DOCSLIB.ORG

Synthesis of High Carbon Materials from Acetylenic Precursors

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis of High Carbon Materials from Acetylenic Precursors Reprinted from The Journal of Organic Chemistry, 1988, Vol. 53, page 2489 Copyright @ 1988 by the American Chemical Society and reprinted by permission of the copyright owner. Synthesis of High Carbon Materials from Acetylenic Precursors. Preparation of Aromatic Monomers Bearing Multiple Ethynyl Groups1 Thomas X. Neenan and George M. Whitesides* Department of Chemistry, Harvard University, Cambridge, Massachusetts 02138 Received October 13, 1987 The synthesis of polyethynyl aromatics as starting materials for the preparation of highly cross-linked organic solids containing high atom fractions of carbon is described. Treatment of bromo- and iodoaromatic compounds with (trimethylsily1)acetylene (TMSA) in the presence of palladium(0)and copper(1) in amine solvents yields (trimethylsily1)ethynyl-substituted aromatics. The TMS protecting groups can be removed by hydrolysis with mild base. Compounds prepared by using this technique include 1,3-diethynylbenzene,2,5-diethynylthiophene, 1,3-diethynyltetrafluorobenzene,1,4-diethynyltetrafluorobenzene, 2-ethynylthiazole, 2,4-diethynylthiazole, 2,7- diethynylnaphthalene, hexakis((trimethylsilyl)ethynyl)benzene, tetraethynylthiophene, 2,5-bis((trimethy1- silyl)ethynyl)-3,4-bis(3-hydroxy-3-methyl-l-butynyl)thiophene,2,5-diethyny1-3,4-bis(3-hydroxy-3-methyl-l-b~- tynyl)thiophene, 2,5-bis(4-(2-thienyl)butadiynyl)-3,4-bis(3-hydroxy-3-methyl-l-butynyl)thiophene,and 2,5-bis- (4-(2-thienyl)butadiynyl)-3,4-diethynylthiophene. Introduction We are engaged in a project aimed at the preparation of organic solids containing a high density of strong, di- rected carbon-carbon bonds. Our objective in this project is to relate the molecular-level structure of the solids to their macroscopic physical properties and to determine if it is possible to replicate in these materials some of the remarkable range of properties exhibited by pure allotropes of carbon (diamond: hardness, high thermal conductivity) (graphite: electrical conductivity, l~bricity).~We expect high-carbon, densely cross-linked organic solids to display high thermal stability and a high degree of hardness. Our strategy for the preparation of these materials involves the initial syntheses of low molecular weight poly(di- acetylenes); these polymers are then molded into desired shapes and processed thermally, photochemically, and/or catalytically to yield the final, highly cross-linked organic solids. This paper details the preparation of several monomeric search at DBM has developed related-materials based upon polyacetylenic aromatic compounds. Certain of these the oxidative coupling of 1,3,5-triethynylben~ene.~ monomers are the precursors to the intermediate polymers; A separate effort directed toward high-carbon solids at others were too reactive and unstable to be useful in po- Hercules concentrated on the polymerization of di- lymerizations but are of interest in their own right as un- ethynylbenzenes by a route involving cyclotrimerization usual ethynylated compounds. We will discuss the po- of the ethynyl group^.^ This procedure yielded polymers lymerization of these monomers and materials processing ostensibly containing polyphenylene units, residual ace- of the resulting polymers in later paper^.