Cationic Oligomerization of Ethylene Oxide
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Cationic/Anionic/Living Polymerizationspolymerizations Objectives
Chemical Engineering 160/260 Polymer Science and Engineering LectureLecture 1919 -- Cationic/Anionic/LivingCationic/Anionic/Living PolymerizationsPolymerizations Objectives • To compare and contrast cationic and anionic mechanisms for polymerization, with reference to free radical polymerization as the most common route to high polymer. • To emphasize the importance of stabilization of the charged reactive center on the growing chain. • To develop expressions for the average degree of polymerization and molecular weight distribution for anionic polymerization. • To introduce the concept of a “living” polymerization. • To emphasize the utility of anionic and living polymerizations in the synthesis of block copolymers. Effect of Substituents on Chain Mechanism Monomer Radical Anionic Cationic Hetero. Ethylene + - + + Propylene - - - + 1-Butene - - - + Isobutene - - + - 1,3-Butadiene + + - + Isoprene + + - + Styrene + + + + Vinyl chloride + - - + Acrylonitrile + + - + Methacrylate + + - + esters • Almost all substituents allow resonance delocalization. • Electron-withdrawing substituents lead to anionic mechanism. • Electron-donating substituents lead to cationic mechanism. Overview of Ionic Polymerization: Selectivity • Ionic polymerizations are more selective than radical processes due to strict requirements for stabilization of ionic propagating species. Cationic: limited to monomers with electron- donating groups R1 | RO- _ CH =CH- CH =C 2 2 | R2 Anionic: limited to monomers with electron- withdrawing groups O O || || _ -C≡N -C-OR -C- Overview of Ionic Chain Polymerization: Counterions • A counterion is present in both anionic and cationic polymerizations, yielding ion pairs, not free ions. Cationic:~~~C+(X-) Anionic: ~~~C-(M+) • There will be similar effects of counterion and solvent on the rate, stereochemistry, and copolymerization for both cationic and anionic polymerization. • Formation of relatively stable ions is necessary in order to have reasonable lifetimes for propagation. -
Poly(Ethylene Oxide-Co-Tetrahydrofuran) and Poly(Propylene Oxide-Co-Tetrahydrofuran): Synthesis and Thermal Degradation
Revue Roumaine de Chimie, 2006, 51(7-8), 781–793 Dedicated to the memory of Professor Mircea D. Banciu (1941–2005) POLY(ETHYLENE OXIDE-CO-TETRAHYDROFURAN) AND POLY(PROPYLENE OXIDE-CO-TETRAHYDROFURAN): SYNTHESIS AND THERMAL DEGRADATION Thomas HÖVETBORN, Markus HÖLSCHER, Helmut KEUL∗ and Hartwig HÖCKER Lehrstuhl für Textilchemie und Makromolekulare Chemie der Rheinisch-Westfälischen Technischen Hochschule Aachen, Pauwelsstr. 8, 52056 Aachen, Germany Received January 12, 2006 Copolymers of tetrahydrofuran (THF) and ethylene oxide (EO) (poly(THF-co-EO) and THF and propylene oxide (PO) (poly(THF-co-PO) were obtained by cationic ring opening polymerization of the monomer mixture at 0°C using boron trifluoride etherate (BF3.OEt2) as the initiator. From time conversion plots it was concluded that both monomers are consumed from the very beginning of the reaction and random copolymers are obtained. For poly(THF-co-PO) the molar ratio of repeating units was varied from [THF]/[PO] = 1 to 10; the molar ratio of monomers in the feed corresponds to the molar ratio of repeating units in the copolymer. Thermogravimetric analysis of the copolymers revealed that both poly(THF-co-EO) and poly(THF-co-PO) decompose by ca. 50°C lower than poly(THF) and by ca. 100°C lower than poly(EO); 50% mass loss is obtained at T50 = 375°C for poly(EO), T50 = 330°C for poly(THF) and at T50 = 280°C for both copolymers. The [THF]/[PO] ratio does not influence the decomposition temperature significantly as well. For the copolymers the activation energies of the thermal decomposition (Ea) were determined experimentally from TGA measurements and by density functional calculations on model compounds on the B3LYP/6-31+G* level of theory. -
