DOCSLIB.ORG

CO2 As a Monomer for the Phosgene-Free Synthesis of New Polycarbonates : Catalyst Development, Mechanistic Investigations and Monomer Screening

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
CO2 As a Monomer for the Phosgene-Free Synthesis of New Polycarbonates : Catalyst Development, Mechanistic Investigations and Monomer Screening CO2 as a monomer for the phosgene-free synthesis of new polycarbonates : catalyst development, mechanistic investigations and monomer screening Citation for published version (APA): Meerendonk, van, W. J. (2005). CO2 as a monomer for the phosgene-free synthesis of new polycarbonates : catalyst development, mechanistic investigations and monomer screening. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR596016 DOI: 10.6100/IR596016 Document status and date: Published: 01/01/2005 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication 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. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 02. Oct. 2021 CO2 as a Monomer for the Phosgene-free Synthesis of New Polycarbonates Catalyst Development, Mechanistic Investigations and Monomer Screening Wouter Johannes van Meerendonk - 1 - The cover picture shows the result of the first successful copolymerization of cyclohexene oxide and CO2 in the high pressure reactor. CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN Meerendonk, Wouter J. van CO2 as a Monomer for the Phosgene-free Synthesis of New Polycarbonates : Catalyst Development, Mechanistic Investigations and Monomer Screening / by Wouter J. van Meerendonk. – Eindhoven : Technische Universiteit Eindhoven, 2005. Proefschrift. – ISBN 90-386-2797-1 NUR 913 Subject headings: copolymerization / polycarbonate ; preparation / polymerization catalysts ; zinc / carbon dioxide / epoxides ; oxiranes / mass spectrometry ; MALDI-ToF-MS / chain transfer Trefwoorden: copolymerizatie / polycarbonaat ; bereiding / polymerisatiekatalysatoren ; zinc / koolstof dioxide / epoxiden ; oxiranen / massaspectrometrie ; MALDI-ToF / ketenoverdracht © 2005, Wouter J. van Meerendonk Printed by PrintService Ipskamp, The Netherlands. Cover design by Ronald Korporaal, Heerenveen, [email protected] This project forms part of the research program of the Dutch Polymer Institute (DPI), Engineering Plastics, DPI project #286. An electronic copy of this thesis is available from the Eindhoven University Library in PDF format (www.tue.nl/bib). - 2 - CO2 as a Monomer for the Phosgene-free Synthesis of New Polycarbonates Catalyst Development, Mechanistic Investigations and Monomer Screening PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de Rector Magnificus, prof.dr.ir. C.J. van Duijn, voor een commissie aangewezen door het College voor Promoties in het openbaar te verdedigen op maandag 17 oktober 2005 om 16.00 uur door Wouter Johannes van Meerendonk geboren te Amersfoort - 3 - Dit proefschrift is goedgekeurd door de promotoren: prof.dr. C.E. Koning en prof.dr. G.J.M. Gruter Copromotor: dr. R. Duchateau - 4 - “The most exciting phrase to hear in science, the one that heralds new discoveries, is not ‘Eureka!’ (I found it!) but ‘That's funny ...’” - Isaac Asimov - 5 - Table of Contents Glossary of symbols and abbreviations 9 Chapter 1 Introduction 11 1.1 Chemical routes to polycarbonates 11 1.2 Aim of this study 12 1.3 Outline of this thesis 13 1.4 References 15 Chapter 2 Literature overview 17 2.1 The monomers 17 2.2 Homopolymerization of oxiranes 19 2.3 Coupling of oxiranes with CO2 25 2.4 Copolymerization of oxiranes with CO2 26 2.5 Known catalysts for the copolymerizations of oxiranes with CO2 29 2.6 Other oxirane monomers 45 2.7 Summary and outlook 46 2.8 References 47 Chapter 3 Silsesquioxane zinc catalysts for the alternating copolymerization of cyclohexene oxide and carbon dioxide 55 3.1 Introduction 55 3.2 Results and discussion 58 3.3 Experimental section 70 3.4 Acknowledgements 74 3.5 