^ tylenic residues, and a small fraction of olefinic units. The commercial development of organic solids from These olefinic groups resulted from a process in which the acetylenic precursors dates from the 1960s when Hay acetylenes underwent a linear rather than a cyclo- showed that the oxidative coupling of 1,Bdiethynylbenzene trimerization polymerization. The Hercules process also (1) yielded a soluble polymers5 The molecular weight and used suitable end-capping groups such as 2 to limit mo- solubility of this; polymer could be controlled by using lecular weight. Soviet workers have also extensively de- mixtures of 1 and phenylacetylene (2) (as an end-capping veloped the cyclotrimerization polymerization of diethynyl group) in the polymerization. This procedure yielded aromatics? Commercialization of materials derived from phenyl-terminated poly(diethyny1benzene) oligomers 3 diethynylbenzene and other acetylenic precursors was that could be further processed at high temperatures to exdored at both General Electric and Hercules. The ab- form carbon films and fibers. Research at General Electric sence of an inexpensive route to the monomers, together expanded this type of chemistry to include a wide range with the limitation of a low elongation-to-break of the of acetylenic aromatic monomer^.^ More recently, re- finished materials, discouraged their full development. A parallel effort to develop acetylene-containing poly- (1) This work was supported by the National Science ~oundaGon; mers as thermoset resins resulted in the development of Grant CHE 85-08702. (2) Diercks, R.; Armstrong, J. C.; Boese, R.; Vollhardt, K. P. C. Angew. Chem.. Int. Ed. Enpl. 1986.25.268-269. (7) Dawson, D. J.; Fleming, W. W.; Lyerla, J. R.; Economy, J. In (3) ?he ~ropert'es of ~iamond;Field, J. E., Ed.;Academic Press: Reactive Oligomers; ACS Symposium Series 282; American Chemical London, 1979. Paxton, R. R. Manufactured Carbon. A Self-Lubricating Societv: Washineton. DC. 1986: DD 63-79. Economv. J.: Flandera. M. Material for Mechanical Devices; CRC: Boca Raton, FL, 1979. A.; ~ii,C.-Y. u.s:P~~:4 25'8079,1981. Economy, J.; ~i&dera,M. A. U.S. (4) Neenan, T. X.; Whitesides, G. M., unpublished. Pat. 4 273906, 1981. (5) Hay, A. S. J. Org. Chem. 1960, 25, 1275-1276. (8) Cessna, L. C., Jr. U.S. Pat. 3882073,1975. Jabloner, H. U.S. Pat. (6) Hay, A. S. U.S. Pat. 3 300456,1967. Hay, A. S. U.S. Pat. 3 332 916, 4070333. 1978. Jabloner. H. U.S. Pat. 4097460. 1978. 1967. Hay, A. S. U.S. Pat. 3519611, 1970. White, D. M.; Klopfer, H. J. (9) ~orshak,V. V.; volpin, M. E.; Sergeev, V. A.; Shitikov, V. K.; U.S. Pat. 3748305,1973. White, D. M. U.S. Pat. 3816374,1974. White, Kolomnikov, I. S. U.S. Pat. 3705 131, 1972. Korshak, V. V.; Gribova, I. D. M. U.S. Pat. 4020265, 1977. Chalk, A. J.; Gilbert, A. R. U.S. Pat. A.; Krasnov, A. P.; Sergeev, V. A,; Shitikov, V. K.; Elerdashvili, G. V. U.S. 4 108942,1978. Pat. 3 756 982, 1973. 2490 J. Org. Chem., Vol. 53, No. 11, 1988 Neenan and Whitesides acetylene-terminated imide oligomers such as the Ther- as an alternative, but deprotedion requires hydroxide base mid-600 series.1° These materials have excellent thermal in high boiling solvent. stability but their high cost and difficulty in curing have restricted their development. Results and Discussion Classical methods for the synthesis of terminal aryl- Ethynylbenzenes. We prepared l,&diethynylbenzene acetylenes involve the manipulation of preformed two- (1) by the reaction of l,&dibromobenzene with TMSA carbon units." Most useful among these are the Vilsmeier using dichlorobis(benzonitrile)palladium, triphenyl- reaction,12 the halogenation-dehydrohalogenation of vinyl phosphine, and copper(1) iodide as catalyst. The TMS- aromatics and ketones,13J4and the dehydrohalogenation protected intermediate (6) is an air- and moisture-stable of P,o-dihalo olefins.16 This latter reaction was employed for the preparation of diethynylbenzene in the research of both General Electric and Hercules. A number of re- actions also introduce ethynyl moieties directly into aro- matic rings. The most widely accepted of these methods has been the Stephens-Castr~'~.'