(12) United States Patent DX
USOO7300.953B2 (12) United States Patent (10) Patent No.: US 7,300,953 B2 Nishino et al. (45) Date of Patent: Nov. 27, 2007 (54) PROCESS FOR PREPARING NITRILE JP 54-122220 A 9, 1979 COMPOUND, CARBOXYLIC ACID JP 59-51251. A 3, 1984 COMPOUND OR CARBOXYLIC ACID JP 8-5O1299. A 2, 1996 ESTER COMPOUND JP 200O281672 A * 10, 2000 WO WO-94/05639 A1 3, 1994 (75) Inventors: Shigeyoshi Nishino, Ube (JP); Kenji Hirotsu, Ube (JP); Hidetaka Shima, OTHER PUBLICATIONS Ube (JP); Keiji Iwamoto, Ube (JP); Lawerence I. Kruse et al., J. Med. Chem. 1990, vol. 33, No. 2, pp. Takashi Harada, Ube (JP) T81 to 789. Christoph Strassier et al., Helvetica Chimica Acta, vol. 80, pp. 1528 (73) Assignee: Ube Industries, Ltd, Ube-shi (JP) to 1554, 1997. (*) Notice: Subject to any disclaimer, the term of this * cited by examiner patent is extended or adjusted under 35 Primary Examiner Kamal A. Saeed U.S.C. 154(b) by 0 days. Assistant Examiner Shawquia Young (74) Attorney, Agent, or Firm—Birch, Stewart, Kolasch & (21) Appl. No.: 10/572,373 Birch, LLP (22) PCT Filed: Sep. 17, 2004 (57) ABSTRACT PCT/UP2004/O13626 (86). PCT No.: The present invention discloses a process for preparing a S 371 (c)(1), nitrile compound, a carboxylic acid compound or a carboxy (2), (4) Date: Mar. 16, 2006 lic acid ester compound represented by the formula (2): (87) PCT Pub. No.: WO2005/0284.10 (2) PCT Pub. Date: Mar. 31, 2005 R (65) Prior Publication Data R 1. R2 US 2006/0287541 A1 Dec. -
US2278550.Pdf
April 7, 1942. D. J. OER E. A. 2,278,550 PREPARATION OF ALKALI METAL ALKOXIDES Filed June 21, 1939 REACTION ------ REGENERATION OFMX FROM M-represents an alkali metal N-represents a number from 2 to 3 R-represents an alkyl group X-represents the anion of a weak acid Donald D. Lee Donald J. Loder NVENTOR BY 232 az - ATTORNEY Patented Apr. 7, 1942 2,278,550 UNITED STATES PATENT OFFICE 2,278,550 PREPARATION OF ALKALI METAL ALKOXDES Donald J. Loder and Donald D. Lee, Wilmington, Del, assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware Application June 21, 1939, Serial No. 280,308 16 Claims. (CI. 260-632) The invention relates to improvements in the and R is an alkyl, or aralkyl radical which may be manufacture of metal alkoxides and more particu Saturated, unsaturated, substituted or unsub larly to the preparation of alkali metal alkoxides stituted. by the interaction of alcohols with alkali metal In Reactions 1 and 2, an alkali metal salt of a salts of weak acids. weak acid is digested with an alcohol at an ap Alkali metal alkoxides have been prepared by propriate temperature, the digestion being Con. direct reaction of the alkali metal as such with tinued until equilibrium has been substantially an alcohol. or by action of an alkali metal hy reached. The equilibrium mixture is filtered for. droxide. upon an alcohol. The higher cost of the the separation of any undissolved (MX or M3X) first of these methods has limited somewhat the O salt and the resulting solution (or filtrate) is industrial use of the alkoxide thus prepared and found to contain an alkali metal alkoxide, or much effort has been expended in endeavors to aralkoxide, (MOR) hereinafter called 'al make the second more commercially practicable. -
Alkoxylated Fatty Esters and Derivatives from Natural