References 74 Chapter 4 High throughput and mechanistic studies of zinc catalysts 79 4.1 Introduction 79 4.2 Results and discussion 81 4.3 Concluding remarks 96 4.4 Experimental section 97 4.5 Acknowledgements 100 4.6 References 101 - 6 - Chapter 5 Alternative monomers for polycarbonate synthesis 105 5.1 Introduction 105 5.2 Results and discussion 107 5.3 Concluding remarks 127 5.4 Experimental section 128 5.5 Acknowledgements 132 5.6 References 133 Chapter 6 Physical properties of compression molded parts and coatings of aliphatic polycarbonates 135 6.1 Introduction 135 6.2 Results and discussion 137 6.3 Concluding remarks 146 6.4 Experimental section 146 6.5 Acknowledgements 149 6.6 References 149 Chapter 7 Epilogue and technology assessment 151 Appendix A Lab scale reactor setup 153 A-1 Introduction 153 A-2 Communication and software setup 154 A-3 LabVIEW 155 A-4 Webcam 156 A-5 References 157 Summary 159 Samenvatting 161 Dankwoord 165 Curriculum Vitae 167 Scientific papers 167 - 7 - Glossary of symbols and abbreviations BDI β-diketiminate ligand CHO Cyclohexene oxide DCM Dichloromethane DMA (or DMTA) Dynamic mechanical (thermal) analysis DMSO Dimethylsulfoxide DSC Differential Scanning Calorimetry EO Ethylene oxide I intensity (% or arbitrary units) M+ Cationization agent (MALDI-ToF-MS analyses) MALDI-ToF-MS Matrix-Assisted-Laser-Desorption-Ionization Time-of-Flight Mass- Spectrometry MPVO Meerwein-Ponndorf-Verley reduction/Oppenauer oxidation MWD Molecular weight distribution M n Number averaged molar mass M w Weight averaged molar mass n Number of repeating units in a polymer chain PCHC Poly(cyclohexene carbonate) PCHO Poly(cyclohexene oxide) PCy3 Tricyclohexyl phosphine PDI Polydispersity index PEO Poly(ethylene oxide) PO Propylene oxide PPC Poly(propylene carbonate) PPO Poly(propylene oxide) PS Polystyrene ROP Ring-Opening Polymerization SEC Size Exclusion Chromatography T Temperature (ºC) TGA Thermogravimetric analyses Tpp Tetraphenyl porphyrin Tg Polymer glass transition temperature (ºC) Tm Polymer melt transition temperature (ºC) - 9 - Chapter 1 Introduction 1.1 Chemical routes to polycarbonates With a global annual demand exceeding 1.5 million tons, polycarbonates form a commercially important class of polymers.1 Due to their toughness and optical clarity, they are widely used for structural parts, impact-resistant glazing, streetlight globes, household appliance parts, components of electrical/electronic devices, compact discs, automotive applications, reusable bottles, food and drink containers, and many other products.2,3 The most important polycarbonate is based on bisphenol-A. Currently, there are two different industrial routes for the synthesis of high molecular weight poly(bisphenol-A carbonate) (BA-PC). The first route involves the interfacial reaction between phosgene and the sodium salt of bisphenol-A in a heterogeneous system. The second route consists of a melt-phase transesterification between a bisphenol-A and diphenyl carbonate (Figure 1-1).1 O + NaO ONa Cl Cl O O O O + HO OH n PhO OPh Figure 1-1. Industrial routes to poly(bisphenol-A carbonate).1 The first route is environmentally undesirable due to the need of the hazardous dichloromethane and phosgene, and the production of large amounts of NaCl as a side product. The second route requires high temperature in order to remove phenol, the high boiling condensation product of this polymerization reaction. A different approach in synthesizing polycarbonates was demonstrated by Inoue et al. in 1969.4 They reported the alternating copolymerization of an oxirane with carbon dioxide, resulting in an aliphatic polycarbonate as is depicted in Figure 1-2. - 11 - Chapter 1 O O O CO2 OO OO R R' R R' R R' n Figure 1-2. Polycarbonate from the copolymerization of an oxirane with CO2 This approach has several advantages over the current industrial processes. In contrast to the step-growth mechanisms applied in the synthesis of BA-PC, the route reported by Inoue is a chain- growth process. Therefore, in theory, a much better control of molecular weight is feasible and monomer conversions do not have to approach unity in order to obtain high molecular weights. Another advantage is that the used monomers do not possess the safety hazards of the current industrial process based on phosgene. Furthermore, since carbon