~reaction between an solid. Treatment of compound 6 with a catalytic amount aromatic halide and a protected cuprous acetylide in re- of base in methanol removes the protecting groups. fluxing pyridine. Difficulty in removing protective groups Compound 1 is a clear colorless liquid that discolors upon has been a limitation of this method. An alternative to prolonged standing. Compound 1 may be purified by the Stephens-Castro method-the coupling between distillation at moderate temperatures and under high arylcopper reagents and (iodoethyny1)trimethylsilane at vacuum. (Note: Our initial attempt to distill 1 at tem- low temperatures18-is limited by the necessity to form the peratures of up to 110 OCand at aspirator pressures organocopper reagents. The palladium-catalyzed reaction resulted in an exothermic reaction followed by an ex- of alkynylzinc reagents with aryl halideslg yields terminal plosion. Compound 1 and all other volatile polyethynyl and internal ethynyl aromatic compounds and does not aromatics should be distilled at high vacuum and at require protection of the alkynyl groups but does require temperatures of less than 60 OCin well-shielded equip- as reactant an aryl iodide or activated aryl bromide. A ment. Only limited quantities should be distilled, stored, system of palladium(0) and copper(1) catalytically couples or manipulated as pure (undiluted) material. All of the acetylenes and aryl iodide~.~O?~lHagihara and Lau im- deprotected ethynyl aromatics mentioned in this paper proved this reaction by using (trimethylsily1)acetylene should be treated as potentially explosive material^.)^^ (TMSA).22 This improvement yields stable, readily ma- The same chemistry can be extended to the preparation nipulated trimethylsilyl-protected ethynyl aromatics as of higher poly- and persubstituted acetylenic aromatic intermediates; mild basic hydrolysis removes the TMS compounds. Reaction of hexaiodobenzene (8) with TMSA group. Electron-withdrawing groups on the aryl ring fa- cilitate the reaction; electron-donating groups are detri- mental. This method offers the advantages of simplicity, ease of workup, and high yields. Vollhardt and co-workers first
Load more

Recommended publications
  • PINE RIVER CONTAMINATION SURVEY St
    PINE RIVER CONTAMINATION SURVEY St. Louis, Michigan [June 2-6, 1980] October 1980 CONTENTS EXECUTIVE SUMMARY INTRODUCTION. .......................... 1 SUMMARY ............................. 2 CONCLUSIONS ........................... 2 RECOMMENDATION. ......................... 3 TECHNICAL ANALYSIS BACKGROUND. ........................... 4 STUDY METHODS .......................... 6 ANALYTICAL RESULTS. ....................... 11 TOXICITY AND HEALTH EFFECTS ................... 14 EVALUATION OF FINDINGS. ..................... 17 APPENDICES A ELUTRIATION STUDY, PINE RIVER SEDIMENT B SUMMARY OF ANALYTICAL METHODOLOGY C TOXIC DATA COMPLETION METHODS TABLES 1 River Water Sampling Stations (RWS) Locations. ....... 8 2 River Sediment Sampling (RSS) Locations. .......... 9 3 Sediment Core Descriptions ................. 10 4 River Sediment Samples (RSS) ................ 13 5 Priority Pollutants. .................... 15 FIGURE 1 River Sampling Locations . EXECUTIVE SUMMARY INTRODUCTION * A survey conducted in 1974 by the Michigan Department oc Natural Re- sources (DNR) indicated severe contamination of the Pine River sediments in ** the St. Louis, Michigan Reservoir and below the Velsicol Chemical Corpo- ration (VCC) plant site. Several organic compounds were identified in the study including: DOT and associated analogs (total DOT: 293 mg/kg), phthalates (19.5 mg/kg), polybrominated biphenyls (PBB : 9.0 mg/kg), and oils (19,000 mg/kg). Flesh analyses of Pine River fish showed high levels of PBB (0.87 mg/kg), polychlorinated biphenyls (PCB 1254: 1.99 mg/kg), and total DOT (1.65 mg/kg). A Michigan Department of Public Health warning against consumption of Pine River fish from St. Louis 60 km downstream to the confluence with the Chippewa River was issued in November 1974, because of PBB contamination. This warning was renewed in 1976 and still remains in effect. A In a publication dated June 15, 1979, concerning the contaminated Pine River the Michigan DNR recommended the following: (1) The St.