(19) TZZ ¥¥ZZ_T (11) EP 2 633 008 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 211/00 (2006.01) 20.03.2019 Bulletin 2019/12 (86) International application number: (21) Application number: 11838497.3 PCT/US2011/057595 (22) Date of filing: 25.10.2011 (87) International publication number: WO 2012/061092 (10.05.2012 Gazette 2012/19) (54) ALKOXYLATED FATTY ESTERS AND DERIVATIVES FROM NATURAL OIL METATHESIS ALKOXYLIERTE FETTESTER UND DERIVATE AUS EINER ERDÖLMETATHESE ESTERS GRAS ALCOXYLÉS ET DÉRIVÉS À PARTIR DE LA MÉTATHÈSE D’HUILES NATURELLES (84) Designated Contracting States: • HOLLAND, Brian AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Deerfield GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO IL 60015 (US) PL PT RO RS SE SI SK SM TR • MALEC, Andrew, D. Chicago (30) Priority: 25.10.2010 US 406556 P IL 60657 (US) 25.10.2010 US 406570 P • MASTERS, Ronald, A. 25.10.2010 US 406547 P Glenview IL 60025 (US) (43) Date of publication of application: • MURPHY, Dennis, S. 04.09.2013 Bulletin 2013/36 Libertyville IL 60048 (US) (73) Proprietor: Stepan Company •SKELTON,Patti Northfield, Illinois 60093 (US) Winder GA 30680 (US) (72) Inventors: • SOOK, Brian • ALLEN, Dave, R. Lawrenceville Chicago GA 30045 (US) IL 60610 (US) • WIESTER, Michael •ALONSO,Marcos Chicago Chicago IL 60625 (US) IL 60645-4922 (US) • WOLFE, Patrick, Shane • BERNHARDT, Randal, J. Palatine Antioch IL 60074 (US) IL 60002 (US) • BROWN, Aaron (74) Representative: Müller, Christian Stefan Gerd Chicago ZSP Patentanwälte -
United States Patent (19) 11) 4,448,977 Warner Et Al
United States Patent (19) 11) 4,448,977 Warner et al. 45 May 15, 1984 54 STABLIZED ACETALACD (56) References Cited COMPOSITIONS U.S. PATENT DOCUMENTS 75 Inventors: Glenn H. Warner, St. Albans; Louis 2,546,018 3/1951 Smith et al. ......................... 549/417 F. Theiling, Jr., Charleston, both of 2,801,216 7/1957 Yoder et al. ........................ 549/47 W. Va.; Marvin G. Freid, Putnam 3,023,243 2/1962 Stansbury et al. .................. 549/416 Valley, N.Y. OTHER PUBLICATIONS Assignee: (73) Union Carbide Corporation, Harries, C. and Tank, L., Chem. Ber. 41, 1701 (1908). Danbury, Conn. Mutterer, F., Morgen, J., Biedermann, J., Fleury, J. and 21) Appl. No.: 411,620 Weiss, R., Bull. Soc. Chim. France, No. 12, 4478-4486 (1969). 22 Filed: Aug. 26, 1982 Kankaanpera, K., Acta. Chem. Scan. 23, 1465-1470 (1969). Related U.S. Application Data Primary Examiner-Nicky Chan 63 Continuation-in-part of Ser. No. 178,133, Aug. 14, 1980, abandoned, which is a continuation of Ser. No. Attorney, Agent, or Firm-Gerald L. Coon; Henry H. 961,714, Nov. 17, 1978, Pat. No. 4,244,876. Gibson 51 Int. Cl. .................... CO7D 309/06; CO7C 41/46; 57 ABSTRACT CO7C47/198 A storage stable composition of glutaraldehyde acetals (52) U.S. C. .................................... 549/201; 568/421; and an organic acidic catalyst, which can be converted 568/581; 568/465; 568/483; 568/486; 252/855 to glutaraldehyde at the site and upon demand, by the addition of water. (58 Field of Search ................ 549/201, 417; 568/421, 568/581, 582, 496, 497,600, 603 9 Claims, No Drawings 4,448,977 2 wherein R has a value of from 1 to 6, preferably from 1 STABLIZED ACETALACID COMPOSITIONS to 3, will produce a mixture of the corresponding 2,6- dialkoxy-tetrahydropyran, dialkoxypentanal and This application is a continuation-in-part of applica 1,1,5,5-tetraalkoxy-pentane; which mixture can be sub tion Ser. -
UNIVERSITY of CALIFORNIA Los Angeles Biodegradation of 1,4