Load more

Recommended publications
  • Alcohols Combined 1405
    ALCOHOLS COMBINED 1405 Formulas: Table 1 MW: Table 1 CAS: Table 2 RTECS: Table 2 METHOD: 1405, Issue 1 EVALUATION: PARTIAL Issue 1: 15 March 2003 OSHA : Table 2 PROPERTIES: Table 1 NIOSH: Table 2 ACGIH: Table 2 COMPOUNDS: (1) n-butyl alcohol (4) n-propyl alcohol (7) cyclohexanol (2) sec-butyl alcohol (5) allyl alcohol (8) isoamyl alcohol (3) isobutyl alcohol (6) diacetone alcohol (9) methyl isobutyl carbinol SYNONYMS: See Table 3. SAMPLING MEASUREMENT SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID (Coconut shell charcoal, 100 mg/50 mg) ANALYTE: Compounds above FLOW RATE: 0.01 to 0.2 L/min DESORPTION: 1 mL 5% 2-propanol in CS2 Compounds: (1-3 ) (4-9) VOL-MIN: 2 L 1 L INJECTION -MAX: 10 L 10 L VOLUME: 1 µL SHIPMENT: Routine TEMPERATURE -INJECTION: 220 °C SAMPLE -DETECTOR: 250 - 300 °C STABILITY: See Evaluation of Method. -COLUMN: 35 °C (7 minutes), to 60 °C at 5 °C/minute, hold 5 minutes, up to BLANKS: 2 to 10 field blanks per set 120 °C at 10 °C /minute, hold 3 minutes. CARRIER GAS: He, 4 mL/min ACCURACY COLUMN: Capillary, fused silica, 30 m x 0.32-mm RANGE STUDIED: Not studied [1, 2]. ID; 0.5 µm film polyethylene glycol, DB- wax or equivalent BIAS: Not determined CALIBRATION: Solutions of analyte in eluent (internal OVERALL standard optional) PRECISION (Ö ): Not determined rT RANGE: See EVALUATION OF METHOD. ACCURACY: Not determined ESTIMATED LOD: 1 µg each analyte per sample PRECISION: See EVALUATION OF METHOD. APPLICABILITY: This method may be used to determine two or more of the specified analytes simultaneously.
    [Show full text]
  • Section 2. Hazards Identification OSHA/HCS Status : This Material Is Considered Hazardous by the OSHA Hazard Communication Standard (29 CFR 1910.1200)
    SAFETY DATA SHEET Nonflammable Gas Mixture: Arsine / Helium / Phosgene Section 1. Identification GHS product identifier : Nonflammable Gas Mixture: Arsine / Helium / Phosgene Other means of : Not available. identification Product use : Synthetic/Analytical chemistry. SDS # : 006605 Supplier's details : Airgas USA, LLC and its affiliates 259 North Radnor-Chester Road Suite 100 Radnor, PA 19087-5283 1-610-687-5253 24-hour telephone : 1-866-734-3438 Section 2. Hazards identification OSHA/HCS status : This material is considered hazardous by the OSHA Hazard Communication Standard (29 CFR 1910.1200). Classification of the : GASES UNDER PRESSURE - Compressed gas substance or mixture ACUTE TOXICITY (inhalation) - Category 4 GHS label elements Hazard pictograms : Signal word : Warning Hazard statements : Contains gas under pressure; may explode if heated. May displace oxygen and cause rapid suffocation. Harmful if inhaled. Precautionary statements General : Read and follow all Safety Data Sheets (SDS’S) before use. Read label before use. Keep out of reach of children. If medical advice is needed, have product container or label at hand. Close valve after each use and when empty. Use equipment rated for cylinder pressure. Do not open valve until connected to equipment prepared for use. Use a back flow preventative device in the piping. Use only equipment of compatible materials of construction. Prevention : Use only outdoors or in a well-ventilated area. Avoid breathing gas. Response : IF INHALED: Remove person to fresh air and keep comfortable for breathing. Call a POISON CENTER or physician if you feel unwell. Storage : Protect from sunlight when ambient temperature exceeds 52°C/125°F. Store in a well- ventilated place.