    [Show full text]
  • Hexachlorobenzene UNITED NATIONS
    UNITED NATIONS RC UNEP/FAO/RC/CRC.5/10/Add.1 Distr.: General 2 December 2008 United Nations English only Environment Programme Food and Agriculture Organization of the United Nations Rotterdam Convention on the Prior Informed Consent Procedure for Certain Hazardous Chemicals and Pesticides in International Trade Chemical Review Committee Fifth meeting Rome, 23–27 March 2009 Item 4 (b) (vii) of the provisional agenda* Listing of chemicals in Annex III to the Rotterdam Convention: review of notifications of final regulatory actions to ban or severely restrict a chemical: hexachlorobenzene Hexachlorobenzene Note by the Secretariat Addendum Supporting documentation provided by Canada The Secretariat has the honour to provide, in the annex to the present note, documentation received from Canada to support its notification of final regulatory action on hexachlorobenzene as an industrial chemical. * UNEP/FAO/RC/CRC.5/1. K0842870 161208 For reasons of economy, this document is printed in a limited number. Delegates are kindly requested to bring their copies to meetings and not to request additional copies. UNEP/FAO/RC/CRC.5/10/Add.1 Annex • Hexachlorobenzene: Priority Substances List Assessment Report, Environment Canada, Health Canada. • Environmental Assessments of Priority Substances Under the Canadian Environmental Protection Act, Guidance Manual, Version 1.0 — March 1997. Environment Canada. • SOR/2005-41; CANADIAN ENVIRONMENTAL PROTECTION ACT, 1999; Prohibition of Certain Toxic Substances Regulations, 2005, Canada Government Gazette. 2 Canadian
    [Show full text]
  • Development of Non-Targeted Approaches to Evidence Emerging Chemical Hazard
    THESE DE DOCTORAT DE ONIRIS COMUE UNIVERSITE BRETAGNE LOIRE ECOLE DOCTORALE N° 605 Biologie Santé Spécialité : Santé Publique Par Mariane POURCHET Development of non-targeted approaches to evidence emerging chemical hazard Identification of new biomarkers of internal human exposure, in order to support human biomonitoring and the study of the link between chemical exposure and human health Thèse présentée et soutenue à Nantes, le 8 octobre 2020 Unité de recherche : LABERCA UMR INRAE 1329 Rapporteurs avant soutenance : Benedikt WARTH Associate professor, University of Vienna, Vienna, Austria Katrin VORKAMP Doctor, Aarhus University, Aarhus, Denmark Development of non-targeted approaches to evidence emerging Composition du Jury : chemical hazard Président : Adrian COVACI Professor, University of Antwerp, Antwerp, Belgium ExaminateursIdentification : Benedikt of WARTHnew biomarkers Associateof internal professor, human University exposure, of Vienna, in Vienna, order Austria to support Katrin VORKAMP Doctor, Aarhus University, Aarhus, Denmark human biomonitoringJana KLANOVA and the studyProfessor, of the Masaryk link University,between Brno, chemical Czech Republic exposure and Adrian COVACI Professor, University of Antwerp, Antwerp, Belgium human health Dir. de thèse : Jean-Philippe ANTIGNAC Doctor, Oniris, Nantes, France Thèse présentée et soutenue à Nantes, le 8 octobre 2020 Unité de recherche : LABERCA UMR INRAE 1329 I would like to express my sincere gratitude to my thesis committee, Benedikt Warth, Associate professor, Department of Food Chemistry and Toxicology, University of Vienna, Austria Katrin Vorkamp, Senior researcher, Department of Environmental Science, Aarhus University, Denmark Adrian Covaci, Professor, Toxicological Centre, University of Antwerp, Belgium Jana Klánová Professor, Research Centre for Toxic Compounds in the Environment (RECETOX), Masaryk University, Brno, Czech Republic for their time in reading and evaluating this manuscript.
    [Show full text]
  • Anaerobic Transformation of Brominated Aromatic Compounds by Dehalococcoides Mccartyi Strain CBDB1
    Anaerobic transformation of brominated aromatic compounds by Dehalococcoides mccartyi strain CBDB1 vorgelegt von Master of Engineering Chao Yang geb. in Henan. China von der Fakultät III – Prozesswissenschaften der Technischen Universität Berlin zur Erlangung des akademischen Grades Doktor der Naturwissenschaften - Dr.-rer. nat. - genehmigte Dissertation Promotionsausschuss: Vorsitzender: Prof. Dr. Stephan Pflugmacher Lima Gutachter: Prof. Dr. Peter Neubauer Gutachter: Prof. Dr. Lorenz Adrian Gutachter: PD Dr. Ute Lechner Tag der wissenschaftlichen Aussprache: 28. August 2017 Berlin 2017 Declaration Chao Yang Declaration for the dissertation with the tittle: “Anaerobic transformation of brominated aromatic compounds by Dehalococcoides mccartyi strain CBDB1” This dissertation was carried out at The Helmholtz Centre for Environmental Research-UFZ, Leipzig, Germany between October, 2011 and September, 2015 under the supervision of PD Dr. Lorenz Adrian and Prof. Dr. Peter Neubauer. I herewith declare that the results of this dissertation were my own research and I also certify that I wrote all sentences in this dissertation by my own construction. Signature Date Acknowledgement This research work was conducted from October, 2011 to September, 2015 in the research group of PD Dr. Lorenz Adrian at the Department of Isotope Biogeochemistry, Helmholtz Centre for Environmental Research Leipzig (UFZ). The research project was funded by the Chinese Scholarship Council and supported by Deutsche Forschungsgemeinschaft (DFG) (FOR1530). It was also supported by Tongji University (in China) and Technische Universität Berlin (in Germany). I would like to say sincere thanks to PD Dr. Lorenz Adrian for the opportunity to work and learn in his unitive and creative research group. Also many thanks to him for leading me into the amazing and interesting microbial research fields, for sharing his extensive knowledge, for the productive discussion and precise supervision, and for his firm support both in work and life.
