DOCSLIB.ORG

Thesis Submitted for the Degree of Doctor of Philosophy

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Thesis Submitted for the Degree of Doctor of Philosophy University of Bath PHD The Selective Trimerisation of alpha-Olefins with Chromium Triazacyclohexane Catalysts Coxon, Alex Award date: 2015 Awarding institution: University of Bath Link to publication Alternative formats If you require this document in an alternative format, please contact: [email protected] General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Download date: 23. Sep. 2021 The Selective Trimerisation of α-Olefins with Chromium Triazacyclohexane Catalysts Alexander Gregory Nicholas Coxon A thesis submitted for the degree of Doctor of Philosophy Department of Chemistry University of Bath November 2015 COPYRIGHT Attention is drawn to the fact that copyright of this thesis rests with its author. A copy of this thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with the author and they must not copy it or use material from it except as permitted by law or with the consent of the author. RESTRICTIONS This thesis may not be consulted, photocopied or lent to other libraries without the permission of the author and Lyondell Basell GmbH for three years from the date of acceptance of the thesis. Signed Contents Abbreviations ............................................................................................................... 4 Catalyst Notation ......................................................................................................... 5 Abstract ......................................................................................................................... 6 1. Olefin Oligomerisation ........................................................................................ 7 1.1 Non-Selective Oligomerisation ....................................................................... 8 1.2 Selective Dimerisation .................................................................................. 11 1.3 Ethylene Trimerisation and Tetramerisation ................................................. 25 1.4 Triazacyclohexanes as Ligands ..................................................................... 66 1.5 Chromium Triazacyclohexane Complexes in Catalysis ................................ 70 1.6 Summary ....................................................................................................... 72 2. Chromium Catalysed Linear α-Olefin Trimerisation .................................... 74 2.1 Catalyst Synthesis ......................................................................................... 76 2.2 Catalyst Optimisation .................................................................................... 84 2.3 Investigation of the Halogen Effect .............................................................. 95 2.4 Kinetic Analysis .......................................................................................... 102 2.5 Counter-Ion Variation Using Chromium Triflates ...................................... 107 2.6 Synthesis of Alternative Chromium Halides and Pseudo-Halides .............. 114 2.7 Single Crystal X-Ray Diffraction Analysis ................................................. 120 2.8 Summary ..................................................................................................... 128 3. Mechanistic Insights into α-Olefin Trimerisation ......................................... 129 13 3.1 Characterisation of the Trimer Products via C Labelling ......................... 132 3.2 Investigation of the Catalytic Intermediates................................................ 156 3.3 Investigation of the Elimination Pathways.................................................. 165 3.4 GCMS Analysis and the Discovery of Dimerisation .................................. 171 3.5 Identification of the Side Products of Activation ........................................ 175 3.6 Direct Observation of Catalytic Intermediates via Mass Spectrometry ...... 181 3.7 Summary ..................................................................................................... 200 4. Ethylene Trimerisation: Optimisation and Product Identification............. 202 4.1 Ambient Pressure Testing ........................................................................... 203 4.2 Pressurised Autoclave Testing .................................................................... 209 4.3 Mechanistic Investigation of Co-trimerisation ............................................ 227 4.4 Analysis of the Higher Oligomers ............................................................... 228 4.5 Summary ..................................................................................................... 