UNIVERSITY OF CALIFORNIA Los Angeles Biodegradation of 1,4-Dioxane in Co-Contaminant Mixtures A dissertation submitted in partial satisfaction of the requirements for the degree Doctor of Philosophy in Civil Engineering by Shu Zhang 2017 © Copyright by Shu Zhang 2017 ABSTRACT OF THE DISSERTATION Biodegradation of 1,4-Dioxane in Co-Contaminant Mixtures by Shu Zhang Doctor of Philosophy in Civil Engineering University of California, Los Angeles, 2017 Professor Shaily Mahendra, Chair Bioremediation is a promising technology to degrade or detoxify various organic and inorganic compounds in polluted environments by using microbiological activity, but it is sensitive to biogeochemical conditions as well as co-occuring compounds at impacted sites. This study focused on biodegradation of 1,4-dioxane, which is a carcinogen and an emerging water contaminant. 1,4-Dioxane was utilized as a stabilizer of chlorinated solvents, such as 1,1,1- trichloroethane (TCA); and it has been found widespread in groundwater. Many US states are implementing lower regulatory advisory levels based on the toxicity profile of 1,4-dioxane and the potential public health risks. However, the unique chemical properties of 1,4-dioxane, such as high water solubility, low Henry’s law constant, and importantly, the co-occurrence with chlorinated solvents and other contaminants, increase the challenges to efficiently cleanup 1,4- ii dioxane contaminations. The objectives of this research were to measure and model the effects of chlorinated solvents on 1,4-dioxane metabolic biodegradation by laboratory pure cultures, elucidate the mechanisms of the inhibition, and test the effects of mixtures of co-contaminants in samples collected from actual 1,4-dioxane contaminated sites. -
Cationic Polymerization of Hexamethylcyclotrisiloxane in Excess Water
molecules Communication Cationic Polymerization of Hexamethylcyclotrisiloxane in Excess Water Quentin Barnes 1, Claire Longuet 2 and François Ganachaud 1,* 1 Ingénierie des Matériaux Polymères, CNRS UMR 5223, INSA-Lyon, Univ Lyon, F-69621 Villeurbanne, France; [email protected] 2 IMT—Mines Ales, Polymers Hybrids and Composites (PCH), 6 Avenue De Clavières, F-30319 Alès, France; [email protected] * Correspondence: [email protected]; Tel.: +33-683-021-802 Abstract: Ring-opening ionic polymerization of cyclosiloxanes in dispersed media has long been discovered, and is nowadays both fundamentally studied and practically used. In this short com- munication, we show some preliminary results on the cationic ring-opening polymerization of hexamethylcyclotrisiloxane (D3), a crystalline strained cycle, in water. Depending on the catalyst or/and surfactants used, polymers of various molar masses are prepared in a straightforward way. Emphasis is given here on experiments conducted with tris(pentafluorophenyl)borane (BCF), where high-molar polymers were generated at room temperature. In surfactant-free conditions, µm-sized droplets are stabilized by silanol end-groups of thus generated amphiphilic polymers, the latter of which precipitate in the course of reaction through chain extension. Introducing various surfactants in the recipe allows generating smaller emulsions in size with close polymerization ability, but better final colloidal stability, at the expense of low small cycles’ content. A tentative mechanism is Citation: Barnes, Q.; Longuet, C.; Ganachaud, F. Cationic finally proposed. Polymerization of Hexamethylcyclotrisiloxane in Keywords: Piers-Rubinsztajn catalyst; surfactant-free polymerization; polydimethylsiloxane Excess Water. Molecules 2021, 26, 4402. https://doi.org/10.3390/ molecules26154402 1. Introduction Academic Editors: Sławomir Silicones are polymers of broad interest, both on industrial and academic sides. -