    [Show full text]
  • OSHA Method 61: Phosgene
    PHOSGENE - (Organic Method #61) Page 1 of 20 U.S. Department of Labor Occupational Safety & Health Administration www.osha.gov Search Advanced Search | A Technical Links > Sampling & Analytical Methods > Index PHOSGENE Method no.: 61 Matrix: Air Target concentration: 100 ppb (0.4 mg/m3) (OSHA PEL) Procedure: Air samples are collected by drawing known volumes of air through sampling tubes containing XAD-2 adsorbent which has been coated with 2­ (hydroxymethyl)piperidine. The samples are desorbed with toluene and then analyzed by gas chromatography using a nitrogen selective detector. Recommended air volume and sampling rate: 240 L at 1 L/min Reliable quantitation limit: 3.5 ppb (0.014 mg/m3) Standard error of estimate at the target concentration: 6.7% (Section 4.7.) Status of method: Evaluated method. This method has been subjected to the established evaluation procedures of the Organic Methods Evaluation Branch. Date: August 1986 Chemist: Warren Hendricks Organic Methods Evaluation Branch OSHA Analytical Laboratory Salt Lake City, Utah 1. General Discussion 1.1. Background 1.1.1. History http://www.osha.gov/dts/sltc/methods/organic/org061/org061.html 7/7/2008 PHOSGENE - (Organic Method #61) Page 2 of 20 The procedures that have been used by OSHA to monitor occupational exposure to phosgene include detector tubes, monitoring dosimeters and infrared gas analyzers. None of these procedures have proven to be completely adequate for use by OSHA. These methods lack either the desired precision and accuracy or they are awkward and inconvenient for field use. This procedure was developed after it was found that phosgene would react quantitatively with 2-(hydroxymethyl)piperidine (2-HMP) to form a stable derivative, 1-aza-8-oxabicyclo[4.3.0.]inonan-9-one.
    [Show full text]
  • Alcoholsalcohols
    AlcoholsAlcohols Chapter 10 1 Structure of Alcohols • The functional group of an alcohol is H an -OH group bonded to an sp3 O 108.9° hybridized carbon. C H – Bond angles about the hydroxyl oxygen H H atom are approximately 109.5°. • Oxygen is sp3 hybridized. –Two sp3 hybrid orbitals form sigma bonds to a carbon and a hydrogen. – The remaining two sp3 hybrid orbitals each contain an unshared pair of electrons. 2 Nomenclature of Alcohols • IUPAC names – The parent chain is the longest chain that contains the OH group. – Number the parent chain to give the OH group the lowest possible number. – Change the suffix -etoe -ol.ol • Common names – Name the alkyl group bonded to oxygen followed by the word alcohol.alcohol 3 Nomenclature of Alcohols OH o o 1o OH 1 2 OH 1-Propanol 2-Propan ol 1-Bu tanol (Pro py l alco ho l) (Isoprop yl alcoh ol) (Bu tyl alcoh ol) OH 2o OH 1o OH 3o 2-Butanol 2-M eth yl-1-p ropan ol 2-M eth yl-2-p ropan ol (sec-Butyl alcohol) (Isobutyl alcohol) (tert -Butyl alcohol) 4 Nomenclature of Alcohols • Compounds containing more than one OH group are named diols, triols, etc. CH2 CH2 CH3 CHCH2 CH2 CHCH2 OH OH HO OH HO HO OH 1,2-Ethanediol 1,2-Propanediol 1,2,3-Propanetriol (Ethylene glycol) (Propylene glycol) (Glycerol, Glycerine) 5 Physical Properties • Alcohols are polar compounds. – They interact with themselves and with other polar compounds by dipole-dipole interactions. • Dipole-dipole interaction: The attraction between the positive end of one dipole and the negative end of another.