240 2 5. Experimental Details ....................................................................................... 242 5.1 Catalyst Synthesis ....................................................................................... 243 5.2 Chromium Triflate Substitution Reactions ................................................. 256 5.3 Optimised Liquid LAO Trimerisation Method ........................................... 258 5.4 LAO Trimerisation Conditions ................................................................... 259 5.5 Defined Aluminate Synthesis and Doping .................................................. 273 13 5.6 C 1-Hexene Labelling ............................................................................... 275 2 5.7 H 1-Hexene Labelling ................................................................................ 276 5.8 Gaseous α-Olefin Trimerisation .................................................................. 279 5.9 Branched Alcohol Synthesis ....................................................................... 280 5.10 Air Sensitive Mass Spectrometry Procedure .............................................. 283 Conclusions ............................................................................................................... 284 Acknowledgements .................................................................................................. 286 References ................................................................................................................. 287 13 Appendix 1 - C NMR Data for the C18 Trimers ................................................. 295 Appendix 2 - Single Crystal X-Ray Diffraction Data ........................................... 301 3 Abbreviations 1-Cn A linear α-olefin containing n carbon atoms 1D / 2D One Dimensional / Two Dimensional 2H Deuterium BP Beyond Petroleum (formerly British Petroleum) Cn A hydrocarbon containing n carbon atoms COSY Correlation Spectroscopy (Two dimensional NMR spectroscopy) CrIV A chromium cation with the oxidation state given in superscript Cy Cyclohexyl DABCO 1,4-Diazabicyclo[2.2.2]octane DCM Dichloromethane DFT Density Functional Theory DMAB Dimethylanilinium tetrakis(pentafluorophenyl)borate Eq. Molar equivalents FID Flame Ionisation Detector GCMS Gas Chromatography – Mass Spectrometry HDPE High Density Polyethylene iBu iso-Butyl IR Infrared L Undefined neutral ligand LAO Linear α-Olefin LLDPE Linear Low Density Polyethylene M An undefined metal atom or ion. (m/z) Mass spectrometry peak representing mass over charge, in all cases the charge is equal to one and therefore the peak value equals the relative atomic mass. M Peak Peak corresponding to the monoisotopic mass of a molecule in a mass spectrometry fragmentation spectrum MAO/DMAO Methylaluminoxane / Dry (Depleted) Methylaluminoxane MMAO Modified Methylaluminoxane Na/K Sodium/Potassium liquid alloy NMR Nuclear Magnetic Resonance PET Petroleum Ether o-C6H4F2 ortho-difluorobenzene PNP Bis(diarylphosphino)amine based compounds PNPNH (Diarylphosphino)(aminoarylphosphino)amine based compounds RT Room Temperature R3TAC 1,3,5-Trisalkyl-1,3,5-triazacyclohexane (R3TAC)CrCl3 A generic chromium chloride triazacyclohexane complex TAC 1,3,5-Triazacyclohexane TACN 1,4,7-Triazacyclononane THF Tetrahydrofuran TM Transition Metal TOF Turnover Frequency TON Turnover Number TOF-MS Time Of Flight – Mass Spectrometry UV/Vis Ultraviolet/Visible light (spectroscopy) nC The isotope of carbon with a relative atomic mass of n amu 4 Catalyst Notation 5 Abstract Described herein is research into the production of hydrocarbons suitable for various industrial applications via α-olefin trimerisation.1 This work has been split into three principal chapters that each describe a different aspect of the research carried out. In addition, a comprehensive review is presented into the development of selective oligomerisation, with an emphasis on the role of metallacyclic intermediates. α-Olefin Trimerisation: Catalyst Synthesis and Optimisation The synthesis and characterisation of eight novel chromium triazacyclohexane catalysts is described, including a series
Load more

Recommended publications
  • Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis
    Top Organomet Chem (2016) 54: 93–178 DOI: 10.1007/3418_2015_120 # Springer International Publishing Switzerland 2015 Published online: 21 June 2015 Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis Mikko M. Ha¨nninen, Matthew T. Zamora, and Paul G. Hayes Abstract The research field surrounding rare earth pincer complexes has reached a stage where a comprehensive review about the reactivity and catalytic behavior of these species is justified. In this contribution, we begin with a brief introduction on common strategies for the preparation of rare earth pincer complexes, continuing with a section devoted to the versatile reactivity observed for this class of com- pound. Thereafter, several types of compounds are discussed, including extremely reactive hydrides, cationic species, and intriguing scandium imido complexes. Finally, the last portion of this chapter sums up the hitherto reported catalytic studies, including discussions on ring-opening polymerization of cyclic esters, polymerization of olefins and hydroamination reactions, as well as several exam- ples of more infrequently encountered catalytic processes. Keywords Catalysis Á Lanthanides Á Pincer ligands Á Rare earth metals Á Reactivity Contents 1 Introduction .................................................................................. 94 2 Preparation of Rare Earth Complexes Supported by Pincer Ligands ..................... 95 2.1 Common Synthetic Routes to Rare Earth Pincer Complexes ....................... 95 2.2 Reactions of Metal Complexes That
    [Show full text]
  • Fuel Geometry Options for a Moderated Low-Enriched Uranium Kilowatt-Class Space Nuclear Reactor T ⁎ Leonardo De Holanda Mencarinia,B,Jeffrey C
    Nuclear Engineering and Design 340 (2018) 122–132 Contents lists available at ScienceDirect Nuclear Engineering and Design journal homepage: www.elsevier.com/locate/nucengdes Fuel geometry options for a moderated low-enriched uranium kilowatt-class space nuclear reactor T ⁎ Leonardo de Holanda Mencarinia,b,Jeffrey C. Kinga, a Nuclear Science and Engineering Program, Colorado School of Mines (CSM), 1500 Illinois St, Hill Hall, 80401 Golden, CO, USA b Subdivisão de Dados Nucleares - Instituto de Estudos Avançados (IEAv), Trevo Coronel Aviador José Alberto Albano do Amarante, n 1, 12228-001 São José dos Campos, SP, Brazil ABSTRACT A LEU-fueled space reactor would avoid the security concerns inherent with Highly Enriched Uranium (HEU) fuel and could be attractive to signatory countries of the Non-Proliferation Treaty (NPT) or commercial interests. The HEU-fueled Kilowatt Reactor Using Stirling Technology (KRUSTY) serves as a basis for a similar reactor fueled with LEU fuel. Based on MCNP6™ neutronics performance estimates, the size of a 5 kWe reactor fueled with 19.75 wt% enriched uranium-10 wt% molybdenum alloy fuel is adjusted to match the excess reactivity of KRUSTY. Then, zirconium hydride moderator is added to the core in four different configurations (a homogeneous fuel/moderator mixture and spherical, disc, and helical fuel geometries) to reduce the mass of uranium required to produce the same excess reactivity, decreasing the size of the reactor. The lowest mass reactor with a given moderator represents a balance between the reflector thickness and core diameter needed to maintain the multiplication factor equal to 1.035, with a H/D ratio of 1.81.
    [Show full text]
  • Delayed Hydride Cracking in Zirconium Alloys in Pressure Tube Nuclear Reactors
    IAEA-TECDOC-1410 Delayed hydride cracking in zirconium alloys in pressure tube nuclear reactors Final report of a coordinated research project 1998–2002 October 2004 IAEA-TECDOC-1410 Delayed hydride cracking in zirconium alloys in pressure tube nuclear reactors Final report of a coordinated research project 1998–2002 October 2004 The originating Section of this publication in the IAEA was: Nuclear Power Technology Development Section International Atomic Energy Agency Wagramer Strasse 5 P.O. Box 100 A-1400 Vienna, Austria DELAYED HYDRIDE CRACKING IN ZIRCONIUM ALLOYS IN PRESSURE TUBE NUCLEAR REACTORS IAEA, VIENNA, 2004 IAEA-TECDOC-1410 ISBN 92–0–110504–5 ISSN 1011–4289 © IAEA, 2004 Printed by the IAEA in Austria October 2004 FOREWORD This report documents the work performed in the Coordinated Research Project (CRP) on Hydrogen and Hydride Degradation of the Mechanical and Physical Properties of Zirconium Alloys. The Project consisted of hydriding samples of Zr-2.5 Nb pressure tube materials used in CANDU-type and RBMK reactors, the measurement of delayed hydride cracking (DHC) rates under specified conditions, and analysis of hydrogen concentrations. The project was overseen by a supervisory group of experts in the field who provided advice and assistance to the participants as required. All of the research work undertaken as part of the CRP is described in this report, which includes a review of the state of the art in understanding crack propagation by DHC and details of the experimental procedures that produced the most consistent set of DHC rates reported in an international round-robin exercise to this date. All of the participants and many of their co-workers in the laboratories involved in the CRP contributed results and material used in the drafting of this report, which contains compilations of all of the results, their analysis, discussions of their interpretation and conclusions and recommendations for further work.