    [Show full text]
  • Chemicals in the Environment (FY2001)
    CHEMICALS IN THE ENVIRONMENT Report on Environmental Survey and Wildlife Monitoring of Chemicals in FY2001 Environmental Health Department Ministry of the Environment Government of JAPAN March 2003 The information contained in this repot was taken from the annual report of the Ministry of the Environment (MOE), “CHEMICALS IN THE ENVIRONMENT, FY2001 (Japanese version).” While the information provided is believed to be accurate, MOE disclaims any responsibility for possible inaccuracies or omissions and consequences which may flow from them. MOE is not liable for any injury, loss, damage or prejudice of any kind that may be caused by any persons who have acted based on their understanding of the information contained in this publication. Material in this publication may be freely quoted or reprinted, but acknowledgement is requested together with a reference to the document number. A copy of the publication containing the quotation or reprint should be sent to MOE of Japan. Limited copies of this report are available from: Environment Health and Safety Division Environment Health Department Ministry of the Environment (MOE) Government of Japan 1-2-2, Kasumigaseki, Chiyoda-ku, Tokyo 100-8975 Japan Phone: +81-3-5521-8260 Fax: +81-3-3580-3596 E-mail: [email protected] http://www.env.go.jp/en/ Contents List of Tables 2 List of Figures 3 List of Acronyms 5 Contents of CD-ROM 6 Introduction 7 Chapter 1 Outline of Environmental Investigation on Chemical Substances 8 Chapter 2 Summary of Fiscal Year 2000 General Inspection Survey of Chemical Substances
    [Show full text]
  • Potential Chemical Contaminants in the Marine Environment
    Potential chemical contaminants in the marine environment An overview of main contaminant lists Victoria Tornero, Georg Hanke 2017 EUR 28925 EN This publication is a Technical report by the Joint Research Centre (JRC), the European Commission’s science and knowledge service. It aims to provide evidence-based scientific support to the European policymaking process. The scientific output expressed does not imply a policy position of the European Commission. Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use that might be made of this publication. Contact information Name: Victoria Tornero Address: European Commission Joint Research Centre, Directorate D Sustainable Resources, Water and Marine Resources Unit, Via Enrico Fermi 2749, I-21027 Ispra (VA) Email: [email protected] Tel.: +39-0332-785984 JRC Science Hub https://ec.europa.eu/jrc JRC 108964 EUR 28925 EN PDF ISBN 978-92-79-77045-6 ISSN 1831-9424 doi:10.2760/337288 Luxembourg: Publications Office of the European Union, 2017 © European Union, 2017 The reuse of the document is authorised, provided the source is acknowledged and the original meaning or message of the texts are not distorted. The European Commission shall not be held liable for any consequences stemming from the reuse. How to cite this report: Tornero V, Hanke G. Potential chemical contaminants in the marine environment: An overview of main contaminant lists. ISBN 978-92-79-77045-6, EUR 28925, doi:10.2760/337288 All images © European Union 2017 Contents Acknowledgements ................................................................................................ 1 Abstract ............................................................................................................... 2 1 Introduction ...................................................................................................... 3 2 Compilation of substances of environmental concern .............................................