    [Show full text]
  • Acetylcholinesterase: the “Hub” for Neurodegenerative Diseases And
    Review biomolecules Acetylcholinesterase: The “Hub” for NeurodegenerativeReview Diseases and Chemical Weapons Acetylcholinesterase: The “Hub” for Convention Neurodegenerative Diseases and Chemical WeaponsSamir F. de A. Cavalcante Convention 1,2,3,*, Alessandro B. C. Simas 2,*, Marcos C. Barcellos 1, Victor G. M. de Oliveira 1, Roberto B. Sousa 1, Paulo A. de M. Cabral 1 and Kamil Kuča 3,*and Tanos C. C. França 3,4,* Samir F. de A. Cavalcante 1,2,3,* , Alessandro B. C. Simas 2,*, Marcos C. Barcellos 1, Victor1 Institute G. M. ofde Chemical, Oliveira Biological,1, Roberto Radiological B. Sousa and1, Paulo Nuclear A. Defense de M. Cabral (IDQBRN),1, Kamil Brazilian Kuˇca Army3,* and TanosTechnological C. C. França Center3,4,* (CTEx), Avenida das Américas 28705, Rio de Janeiro 23020-470, Brazil; [email protected] (M.C.B.); [email protected] (V.G.M.d.O.); [email protected] 1 Institute of Chemical, Biological, Radiological and Nuclear Defense (IDQBRN), Brazilian Army (R.B.S.); [email protected] (P.A.d.M.C.) Technological Center (CTEx), Avenida das Américas 28705, Rio de Janeiro 23020-470, Brazil; 2 [email protected] Mors Institute of Research (M.C.B.); on Natural [email protected] Products (IPPN), Federal (V.G.M.d.O.); University of Rio de Janeiro (UFRJ), CCS,[email protected] Bloco H, Rio de Janeiro (R.B.S.); 21941-902, [email protected] Brazil (P.A.d.M.C.) 32 DepartmentWalter Mors of Institute Chemistry, of Research Faculty of on Science, Natural Un Productsiversity (IPPN),
    [Show full text]
  • Manganese-Catalyzed Β‑Alkylation of Secondary Alcohols with Primary Alcohols Under Phosphine-Free Conditions
    Letter Cite This: ACS Catal. 2018, 8, 7201−7207 pubs.acs.org/acscatalysis Manganese-Catalyzed β‑Alkylation of Secondary Alcohols with Primary Alcohols under Phosphine-Free Conditions † ‡ † † † § Tingting Liu, , Liandi Wang, Kaikai Wu, and Zhengkun Yu*, , † Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, P. R. China ‡ University of Chinese Academy of Sciences, Beijing 100049, P. R. China § State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. China *S Supporting Information ABSTRACT: Manganese(I) complexes bearing a pyridyl-supported pyr- azolyl-imidazolyl ligand efficiently catalyzed the direct β-alkylation of secondary alcohols with primary alcohols under phosphine-free conditions. The β-alkylated secondary alcohols were obtained in moderate to good yields with water formed as the byproduct through a borrowing hydrogen pathway. β-Alkylation of cholesterols was also effectively achieved. The present protocol provides a concise atom-economical method for C−C bond formation from primary and secondary alcohols. KEYWORDS: manganese, alcohols, alkylation, borrowing hydrogen, cholesterols onstruction of carbon−carbon bonds is of great impor- metals. In particular, it is capable of existing in several C tance in organic synthesis.1 More and more concern on oxidation states. Milstein and co-workers reported α- the consequence of climate change and dwindling crude oil olefination of nitriles,14a dehydrogenative cross-coupling of reserves results in the search for alternative carbon resources alcohols with amines,14b N-formylation of amines with 2 for the formation of C−C bonds. Thus, readily available methanol,15 and deoxygenation of alcohols16 catalyzed by alcohols have recently been paid much attention to be utilized pincer-type Mn-PNP complexes.