    [Show full text]
  • NETS 2020 Template
    بÀƵƧǘȁǞƧƊǶ §ȲȌǐȲƊǿ ƊƧDzɈȌɈǘƵwȌȌȁƊȁƮȌȁ ɈȌwƊȲȺɈǘȲȌɐǐǘƊƮɨƊȁƧǞȁǐ خȁɐƧǶƵƊȲɈƵƧǘȁȌǶȌǐǞƵȺƊȁƮ ǞȁȁȌɨƊɈǞȌȁ ǞȺ ȺȯȌȁȺȌȲƵƮ Ʀɯ ɈǘƵ ƊDz ªǞƮǐƵ yƊɈǞȌȁƊǶ ׁׂ׀ׂ y0À² ÀǘǞȺ ƧȌȁǏƵȲƵȁƧƵ خׁׂ׀ׂ ةɈǘ׀׃ƊȁƮ ɩǞǶǶƦƵ ǘƵǶƮ ǏȲȌǿȯȲǞǶ ׂ׆ɈǘٌةmƊƦȌȲƊɈȌȲɯ ɩǞǶǶ ƦƵ ǘƵǶƮ ɨǞȲɈɐƊǶǶɯ ȺȌ ɈǘƊɈ ɈǘƵ ƵȁɈǞȲƵ y0À² خƧȌǿǿɐȁǞɈɯǿƊɯȯƊȲɈǞƧǞȯƊɈƵǞȁɈǘǞȺƵɮƧǞɈǞȁǐǿƵƵɈǞȁǐ ǐȌɨخȌȲȁǶخخׁׂ׀ȁƵɈȺׂششبǘɈɈȯȺ Nuclear and Emerging Technologies for Space Sponsored by Oak Ridge National Laboratory, April 26th-30th, 2021. Available online at https://nets2021.ornl.gov Table of Contents Table of Contents .................................................................................................................................................... 1 Thanks to the NETS2021 Sponsors! ...................................................................................................................... 2 Nuclear and Emerging Technologies for Space 2021 – Schedule at a Glance ................................................. 3 Nuclear and Emerging Technologies for Space 2021 – Technical Sessions and Panels By Track ............... 6 Nuclear and Emerging Technologies for Space 2021 – Lightning Talk Final Program ................................... 8 Nuclear and Emerging Technologies for Space 2021 – Track 1 Final Program ............................................. 11 Nuclear and Emerging Technologies for Space 2021 – Track 2 Final Program ............................................. 14 Nuclear and Emerging Technologies for Space 2021 – Track 3 Final Program ............................................. 18
    [Show full text]
  • Catalytic Systems Based on Cp2zrx2 (X = Cl, H), Organoaluminum
    catalysts Article Catalytic Systems Based on Cp2ZrX2 (X = Cl, H), Organoaluminum Compounds and Perfluorophenylboranes: Role of Zr,Zr- and Zr,Al-Hydride Intermediates in Alkene Dimerization and Oligomerization Lyudmila V. Parfenova 1,* , Pavel V. Kovyazin 1, Almira Kh. Bikmeeva 1 and Eldar R. Palatov 2 1 Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia; [email protected] (P.V.K.); [email protected] (A.K.B.) 2 Bashkir State University, st. Zaki Validi, 32, 450076 Ufa, Russia; [email protected] * Correspondence: [email protected]; Tel.: +7-347-284-3527 i i Abstract: The activity and chemoselectivity of the Cp2ZrCl2-XAlBu 2 (X = H, Bu ) and [Cp2ZrH2]2- ClAlEt2 catalytic systems activated by (Ph3C)[B(C6F5)4] or B(C6F5)3 were studied in reactions with 1-hexene. The activation of the systems by B(C6F5)3 resulted in the selective formation of head- to-tail alkene dimers in up to 93% yields. NMR studies of the reactions of Zr complexes with organoaluminum compounds (OACs) and boron activators showed the formation of Zr,Zr- and Zr,Al-hydride intermediates, for which diffusion coefficients, hydrodynamic radii, and volumes were estimated using the diffusion ordered spectroscopy DOSY. Bis-zirconium hydride clusters of type x[Cp ZrH ·Cp ZrHCl·ClAlR ]·yRnAl(C F ) − were found to be the key intermediates of alkene 2 2 2 2 6 5 3 n dimerization, whereas cationic Zr,Al-hydrides led to the formation of oligomers. Citation: Parfenova, L.V.; Kovyazin, P.V.; Bikmeeva, A.K.; Palatov, E.R.
