DOCSLIB.ORG

United States Patent Office Patented Mar

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent Office Patented Mar 2,930,777 United States Patent Office Patented Mar. 29, 1960 1. 2 mer rubber. However, it has now been discovered that 2,930,777 treating rubber with an aliphatic amine or mixed aliphatic SYNERGISTC STABILIZER COMPOSITIONS FOR aromatic monoamine, either the free amine or in the RUBBER COMPRESING AN N-NETROSO ARO. form of a salt, in conjunction with a nitroso aromatic KN AMINE AND AN ALPHATIC MONO amine achieves advantages unobtainable with either in gredient alone. The combination exerts a synergistic Harold M. Leeper and Dudley B. Merrifield, Charleston, effect against aging, mitigates activation of cure, im W. Va., assignors to Monsanto Chemical Company, St. proves the resistance to exposure cracking, especially in Louis, Mo., a corporation of Delaware synthetic rubber, lowers hysteresis and in general pro vides economical protection to rubber against degradation No Drawing. Application July 19, 1955 10 as well as improving the processing of the raw stocks and Serial No. 523,118 the physical properties of the vulcanizates. 10 Claims. (CI. 260-45.9) The amines suitable for practicing the invention in clude common aliphatic monoamines whether primary, The present invention relates to improvements in rub-. secondary, tertiary or mixtures thereof, and simple mixed ber compounding and is particularly directed to the prob 5 aliphatic-aromatic monoamines. The organic substituent lem of preventing degradation of natural and synthetic on the nitrogen will usually be a hydrocarbon radical rubbers. but substitution is permissible, notably by cyano, halo The causes of degradation vary and a general object gen, hydroxy, keto, and lower alkoxy groups. Aliphatic of the invention is to inhibit the various deleterious in groups include benzyl which is predominately aliphatic fluences to which rubbers are subjected in service. A 20 in properties, saturated bivalent radicals attached to a particular object of the invention is to prevent exposure central nitrogen atom to complete a saturated heter cracking of sulfur vulcanizable rubbers. A further object ocyclic ring and alicyclic as well as saturated and un is to provide rubber compositions containing amine anti saturated open carbon chain radicals. Addition of the degradation agents which can be readily processed. A amine in the form of a salt is usually preferred and has further object is to inhibit prevulcanization or scorch 25 the advantage of lowering volatility. in rubber compositions containing cure-activating amines. Salts of dicyclohexylamine have been studied exten Another object is to prevent the heat embrittlement of sively and found to be generally effective. Fatty acid butadiene-styrene copolymer rubber. Still another ob salts are fully equivalent to the free amine if added to ject is to inhibit the aging of sulfur vulcanizable rubbers, provide an equivalent amine content. The preferred whether natural or synthetic. A further object is to 30 salts are the stearate, acetate, oleate, adipate, oxalate, provide a combination of anti-degradation agents which formate, nitrite, toluene sulfonate and dodecylbenzene exert a synergistic effect. Also, another object is to sulfonate. Less desirable are the benzoate, salicylate and provide a combination of anti-degradation agents which phthalate. A combination of dicyclohexylamine and a economically inhibit degradation. Still another object is nitroso aromatic amine is an outstanding general pur to improve the hysteresis of rubber vulcanizates. 35 pose anti-degradation agent for natural and synthetic One of the major problems of the rubber industry is rubbers. the protection of vulcanizates of sulfur vulcanizable Many other aliphatic amines inhibit exposure crack rubbers against exposure cracking, that is degradation of ing, especially of natural rubber. Examples of aliphatic the vulcanizates due to ozone while under static or amines which have been tested and found suitable for dynamic stress. The problem is a serious one, particu 40 use in practicing the invention comprise: cyclohexyl larly with respect to the service life of rubber tires, and amine stearate, N-methylcyclohexylamine, N-methyl is aggravated by the fact that in general chemical anti cyclohexylamine acetate, N - methylcyclohexylamine oxidants have little or no value in protecting vulcanizates stearate, N-2-cyanoethylcyclohexylamine, N-2-chloro against deterioration by ozone. Waxes which form a allylcyclohexylamine, N-(3-chloro-2-butenyl)cyclohexyl protective surface film are useful to inhibit exposure amine, N-nonenylcyclohexylamine, N-dodecenylcyclo cracking if the rubber is not flexed but protection is lost 45 hexylamine, N-dodecylcyclohexylamine, N-methyldicyclo once the film breaks. When a rubber surface, whether hexylamine, N-methyldicyclohexylamine formate, N natural or synthetic, comes