    [Show full text]
  • Phosphine Solubilities 281 1. Phosphine; PH3; 2. Organic Liquids. [7803-51-2] P. G. T. Fogg, School of Chemistry, Polytechnic Of
    Phosphine Solubilities 281 COHPONENTS: EVALUATOR: P. G. T. Fogg, 1. Phosphine; PH ; [7803-51-2] School of Chemistry, 3 Polytechnic of North London, 2. Organic liquids. Holloway, London N7 8DB United Kingdom. August 1983 CRITICAL EVALUATION: Data obtained by Palmer et aZ (1) and by Devyatykh et aZ (2) have been discussed in detail by Gerrard (3). Mole fraction solubilities calculated from measurements by Palmer et aZ. fall into a consistent pattern with a lower solubility in hydrogen bonded solvents compared with other solvents. There is also an increase in mole fraction solubility with increase in chain length in the case of straight chain alkanes. Solubilities are in the order: in benzene < in cyclohexene < in cyclohexane and in benzene < in toluene < in xylene. The variation of solubility in nitrobenzene, with change in temperature, was measured by both Palmer et aZ. and by Devyatykh et aZ. The ratio V01'PH3/vOl'solvent for a temperature of 295.2 K has been estimated by the compiler from data given by Devyatykh et aZ. to be 8.4. This may be compared with the value of 3.06 given by Palmer et aZ. for a pressure of 1 atm. There is a similar discrepancy between the solubility in liquid paraffin calculated from the data of Devyatykh et aZ and that measured by Palmer. There is also a marked difference between the solubility of phosphine in didecyl phthalate calculated from data given by Devyatykh and that in dibutyl phthalate measured by Palmer. Expressed as V01'PH3/vOl'solvent at 295.7 K the former gives 22.2 and the latter 3.23.
    [Show full text]
  • Electronic Supporting Information for Alcohol Oxidation with H2O2
    Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2016 Electronic Supporting Information for Alcohol Oxidation with H2O2 Catalyzed by a Cheap and Promptly Available Imine Based Iron Complex. Giorgio Olivo,a,b Simone Giosia,a Alessia Barbieri,a Osvaldo Lanzalunga,a and Stefano Di Stefano*,b aDipartimento di Chimica, Università degli Studi di Roma “La Sapienza” and Istituto CNR di Metodologie Chimiche (IMC-CNR), Sezione Meccanismi di Reazione, c/o Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, P.le A. Moro 5, I-00185 Rome, Italy bCurrent address: Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071 Girona, Spain S1 Table of contents Instruments and General Methods........................................................................................................3 Materials...............................................................................................................................................3 0.5 gram-scale oxidation ......................................................................................................................4 Cyclohexanol....................................................................................................................................4 Cycloheptanol...................................................................................................................................4 Competitive Oxidation
    [Show full text]
  • Aum Shinrikyo's
    Chronology of Aum Shinrikyo’s CBW Activities Introduction Six years ago, on March 20, 1995, five members of the Japanese cult Aum Shinrikyo (Supreme Truth) boarded subway trains in Tokyo, Japan, and released the deadly chemical nerve agent sarin. The attack killed 12 people and injured over 1,000, of whom 17 were critically injured (requiring intensive care), 37 were severely injured (with muscular twitching and gastrointestinal problems), and 984 were slightly injured (with pinpoint pupils but no other symptoms). Aum’s interest in chemical and biological weapons (CBW) terrorism can be traced back to 1990. Between 1990 and 1995, Aum launched 17 known CBW attacks, with motivations ranging from assassination to mass murder. Of these attacks, 10 were carried out with chemical weapons (four with sarin, four with VX, one with phosgene, and one with hydrogen cyanide) and seven attempted attacks were carried out with biological agents (four with anthrax and three with botulinum toxin, although in both cases the microbial strains were apparently nonvirulent). In addition to these cases, Aum is alleged to have killed 20 of its dissident members with VX and has been linked more tenuously to more than 19 other CBW attacks and attempted attacks (13 attacks where Aum involvement is suspected and six possible copycats). Since 1995, many of the perpetrators of the Tokyo subway attack have been jailed and are awaiting trial, and others have been sentenced to life in prison or to death by hanging. Although Aum has changed its name to Aleph, has decreased significantly in numbers, and claims to focus on its computer software company, its dangerous apocalyptic ideology remains.