    [Show full text]
  • Formation of Superhexagonal Chromium Hydride by Exposure of Chromium Thin Film to High Temperature, High Pressure Hydrogen in a Ballistic Compressor
    Portland State University PDXScholar Dissertations and Theses Dissertations and Theses 1991 Formation of Superhexagonal Chromium Hydride by Exposure of Chromium Thin Film to High Temperature, High Pressure Hydrogen in a Ballistic Compressor Yi Pan Portland State University Follow this and additional works at: https://pdxscholar.library.pdx.edu/open_access_etds Let us know how access to this document benefits ou.y Recommended Citation Pan, Yi, "Formation of Superhexagonal Chromium Hydride by Exposure of Chromium Thin Film to High Temperature, High Pressure Hydrogen in a Ballistic Compressor" (1991). Dissertations and Theses. Paper 1243. https://doi.org/10.15760/etd.1242 This Dissertation is brought to you for free and open access. It has been accepted for inclusion in Dissertations and Theses by an authorized administrator of PDXScholar. Please contact us if we can make this document more accessible: [email protected]. FORMATION OF surPERHEXAGONAL CHROMIUM HYDRIDE BY EXPOSURE OF CHIW~[IUM THIN !FILM TO HIGH TEMPERATURE, HIGH PRESSURE: l![YDROGEN IN A BALLISTIC COMPRESSOR by YI PAN A dissertation submitted inlpartial fulfillment of the requirement for the degree of DOCTOR OF PHILOSOPHY in ENVIRONMENT}\L I SCIENCES I AND RESOURCES: PHYSICS Portland State University 1991 TO THE OFFICE OF GRADUATE STUDIES: The memlbers of the Committee approve the dissertation of Yi Pan presented in June 27, 1991. Donald Howard odegom APPROVED: C. William Savery, Vice Provost(/for Graduate Studies and Researclil AN ABSTRACT OF THE DISSERTATION OF Yi Pan for
    [Show full text]
  • 2013 Book Modernorganoalum
    41 Topics in Organometallic Chemistry Editorial Board: M. Beller l J. M. Brown l P. H. Dixneuf A. Fu¨rstner l L. J. Gooßen l L. S. Hegedus P. Hofmann l T. Ikariya l L. A. Oro l Q.-L. Zhou Topics in Organometallic Chemistry Recently Published Volumes Organometallic Pincer Chemistry Photophysics of Organometallics Volume Editors: Gerard van Koten, Volume Editor: A. J. Lees David Milstein Vol. 29, 2010 Vol. 40, 2013 Molecular Organometallic Materials Organometallics and Renewables for Optics Volume Editors: Michael A. R. Meier, Volume Editors: H. Le Bozec, V. Guerchais Bert M. Weckhuysen, Pieter C. A. Bruijnincx Vol. 28, 2010 Vol. 39, 2012 Transition Metal Catalyzed Enantioselective Conducting and Magnetic Organometallic Allylic Substitution in Organic Synthesis Molecular Materials Volume Editor: Uli Kazmaier Volume Editors: M. Fourmigue´, L. Ouahab Vol. 38, 2011 Vol. 27, 2009 Bifunctional Molecular Catalysis Metal Catalysts in Olefin Polymerization Volume Editors: T. Ikariya, M. Shibasaki Volume Editor: Z. Guan Vol. 37, 2011 Vol. 26, 2009 Asymmetric Catalysis from a Chinese Perspective Bio-inspired Catalysts Volume Editor: Shengming Ma Volume Editor: T. R. Ward Vol. 36, 2011 Vol. 25, 2009 Higher Oxidation State Organopalladium Directed Metallation and Platinum Chemistry Volume Editor: N. Chatani Volume Editor: A. J. Canty Vol. 24, 2007 Vol. 35, 2011 Regulated Systems for Multiphase Catalysis Iridium Catalysis Volume Editors: W. Leitner, M. Ho¨lscher Volume Editor: P. G. Andersson Vol. 23, 2008 Vol. 34, 2011 Iron Catalysis – Fundamentals and Organometallic Oxidation Catalysis Applications Volume Editors: F. Meyer, C. Limberg Volume Editor: B. Plietker Vol. 22, 2007 Vol. 33, 2011 N-Heterocyclic Carbenes in Transition Medicinal Organometallic Chemistry Metal Catalysis Volume Editors: G.