Complexes Ivan Habuš, Zlata Raza, and Vitomir Šunjić*
CROATICA CHEMICA ACTA CCACAA 61 (4) 857-866 (1988) OriginaL ScientiJic Paper CCA-1833 UDC 54.05 YU ISSN 0011-1643 Preparation of Chiral Diphenylphosphines from D-Glucose and Enantioselective Hydrogenation with Their Rh(l) Complexes Ivan Habuš, ZLata Raza, and Vitomir Šunjić* Rudjer Bošković Institute, Department of Organic Chemistry and Biochemistry, P.O.B. 1016, 41001 Zagreb, YugosLavia Received DecembeR 7, 1987 (2R,3S)-2-MethYlsulfonyloXYmeihyl-3-meThYlSulfonYloXY-teTRa- hydropyran (4), derived from n-glucose, is diphenYlphoSphinated to (2R,3R)-2-diphenYlphosphinomethyl-3-diphenYlphosphino-tetrahy- dropyran (7), which is formed as aminor prodUcT. Compound 8 iS the predominant prodUct, formed on 3,4-elimination. PrepaRation and characteRization of The rhodium(I) complexes 10-12 iS deS- cribed. Complex 10 of bidentate Iigand 7 exhibits in hYdrogenation of Z-a-N-acetylaminocinnamic acid enanTioselecTiviTY comparable To That obtained with Rhodium(I) complex of (-)-DIOP (-70010e. e.). SaTUrated monophosphine, (2S)-2-diphenYlphoSphinomethYl-tetra- hYdropYran (9) affords mixed Rhodium(I) compleX (11, 12), Which exhibits low enantioselectiViTY. INTRODUCTION The aSYmmetric catalYTic hYdRogenation of prochiRal alefinS conSTituteS one of The most impressive achieVements to date in catalYtic SelectiviTY. Many RevieWS on thiS topic are available.v? PreviouSlY, we investigated The homo- geneaUS catalytic hYdrogenation of VariouS pRochiral SUbStrates, caTalyzed bY Same known ar neWlY developed Rhodium(I) complexeS of chiral diphe- nylphosphines ar diphenylphoSphinites.š -! We wiSh to describe here The investigation of preparation and enantioselective hydrogenation with chiral diphenYlphoSphines derived from D-glucose, the most widespread monosaccha- ride in nature. These resUlts are of interest in view of The knoWn difficulTieS encountered by others in preparatian of bis-diphenYlphosphineS derived from cyclic diols bY nucleophilic SUbstitution of TheiR activated esteRS, usuaUY TosylaTes ar mesylaTes. -
A Study of the Solvolysis Reactions of Tetrahydrofurfuryl Tosylate
Illinois Wesleyan University Digital Commons @ IWU Honors Projects Chemistry 4-25-2000 A Study of the Solvolysis Reactions of Tetrahydrofurfuryl Tosylate Rebecca Centko '00 Illinois Wesleyan University Follow this and additional works at: https://digitalcommons.iwu.edu/chem_honproj Part of the Chemistry Commons Recommended Citation Centko '00, Rebecca, "A Study of the Solvolysis Reactions of Tetrahydrofurfuryl Tosylate" (2000). Honors Projects. 32. https://digitalcommons.iwu.edu/chem_honproj/32 This Article is protected by copyright and/or related rights. It has been brought to you by Digital Commons @ IWU with permission from the rights-holder(s). You are free to use this material in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s) directly, unless additional rights are indicated by a Creative Commons license in the record and/ or on the work itself. This material has been accepted for inclusion by faculty at Illinois Wesleyan University. For more information, please contact [email protected]. ©Copyright is owned by the author of this document. A Study of The Solvolysis Reactions of Tetrahydrofurfuryl Tosylate Rebecca Centko Advisor: Dr. Ram S. Mohan Chemistry Research Honors Thesis Illinois Wesleyan University April 25,2000 Approval Page A Study of The Solvolysis Reactions of Tetrahydrofurfurfyl Tosylate BY Rebecca Centko A PAPER SUBMITTED AS PART OF THE REQUIREMENT FOR RESEARCH HONORS IN CHEMISTRY Approved: Ram S. Mohan, Ph. D., Research Advisor Illinois Wesleyan University, 1999-2000 Acknowledgements I would like to thank Dr. Ram S. Mohan for the opportunity to work with him and for the countless hours that he has spent with me working on this project. -