    [Show full text]
  • Acenaphthene 83-32-9 5000 N 45000 N 100000 L 110 N 530 N Acephate 30560-19-1 110 N 980 N 2100 N 0.11 N 24 N Acetaldehyde 75-07-0
    Table A-6: 2021 Screening Levels Soil Exposure Ground Water Vapor Exposure Chemical Direct Contact Soil MTG Tap Ground Water Indoor Air Residential Com/Ind Excavation Residential Residential Residential Com/Industrial Residential Com/Ind Name CASRN (mg/kg) (mg/kg) (mg/kg) (mg/kg) (ug/L) (ug/L) (ug/L) (ug/m3) (ug/m3) Acenaphthene 83-32-9 5000 N 45000 N 100000 L 110 N 530 N Acephate 30560-19-1 110 N 980 N 2100 N 0.11 N 24 N Acetaldehyde 75-07-0 110 N 340 N 1900 N 0.077 N 19 N 9.4 N 39 N Acetochlor 34256-82-1 1800 N 16000 N 34000 N 5.6 N 350 N Acetone 67-64-1 85000 N 100000 L 100000 L 57 N 14000 N 32000 N 140000 N Acetone Cyanohydrin 75-86-5 100000 L 100000 L 100000 L 2.1 N 8.8 N Acetonitrile 75-05-8 1100 N 3400 N 19000 N 0.54 N 130 N 63 N 260 N Acetophenone 98-86-2 2500 S 2500 S 2500 S 12 N 1900 N Acetylaminofluorene, 2- 53-96-3 2 C 6 C 320 C 0.015 C 0.16 C 0.022 C 0.094 C Acrolein 107-02-8 0.2 N 0.6 N 3.4 N 0.00017 N 0.042 N 0.021 N 0.088 N Acrylamide 79-06-1 3.4 C 46 C 2400 C 0.0021 C 0.5 C 0.1 C 1.2 C Acrylic Acid 79-10-7 140 N 420 N 2300 N 0.0085 N 2.1 N 1 N 4.4 N Acrylonitrile 107-13-1 3.5 C 11 C 370 N 0.0023 C 0.52 C 0.41 C 1.8 C Adiponitrile 111-69-3 100000 L 100000 L 100000 L 6.3 N 26 N Alachlor 15972-60-8 140 C 410 C 18000 N 0.033 M 2 M Aldicarb 116-06-3 88 N 820 N 1800 N 0.015 M 3 M Aldicarb Sulfone 1646-88-4 88 N 820 N 1800 N 0.0088 M 2 M Aldicarb sulfoxide 1646-87-3 0.018 M 4 M Aldrin 309-00-2 0.55 C 1.8 C 59 N 0.03 C 0.0092 C 0.0057 C 0.025 C Allyl Alcohol 107-18-6 4.9 N 15 N 83 N 0.00086 N 0.21 N 0.1 N 0.44 N Allyl Chloride
    [Show full text]
  • ANR Rule Filing Package
    Emergency Rule Coversheet Julie S. Moore, Secretary Agency of Natural Resources Revised Aug 14, 2018 page 2 Emergency Rule Coversheet 1. TITLE OF RULE FILING: Investigation and Remediation of Contaminated Properties Rule 2. ADOPTING AGENCY: Agency of Natural Resources 3. PRIMARY CONTACT PERSON: (A PERSON WHO IS ABLE TO ANSWER QUESTIONS ABOUT THE CONTENT OF THE RULE). Name: Chuck Schwer Agency: Agency of Natural Resources Mailing Address: 1 National Life Drive, Davis 1, Montpelier, Vermont 05620 Telephone: 802 249 - 5324 Fax: - E-Mail: Web URL(WHERE THE RULE WILL BE POSTED): http://dec.vermont.gov/commissioners-office/pfoa 4. SECONDARY CONTACT PERSON: (A SPECIFIC PERSON FROM WHOM COPIES OF FILINGS MAY BE REQUESTED OR WHO MAY ANSWER QUESTIONS ABOUT FORMS SUBMITTED FOR FILING IF DIFFERENT FROM THE PRIMARY CONTACT PERSON). Name: Diane Sherman Agency: Agency of Natural Resources Mailing Address: 1 National Life Drive, Davis 2, Montpelier, Vermont 05620 Telephone: 802 505 - 0125 Fax: - E-Mail: [email protected] 5. RECORDS EXEMPTION INCLUDED WITHIN RULE: (DOES THE RULE CONTAIN ANY PROVISION DESIGNATING INFORMATION AS CONFIDENTIAL; LIMITING ITS PUBLIC RELEASE; OR OTHERWISE EXEMPTING IT FROM INSPECTION AND COPYING?) No IF YES, CITE THE STATUTORY AUTHORITY FOR THE EXEMPTION: PLEASE SUMMARIZE THE REASON FOR THE EXEMPTION: 6. LEGAL AUTHORITY / ENABLING LEGISLATION: Revised Aug 14, 2018 page 3 Emergency Rule Coversheet (THE SPECIFIC STATUTORY OR LEGAL CITATION FROM SESSION LAW INDICATING WHO THE ADOPTING ENTITY IS AND THUS WHO THE SIGNATORY SHOULD BE. THIS SHOULD BE A SPECIFIC CITATION NOT A CHAPTER CITATION). 10 V.S.A. § 6603 7. EXPLANTION OF HOW THE RULE IS WITHIN THE AUTHORITY OF THE AGENCY: SECTION 6603 OF TITLE 10 OF THE VERMONT STATUTES ANNOTATED ASSIGNS THE AGENCY OF NATURAL RESOURCES WITH THE RESPONSIBILITY TO ADOPT RULES IMPLEMENTING THE PROVISIONS OF THE CHAPTER, INCLUDING THE DEFINITION OF HAZARDOUS MATERIAL IN 10 V.S.A.