    [Show full text]
  • A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State Anne K
    Article Cite This: J. Am. Chem. Soc. 2019, 141, 11970−11975 pubs.acs.org/JACS A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State Anne K. Hickey,† Samuel M. Greer,|,§ Juan A. Valdez-Moreira,† Sean A. Lutz,† Maren Pink,† Jordan A. DeGayner,‡ T. David Harris,‡ Stephen Hill,|,∧ Joshua Telser,∥ and Jeremy M. Smith*,† † Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States | National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States § ∧ Department of Chemistry & Biochemistry and Department of Physics, Florida State University, Tallahassee, Florida 32306, United States ‡ Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States ∥ Department of Biological, Physical and Health Sciences, Roosevelt University, Chicago, Illinois 60605, United States *S Supporting Information :44:57 (UTC). ABSTRACT: Structural and spectroscopic characterization of the dimeric iron t hydride complex [Ph2B( BuIm)2FeH]2 reveals an unusual structure in which a tetrahedral iron(II) site (S = 2) is connected to a square planar iron(II) site (S =1) by two bridging hydride ligands. Magnetic susceptibility reveals strong ferromagnetic coupling between iron centers, with a coupling constant of J = −1 o legitimately share published articles. +110(12) cm , to give an S = 3 ground state. High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy confirms this model. A qualitative molecular orbital analysis of the electronic structure, as supported by electronic structure calculations, reveals that the observed spin configuration results from the orthogonal alignment of two geometrically distinct four-coordinate iron fragments held together by highly covalent hydride ligands.
    [Show full text]
  • ( 12 ) United States Patent
    US010450388B2 (12 ) United States Patent (10 ) Patent No. : US 10 ,450 , 388 B2 Duchateau et al. (45 ) Date of Patent: Oct . 22, 2019 6 , 028 , 151 A 2 / 2000 Wasserman et al . ( 54 ) PROCESS FOR THE PREPARATION OF A 6 , 248 ,837 B1 6 /2001 Chung et al. BRANCHED POLYOLEFIN 6 , 258 , 902 B1 7 /2001 Campbell, Jr . et al. 2008 /0311812 A1 * 12/ 2008 Arriola CO8F 10 / 00 (71 ) Applicant: SABIC GLOBAL TECHNOLOGIES 442 /327 B . V . , Bergen op Zoom (NL ) 2009 /0048399 AL 2 /2009 Reijntjens et al . 2014 / 0039138 A1 2 /2014 Giesbrecht et al. 2014 / 0039139 A1 2 / 2014 Giesbrecht et al . (72 ) Inventors: Robbert R . Duchateau , Eindhoven 2014 /0039140 A1 2 /2014 Giesbrecht et al. (NL ) ; Miloud Bouyahyi , Eindhoven 2014 /0055250 A12 /2014 Speegle et al . (NL ) ; Lidia Jasinska - Walc , Eindhoven 2014 /0350200 A1 11 /2014 Baintas - Geurts et al . (NL ) ; Martin Alexander Zuideveld , Kelmis (BE ) FOREIGN PATENT DOCUMENTS (73 ) Assignee : SABIC GLOBAL TECHNOLOGIES EP 1092730 A14 / 2001 EP 1283222 A1 2 / 2003 B . V . , Bergen op Zoom (NL ) EP 1605000 AL 12 / 2005 WO 9319104 AL 9 / 1993 ( * ) Notice : Subject to any disclaimer , the term of this WO 9613529 A15 / 1996 patent is extended or adjusted under 35 WO 9632427 Al 10 / 1996 U . S . C . 154 (b ) by 0 days . WO 9742232 A1 11/ 1997 WO 9742236 AL 11 / 1997 (21 ) Appl. No. : 15 /537 , 926 WO 0043426 Al 7 / 2000 WO 0123441 A1 4 / 2001 WO 03014046 A1 2 / 2003 (22 ) PCT Filed : Dec . 23 , 2015 Wo 2004081064 AL 9 / 2004 wo 2007134851 AL 11 / 2007 ( 86 ) PCT No .