into contact with an at methyldicyclohexylamine stearate, 2-dicyclohexylamino mosphere containing even a few parts ozone per million ethanol, dicyclohexylamino-2-propanone, N-butyldicyclo a myriad of cracks form on the surface. The cracks hexylamine, N,N-dimethylcyclohexylamine, N,N-di cohntinue to grow so that the useful life of the article 50 methylcyclohexylamine, stearate, dibutylamine, dibutyl rapidly terminates. The severity of the problem when amine oleate, diamylamine, dioctylamine, diethanolamine, . rubber articles must be stored for a long time will be morpholine, morpholine stearate, N-2-cyanoethylbutyl readily appreciated. amine. ... .". Deterioration of rubber due to aging is another well The mixed aliphatic-aromatic amines contemplated defined problem. The degradation is manifested in the 55 contain in addition to an aliphatic substituent which is . case of natural rubber by loss of tensile strength and it preferably one or more cyclohexyl groups, one mono-, i. is usually attributed to absorption of oxygen. It has valent aromatic substituent attached to nitrogen. By long been known that such deterioration can be greatly monovalent is meant that the aromatic group is linked retarded by treating the rubber before or after vulcaniza to the residue of the molecule containing the amino tion with substances known as age resisters or anti 60 substituent by a single valence and is linked to only one oxidants. The age resisting characteristics of a Vulcan amino substituent. Examples of mixed amines which ized rubber product can be readily ascertained by Sub have been tested and found suitable for practicing the . jecting samples of the vulcanized rubber to the action invention comprise, N-cyclohexylaniline, N-cyclohexyl of air or oxygen at elevated temperatures. 65 p-phenetidine, N-cyclohexyl-o-hydroxyaniline, N-2-cyano Aliphatic and mixed aliphatic-aromatic amines inhibit ethylaniline, N-2-cyanoethyl-p-toluidine, N-2-cyanoethyl exposure cracking but the utility of common aliphatic p-amylaniline, N-ethyl-p-phenetidine, N-benzyl-p-pheneti and mixed amines is limited. They are accelerators and dine, N-2-cyanoethyl-p-phenetidine, N-2-cyanoethyl-o- accelerator activators with a low critical temperature, phenetidine, N-allyl-p-phenetidine, N,N-diethyl-p-phenet weak age resisters and are generally deficient for pre idine and N,N-dimethylaniline stearate. it is venting exposure cracking of butadiene-styrene copoly 70 Nitroso aromatic amines suitable for use in practicing 2,930,777 3 4. the invention have been disclosed in the chemical and Using these base formulae stocks were compounded by patent literature. These include age and exposure crack adding the ingredients shown below. The resistance of ing resistors but vulcanizates containing sufficient nitroso the raw compounds to scorch was evaluated by means compound to afford a practical level of protection are of a Mooney plastometer. The scorch point was taken deficient in hysteresis. However, the effect can be over as the point on the plasticity curve when the plasticity come and compensated completely by use in conjunc had risen 10 points above the minimum value. tion with an amine. Nitroso aromatic amines are rep resented by N-nitroso-di-3-naphthylamine, N-nitroso diphenylamine, N-nitroso-di-o-naphthylamine, N-nitroso Table I phenyl - B - naphthylamine, N - nitrosophenyl - or - naph O thylamine, N-nitroso-di-o-tolylamine, N-nitrosophenyl-o- Stock----------------------------------------------- 2 3 tolylamine, N-nitrosophenyl-p-tolylamine, N-nitrosoben zylphenylamine, N-nitroso-N-methylaniline, N-nitroso Parts by weight N - ethylaniline, N - nitroso - N - B - naphthylpheneti dine, N,N' - dinitrosodiphenyl - p - phenylenediamine, 5 N,N'-Dinitroso-N,N-diphenyl-p-phenylenediamine.-------Dicyclohexylamine stearate.------------------------ 5 f5 - Ethoxy - 1,2-dihydro - 2,2,4-trimethyl-1-nitro N,N' - dinitroso - dinaphthyl - p - phenylenediamine and Soquinoline--------------------------------------------------- 0.5 the N-nitroso derivative of the reaction product of di Mooney Scorch, Iminutes: phenylamine and acetone. The latter is described in Natural rubber, 121 C---------- 12 17 U.S. Patent 1,945,577 to ter Horst. Still other examples GR-S rubber, 135 C--------------------------- 17 18 are the N-nitroso-2,2,4-trimethyl-1,2-dihydroquinolines 20 disclosed in U.S. Patent 2,268,419 to Paul. Further ex amples of effective compounds are N-nitroso-N-aryl-N- It will be noted that the addition of a nitroso aromatic alicyclic or alkyl p-phenylenediamines, as for example amine significantly increases the resistance to scorch. In N-cyclohexyl-N,N'- dinitroso - N' - phenyl - p - phenyl another experiment, replacing 0.5 part of the dicyclo enediamine,
Load more

Recommended publications
  • Synthetic Turf Scientific Advisory Panel Meeting Materials
    California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update .....