    [Show full text]
  • Emerging “New” Brominated Flame Retardants in Flame 2462 Retarded Products and the Environment 2009
    Current State of Knowledge and Monitoring requirements EMERGING “NEW” BROMINATED FLAME RETARDANTS IN FLAME 2462 RETARDED PRODUCTS AND THE ENVIRONMENT 2009 Current state of knowledge and monitoring requirements - Emerging "new" brominated flame retardants in flame retarded products and the environment (TA-2462/2008) Current State of Knowledge and Monitoring requirements Emerging “new” Brominated flame retardants in flame retarded products and the environment Mikael Harju, Eldbjørg S. Heimstad, Dorte Herzke Torkjel Sandanger, Stefan Posner and Frank Wania 2 Current state of knowledge and monitoring requirements - Emerging "new" brominated flame retardants in flame retarded products and the environment (TA-2462/2008) Preface Brominated flame retardants are a group of chemicals that inhibit combustion. They are extensively used in electrical and electronic equipment, transport equipment, building materials, paint and insulation foams. However, many of the brominated flame retardants have undesirable effects on the environment and on human health. Therefore it is a nationnal target to substantially reduce the release of five prioritized brominated flame retardants before 2010 and completely eliminate the discharge of these five substances before 2020. The overall aim of this study is to perform a review of the current state of the knowledge on emerging “new” brominated flame retardants. This includes the use of the selected substances, environmental levels, data on toxicity and ecotoxicity, potential to biocon- centrate and bioaccumulate in the food web, analytical possibilities, potential for long range transport and their persistence in the environment. Further, this information is used to select compounds that based on the current knowledge can be relevant for further monitoring. The Norwegian Pollution Control Authority (SFT) has commissioned the environmental research institute NILU (Norway), Swerea IVF (Sweden) and WECC Wania Environ- mental Chemist Corp.
    [Show full text]
  • 8323 Hexabromobenzene
    H0363 Material Safety Data Sheet HAZARD WARNINGS RISK PHRASES PROTECTIVE CLOTHING Irritating to skin, eyes, and the respiratory system. Section I. Chemical Product and Company Identification Chemical Name Hexabromobenzene Catalog Number H0363 Supplier TCI America 9211 N. Harborgate St. Synonym Perbromobenzene Portland OR 1-800-423-8616 Chemical Formula C6Br6 In case of Chemtrec® CAS Number 87-82-1 Emergency (800) 424-9300 (U.S.) Call (703) 527-3887 (International) Section II. Composition and Information on Ingredients Chemical Name CAS Number Percent (%) TLV/PEL Toxicology Data Hexabromobenzene 87-82-1 Min. 99.0 Not available. Not available. (GC) Section III. Hazards Identification Acute Health Effects Irritating to eyes and skin on contact. Inhalation causes irritation of the lungs and respiratory system. Inflammation of the eye is characterized by redness, watering, and itching. Skin inflammation is characterized by itching, scaling, reddening, or, occasionally, blistering. Follow safe industrial hygiene practices and always wear proper protective equipment when handling this compound. Chronic Health Effects CARCINOGENIC EFFECTS : Not available. MUTAGENIC EFFECTS : Not available. TERATOGENIC EFFECTS : Not available. DEVELOPMENTAL TOXICITY: Not available. There is no known effect from chronic exposure to this product. Repeated or prolonged exposure to this compound is not known to aggravate existing medical conditions. Section IV. First Aid Measures Eye Contact Check for and remove any contact lenses. DO NOT use an eye ointment. Flush eyes with running water for a minimum of 15 minutes, occasionally lifting the upper and lower eyelids. Seek medical attention. Treat symptomatically and supportively. Skin Contact After contact with skin, wash immediately with plenty of water.