    [Show full text]
  • The Selective Oligomerization of Ethylene Using Chromium Diphosphine Catalysts
    The Selective Oligomerization of Ethylene Using Chromium Diphosphine Catalysts and The Synthesis and Reactivity of Group 7 Carbonyl Derivatives Relevant to Synthesis Gas Conversion Thesis by Paul Richard Elowe In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, California 2009 (Defended July 17, 2008) 2009 Paul Richard Elowe All Rights Reserved ii Dédiée à ma famille, and to An iii Acknowledgments Spending the last five years of my life at Caltech has been quite an experience. When my undergraduate advisor Donald Berry told me that graduate studies at Caltech are unique, I could not realize how true that was at the time. There have been many good moments, and surely many challenging ones as well. I went from being John Bercaw’s academic grandson to his son in a matter of a few months in the summer of 2003. John has allowed me from the very beginning to work on the projects I was most interested in. His hands-off approach was instrumental in my rapid development as a chemist over the last few years. Thank you for everything you have brought me all these years. I also want to acknowledge Jay Labinger for his guidance. Always available, Jay answered many questions and helped out whenever I was stuck on a problem. I truly enjoyed playing tennis with you. I should also thank my thesis committee, Harry Gray, David Tirrell, and Jacqueline Barton, for great advice during candidacy, as well as throughout the proposals and thesis exams.
    [Show full text]
  • Phase Transformations, Crystal and Magnetic Structures of High-Pressure Hydrides of D-Metals V.E
    L Journal of Alloys and Compounds 330±332 (2002) 110±116 www.elsevier.com/locate/jallcom Phase transformations, crystal and magnetic structures of high-pressure hydrides of d-metals V.E. Antonov* Institute of Solid State Physics, Russian Academy of Sciences, 142432 Chernogolovka, Moscow District, Russia Abstract This paper will brie¯y discuss the high-pressure-hydrogen techniques used at the Institute of Solid State Physics, Russian Academy of Sciences, the T±P diagrams of the studied binary metal±hydrogen systems and the crystal and magnetic structures of high-pressure hydrides formed in those systems. A compilation of the available experimental data and a list of relevant publications are provided for reference purposes. 2002 Elsevier Science B.V. All rights reserved. Keywords: Metal hydrides; Crystal structure; Magnetic properties 1. Introduction copper when the temperature is raised and forms Cu±Ga alloys of increasing thermal stability as its concentration in Most transition metals form hydrides at suf®ciently high the copper matrix decreases. Te¯on, Cu and Ga are largely pressures of hydrogen. The technique for compressing impermeable to hydrogen. The dead space in the copper gaseous hydrogen to pressures of up to 9 GPa at tempera- capsule is ®lled with kaolin wool which does not react tures up to 5008C [1], and recently to 10008C [2], with H2 , Cu and d-metals in the T±P range of interest. developed at the Institute of Solid State Physics, Russian Due to the hardness of its ®bres, the wool remains porous Academy of Sciences (ISSP RAS), made it possible to even at high pressures, leaving enough room for the synthesise hydrides of all 3d-metals and of all 4d-metals hydrogen gas inside the capsule and ensuring good access except Ru.
    [Show full text]
  • 中文名稱英文名稱CAS.NO. 二乙縮醛acetal 105-57-7 乙醛
    中文名稱 英文名稱 CAS.NO.
    [Show full text]