2 (1. Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 2. Yanshan Petrochemical Company, SINOPEC, Beijing 102503)

By analysis of the component and structure of a real high olefinic FCC naphtha, a technology of deep desulfurization and olefin saturation with minimal octane loss is developed, which is named RIDOS. The multi functions of RIDOS technology are achieved by using a series of new catalysts, which show the good feed adaptability and operation flexibility. The results of the first commercial RIDOS unit showed that an ultra low sulfur (olefin(<20%) gasoline was produced, while the road octane number lost only 1.3 unit. RIDOS technology provides the possibility for producing the clean fuels meeting most strict specifications.

关键词： FCC naphtha RIDOS olefin sulfur isomerization

Commercial Availability of Nine Developmental olefin Block Copolymers

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China Chemical Reporter 2008年第13期19卷 23-23页

On April 10th,2008 the Dow Chemical Company announced the widespread availabil-ity of nine developmental olefin block copolymers(OBCs).Customers around the world can purchase large-volume quantities of these developme... 详细信息

关键词： developmental quantities purchase olefin widesprea

Development of olefin Polymerization Catalysts and Their Commercialization

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工程科学（英文版） 2003年第2期1卷 75-79页

作者： Mao Bingquan, Yang Yuanyi (Beijing Research Institute of Chemical Industry, SINOPEC, Beijing\ 100013)

As one of the most important products in petrochemical industry, polyolefin, including mainly polyethylene, polypropylene and α\|olefin polymers, is also a major raw material for plastics industry. The market demand for polyolefin in 2002 reached 88 Mt, making two thirds of the demand for thermoplastics. The growth rate of demand will be 5%-7 % in the next five years\+\{\\}. Because of its close relation to nations economy and its peoples daily life, the output of polyolefin becomes an important index of the nations industria lization and modernization level.

关键词： olefin polymerization catalysts development commercialization

Ethylene Polymerization and Copolymerization with Polar Monomers by Benzothiophene-bridged BPMO-Pd Catalysts

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Chinese Journal of Polymer Science 2020年第6期38卷 579-586页

作者： Hong-Liang Mu Jun-Hao Ye Guang-Lin Zhou Kang-Kang Li Zhong-Bao Jian State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China

A series of new bisphosphine-monoxide(BPMO)ligands based on benzothiophene backbone and the corresponding palladium complexes{k2-P(O)(Ph)2-3-PR1R2-C8H4S}PdMeCl{2a:R1=R2=Ph;2b:R1=R2=2-0Me-Ph;2c:R1=R2=2-CF3-Ph;2d:Rl=Ph,R2=2-(2',6'-(OMe)2C6Hz)-C6H4}were synthesized and fully characterized by1H-,13C-,31P-,and 2D-NMR spectroscopy and single-crystal X-ray dfraction.In the presence of Na+B[3,5-(CF3)2C6H3]4(NaBArF),these complexes showed very high activities(up to 2.0 x 10’g-mol-1.h-)for ethylene polymerization.More significantly,these catalysts enabled the copolymerization of ethylene with a broad scope of commercially available polar comonomers such as acrylates,acrylic acid,acrylonitrile,vinyltrialkoxysilane,allyl acetate,and long-chain 6-chloro-1-hexene to give functionalized polyethylene with reasonable catalytic activities(up to 105 g-mol-l.h-)and incorporations(up to 5.3 mol96).This contribution suggests that,besides the modulation of conventionally steric and electronic factors,the connectivity(at dfferent linking positions)of BPMO(P,O)donors to the heteroaryl backbone also greatly infuences the catalyst properties in terms of catalytic activity,polymer branching content,comonomer scope,and comonomer incorporation.

关键词： olefin polymerization Bisphosphine monoxide Plladium Polar monomers Heteroaryl backbone

Asymmetric Hydroformylation of olefins Catalyzed by a Chiral Diphosphite-Rhodium Complex

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Chinese Journal of Chemistry 2004年第2期22卷 203-206页

作者：鄢明黎星术陈新滋 Department of Chemistry and Chemical Engineering Suzhou University Suzhou Jiangsu 215006 China Open Laboratory of Chirotechnology of the Institute of Molecular Technology for Drug Discovery & Synthesis Department of Applied Biology and Chemical Technology The Hong Kong Polytechnic University Hong Kong China

A C2-symmetrical aryl diphosphite derived from chiral binaphthol was prepared and its rhodium complex was used as catalysts in the asymmetric hydroformylation of olefins. High catalytic activity and good regioselectivity were observed. Up to 31.2% ee and 38.1% ee were achieved for the hydroformylation of 4-fluoro-styrene and vinyl acetate respectively. The influences of ligand-to-metal ratio, reaction temperature and the pressure of syn-gas on the enantioselectivity and regioselectivity were also studied.

关键词： diphosphite chiral ligand asymmetric hydroformylation olefin rhodium complex

Hydrogenation of olefins Catalyzed by Highly Active Titanocene/NaH or n-BuLi Catalyst Systems

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Chemical Research in Chinese Universities 2002年第3期18卷 307-310页

作者： SUN Qi SUN Ren-an Department of Chemistry Liaoning Normal UniversityDalian 116029P.R.China

The effects of the substituents on the cyclopentadienyl ring and the reducing agents on the catalytic activity and the stability of titanocene/NaH or n BuLi systems for the hydrogenation of olefins were investigated. For the catalyst systems composed of titanocene/NaH or n BuLi, the nature and the number of the substituents on the cyclopentadienyl ring control the catalytic behavior of those two systems. The effect of the reducing agent on the catalytic activity is relatively small. In addition, the characters of the hydrogenation of various olefins catalyzed respectively by Cp 2TiCl 2/NaH or n BuLi systems were compared.

关键词： Titanocene Nanometric sodium hydride n Butyllithium Hydrogenation catalyst olefin

(Arylimido)vanadium(V)-Alkylidene Complexes as Catalysts for Ring-opening Metathesis Polymerization(ROMP) of Cyclic olefins: Ligand Design for Exhibiting the High Activity

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Chinese Journal of Polymer Science 2019年第10期37卷 943-950,I0002页

作者： Kotohiro Nomura Sapanna Chaimongkolkunasin Department of Chemistry Graduate School of Science Tokyo Metropolitan University

(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalytic activities for ringopening metathesis polymerization(ROMP) of norbornene(NBE). The catalytic activities were affected by the ligand substituents, and V(CHSiMe3)(N-2,6-Cl2C6H3)(OC6X5)(PMe3)2(X = F, Cl) demonstrated the exceptionally high catalytic activities for ROMP of NBE.The complexes polymerized cycloheptene(CHPE) and cis-cyclooctene(COE), and ROMP of COE by the OC6 Cl5 analogue proceeded in a living manner even at 80℃, and the activity increased with increasing the temperature up to 120 ℃. Highly active catalysts for ROMP of cyclic olefins(NBE, cyclopentene, and CHPE) can be generated in situ by premixing isolated V(CHSiMe3)(NC6F5)(O-2,6-iPr2C6H3)(PMe3)2 with 1.0 equiv. of C6F5OH or C6Cl5OH via immediate phenoxy exchange;the activity was affected by the kind of phenol added [TOF in the ROMPs of NBE: 4.62 × 10^4 min^–1(upon addition of C6F5OH) versus 37.3 min^–1(none)].

关键词： olefin metathesis Molecular catalyst Ring-opening metathesis polymerization Cyclic olefin Vanadium catalyst