    [Show full text]
  • Lecture Bottle Technical Evaluation
    ARCADIS 801 Corporate Center Drive Suite 300 Raleigh North Carolina 27607 MEMO Tel 919.854.1282 To: Copies: Fax 919.854.5448 Larry Daw Mary Beth Koza – UNC EHS UNC Environment, Health & Safety Alan Pinnix - ARCADIS Don Malone – ARCADIS Jim Shilliday – ARCADIS Ruddie Clarkson - ARCADIS From: David Proffitt Date: ARCADIS Project No.: June 27, 2008 NC000239.0017 Subject: UNC Airport Road Waste Disposal Area Lecture Bottle Technical Evaluation Due to the recent discovery of small compressed gas cylinders at the UNC Airport Road Waste Disposal Area, ARCADIS was asked to re-evaluate the site remediation practices and engineering controls to help minimize the potential for impacts to site workers and the surrounding community, including personnel and animals at the Orange County Animal Shelter. To facilitate this additional evaluation ARCADIS integrated an air monitoring and sampling expert into the project team to review the site practices and conditions. The overall project team reviewed all aspects of the recent cylinder event including discovery, intermediate handling, over-pack application, and finally shipping from the site. Several aspects were noted as having a higher potential to greatly affect capture and dispersion of an emission event from a cylinder. These aspects included: 1- The embossed number on one of the cylinders suggests it could have originally contained one of the following compounds: phosphine, arsine, diborane, nitric oxide, and nitrogen dioxide. The color of an additional cylinder suggests that it could potentially contain phosgene. The evaluation discussed in this memo used arsine and phosgene as a worst-case condition model. 2 - The arrangement of the pit and the tent-like enclosure over the work area allows direct wind only from its open ends.
    [Show full text]
  • Concept for CBRN Full Facepiece Air Purifying Respirator Standard
    June 15, 2002 (DRAFT FOR DISCUSSION) Concept for CBRN Full Facepiece Air Purifying Respirator Standard (1) Goal: Develop a NIOSH, NPPTL, tight fitting, full facepiece, air purifying respirator standard that addresses CBRN materials identified as inhalation hazards and/or possible terrorist hazards using a minimum number of filters for emergency responders. Target: Four (4) filters Short Duration Long Duration TIMs 15 minutes* 60 minutes* TIMs plus CO 15 minutes* 60 minutes* * Indicated times are for illustration only. Actual times will be established from hazard modeling and developmental test results. (2) Hazards: NIOSH has been evaluating various lists of chemicals that could be deployed as a result of a terrorist incident. In an effort to reduce the number of certification tests necessary as part of a Chemical Biological Radiological Nuclear (CBRN) Air-Purifying Respirator (APR) standard, efforts have been underway to categorize potential respiratory hazards into families with a representative test chemical identified for each family. The following information is a synopsis of this effort to date. The current carbon technology used in canisters and cartridges were reviewed from existing certification standards. The current standards for gas masks in Europe and the U.S. (NIOSH) were reviewed. The military purchasing specification for ASZM-T carbon for C2A1 military canisters was also reviewed. The most common parameters identified from the review of the military specification and the certification standards were the middle range certification challenges. Some of the test chemicals were considered to be redundant, since other test chemicals would guarantee the carbon effectiveness against the chemicals in question (Chlorine, Hydrogen Chloride, Hydrogen Fluoride, Phosphine, CS & CN Tear Gases).
    [Show full text]
  • Website Chlorine Pwdr Sugar Water Phosgene Tear
    Phosgene 2 Gases 44P make Hydrogen website Tear Gas,2 KCN 2, make somoom Chemical Agents Chlorine pwdr Ricin CHLORINE,2 Sugar water Phosgene Phosgene, also known as carbonic dichloride, colorless, extremely toxic gas of formula COCl2 with an unpleasant, irritating odor at high concentrations. It is prepared by the reaction of carbon monoxide with chlorine in the presence of a catalyst. Phosgene is poisonous in concentrations above 50 parts per million of air, and if inhaled, it causes severe and often fatal edema of the lungs within a few hours. It was used in World War I as a poison gas but today is used principally as an intermediate in the synthesis of organic compounds, including carbonic esters, isocyanates, polyurethanes, and dyes. Phosgene is 3.43 times heavier than air; the gas melts at -118° C (-180.4° F) and boils at 8.3° C (46.9° F). Look here Chemical war section. Tear Gas I INTRODUCTION Tear Gas, chemical substance that produces a primary physical effect of stinging or tearing eyes. Tear gas also irritates other mucous membranes and causes choking and coughing. People exposed to higher concentrations may experience burning, itching, or even blistering skin. As a form of riot control, police often use clouds of tear gas to break up crowds of people. A rifle-fired grenade or a thrown canister usually delivers tear gas, but smaller hand- held spray devices also exist. Tear gas may also be used to force the surrender of fugitives hiding in a building. Dogs and horses are relatively unaffected by tear gas, so they can add to the riot-control effect of the gas.
    [Show full text]