(Z)-And (E)-8-Chlorocinnamohydroximoyl Chlorides with Methoxide
REACTION OF (Z)- AND (E)-8-CHLOROCINNAMOHYDROXIMOYL CHLORIDES WITH METHOXIDE ION A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN THE GRADUATE SCHOOL OF THE TEXAS WOMAN'S UNIVERSITY COLLEGE OF ARTS AND SCIENCES BY JIN LIU, B.S. •· ·--···-DENTON, TEXAS DECEMBER 2008 TEXAS WOMAN'S UNIVERSITY DENTON, TEXAS November 7, 2008 To the Dean of the Graduate School: I am submitting herewith a thesis written by Jin Liu entitled "reaction of (z)- and (e)-B-chlorocinnamohydroximoyl chlorides with methoxide ion." I have examined this thesis for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Master of Science with a major in Chemistry. We have read this thesis and recommend its acceptance: Accepted: Dean of the Graduate School ACKNOWLEDGMENTS I cordially thank everyone who helped, supported and encouraged me during my studies in the Department of Chemistry and Physics at Texas Woman's University. I especially thank Dr James E. Johnson for the opportunity to conduct research in his laboratory. Without his patient help and guidance, it would have been impossible to complete the thesis. It is my honor and privilege to work under his instruction. iii ABSTRACT JIN LIU REACTION OF (Z}- AND (E)-~-CHLOROCINNAMOHYDROXIMOYL CHLORIDES WITH METHOXIDE ION DECEMBER 2008 New a,~-unsaturated hydroximoyl chlorides and hydroximates were synthesized and characterized. 13C NMR, 1H NMR, IR and elemental analysis were determined for each new compound. The kinetics of methoxide ion substitution on (Z)- and (E)- ~ chlorocinnamohydroximoy l chloride were measured. -
Anionic Polymerisation of Aziridines
MAX-PLANCK-INSTITUT FÜR POLYMERFORSCHUNG JOHANNES GUTENBERG‐UNIVERSITÄT MAINZ Anionic Polymerisation of Aziridines Diplomarbeit zur Erlangung des Grades eines Diplom‐Chemikers am Institut für Organische Chemie des Fachbereiches Chemie, Pharmazie und Geowissenschaften der Johannes Gutenberg-Universität Mainz vorgelegt von Laura Thomi geboren in Frankfurt am Main Mainz 2013 Diese Arbeit wurde in der Zeit von November 2012 bis Juli 2013 am Institut für Organische Chemie der Johannes Gutenberg‐Universität Mainz und am Max-Planck-Institut für Polymerforschung in Mainz unter der Betreuung von Herrn Prof. Dr. Holger Frey und Frau Prof. Dr. Katharina Landfester durchgeführt. für meine Eltern “We live on an island surrounded by a sea of ignorance. As our island of knowledge grows, so does the shore of our ignorance.” - John Archibald Wheeler Danksagung Mein Dank gilt Herrn Prof. Dr. Holger Frey und Frau Prof. Dr. Katharina Landfester für die Bereitstellung des Themas und die ausgezeichneten Arbeitsbedingungen. Zudem danke ich Herrn Dr. Frederik Wurm für die freundliche Aufnahme in seine Gruppe und die hervorragende Betreuung der Arbeit. Bei allen Mitgliedern der Arbeitsgruppe Frey bedanke ich mich für die wunderbare Arbeitsatmosphäre und die Unterstützung bei dieser Arbeit. Herrn Christian Moers und Herrn Jan Seiwert danke ich, dass sie mir die anionische Polymerisation von Styrol und Ethylenoxid näher gebracht haben. Bei Frau Anna Hesse und Herrn Christian Moers bedanke ich mich für das Korrekturlesen dieser Arbeit. Frau Katja Weber danke ich für die Bereitstellung des 2-Methyl-N-tosylaziridins. Für die GPC Messungen danke ich Frau Christine Rosenauer und insbesondere Frau Monika Schmelzer. Bei Frau Dr. Elena Berger-Nicoletti möchte ich mich für zahlreiche MALDI Messungen bedanken.