    [Show full text]
  • RED LIST DECLARATION Manufacturer: Product Name
    RED LIST DECLARATION Manufacturer: Koninklijke Mosa bv Product Name: Mosa Cradle to Cradle Silver certified ceramic wall tiles and porcelain floor tiles Commonly referred to as “the Red List”, the following list of materials has been complied by the Living Future Institute as the worst in class materials prevalent in the building industry. I certify that the following are/are not in the product listed above (at any concentration): Yes No ☐ ☒ Alkylphenols ☐ ☒ Asbestos ☐ ☒ Bisphenol A (BPA) ☐ ☒ Cadmium ☐ ☒ Chlorinated Polyethylene & Chlorosulfonated Polyethlene ☐ ☒ Chlorobenzenes ☐ ☒ Chlorofluorocarbons (CFCs) & Hydrochlorofluorocarbons (HCFCs) ☐ ☒ Chloroprene (Neoprene) ☐ ☒ Chromium VI ☐ ☒ Formaldehyde (added) ☐ ☒ Halogenated Flame Retardants (HFRs) ☐ ☒ Lead (added) ☐ ☒ Mercury ☐ ☒ Polychlorinated Biphenyls (PCBs) ☐ ☒ Perfluorinated Compounds (PFCs) ☐ ☒ Phthalates ☐ ☒ Polyvinyl Chloride (PVC), Chlorinated Polyvinyl Chloride (CPVC) or Polyvinylidene Chloride (PVDC) ☐ ☒ Short Chain Chlorinated Paraffins ☐ ☒ Volatile Organic Compounds (VOCs) in wet applied products ☐ ☒ Wood treatments containing Creosote, Arsenic or Pentachlorophenol Notes: The above applies to all Mosa Cradle to Cradle Silver certified wall and floor tiles, which have a C2C Gold score for Material Health. Certificates are available at www.mosa.com/sustainability or https://www.c2ccertified.org/products/scorecard/wall_tiles and https://www.c2ccertified.org/products/scorecard/floor_tiles Signature: Date: April 20th, 2019 Name: D. H. van der Weele Title: Manager Sustainability Contact Info: [email protected] APPENDIX ALKYLPHENOLS are a large family of organic compounds used in a wide variety of products, including cleaning products, beauty products, contraceptives, coatings, fragrances, thermoplastics, carbonless copy paper, and agrochemicals. Most concerns are focused on alkylphenol ethoxylates (APEs), which bioaccumulate and have been shown to cause endocrine disruption in fish. APEs are in cleaning products that end up in waterways from wastewater treatment effluent.
    [Show full text]
  • Home Number °5333 D N0t Scanned
    5333 Home Number ° D N0t scanned Author Dryden, Forrest E. Corporate Author Walk, Haydel & Associates, Inc., New Orleans, Louisian RODOrt/ArtiClBTitlO Dioxins: Volume III. Assessment of Dioxin-Forming Chemical Processes Journal/Book Title YBaP Month/Day June Color n Number of Images ° Volume III of a three-volume series. Contract No. 68-03- 2579; EPA-600/2-80-158 Tuesday, March 05, 2002 Page 5333 of 5363 United States Industrial Environmental Research EPA-600/2-80-158 Environmental Protection Laboratory June 1980 Agency Cincinnati OH 45268 Research and Development &EPA Dioxins Volume III. Assessment of Dioxin-Forming Chemical Processes RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into nine series. These nine broad cate- gories were established to facilitate further development and application of en- vironmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy-Environment Research and Development 8. "Special" Reports 9. Miscellaneous Reports This report has been assigned to the ENVIRONMENTAL PROTECTION TECH- NOLOGY series. This series describes research performed to develop and dem- onstrate instrumentation, equipment, and methodology to repair or prevent en- vironmental degradation from point and non-point sources of pollution. This work provides the new or improved technology required for the control and treatment of pollution-sources to meet environmental quality standards.
    [Show full text]