    [Show full text]
  • And Ruthenium-Catalyzed N-Alkylation of Amines with Alcohols and Amines
    Downloaded from orbit.dtu.dk on: Oct 11, 2021 Iridium- and Ruthenium-Catalyzed N-alkylation of Amines with Alcohols and Amines Lorentz-Petersen, Linda Luise Reeh Publication date: 2012 Document Version Publisher's PDF, also known as Version of record Link back to DTU Orbit Citation (APA): Lorentz-Petersen, L. L. R. (2012). Iridium- and Ruthenium-Catalyzed N-alkylation of Amines with Alcohols and Amines. DTU Chemistry. 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 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. Iridium- and Ruthenium-Catalyzed N-alkylation of Amines with Alcohols and Amines PhD thesis Linda Luise Reeh Lorentz-Petersen February 2012 Department of Chemistry Technical University of Denmark Preface Preface This thesis describes the work carried out at the Department of Chemistry at the Technical University of Denmark from January 2007 to February 2012 supervised by Professor Robert Madsen. In that period a 6 month external stay at The Scripps Research Institute, San Diego, California, USA, from September 2008 till the end of February 2009 was conducted under supervision by Professor Phillip E.
    [Show full text]
  • Supporting Information
    Electronic Supplementary Material (ESI) for Catalysis Science & Technology. This journal is © The Royal Society of Chemistry 2018 Supporting information Direct Liquid-Phase Phenol-to-Aniline Amination Using Pd/C Thomas Cuypers†, Patrick Tomkins† and Dirk E. De Vos*,† † Centre for Surface Chemistry and Catalysis, Department of Microbial and Molecular Systems, KU Leuven – University of Leuven, Leuven Chem&Tech, Celestijnenlaan 200F, Post Box 2461, 3001 Heverlee, Belgium *E-mail: [email protected] 1. Chemicals and catalyst All chemicals used in reactions and/or analysis were obtained from commercial sources and were used without further purification: toluene (>99.8%, Acros Organics), phenol (>99%, Sigma Aldrich), NH3 (gas, 99.98%, Air Liquide), n-nonane (99%, Acros Organics), cyclohexanone (>99%, TCI Europe), cyclohexylamine (>99%, TCI Europe), aniline (>98%, TCI Europe), dicyclohexylamine (>99%, Acros Organics), N-cyclohexylaniline (97%, Acros Organics), diphenylamine (99%, Acros Organics), o-cresol (≥99%, Sigma Aldrich), m-cresol (99%, Sigma Aldrich), p-cresol (99%, Alfa Aesar), 2-methylcyclohexanone (99%, Sigma Aldrich), 3-methylcyclohexanone (97%, Sigma Aldrich), 4-methylcyclohexanone (99%, Sigma Aldrich). All tested catalysts, loaded with 5 wt% metal, were obtained from commercial sources: Pd/C (Johnson Matthey), Pt/C (Johnson Matthey), Rh/C (Alfa Aesar), Ru/C (Alfa Aesar). 2. Amination reactions All amination reactions were performed in a 60 mL high-pressure stainless steel Premex Vivor batch reactor equipped with a digital pressure sensor. In a standard reaction, the reactor was loaded with phenol (2 mmol) in toluene (20 mL), catalyst (5 mol% metal relative to phenol) and a magnetic stirring rod. After purging three times with N2, the reactor was subsequently pressurized with 3.5 bar N2, 0.5 bar H2 and 2 bar NH3 at room temperature.
    [Show full text]
  • The Direct Conversion of Phenol to Cyclohexylamines – a New and Sustainable Pathway to Aliphatic Polyurethanes?
    The Direct Conversion of Phenol to Cyclohexylamines – a New and Sustainable Pathway to Aliphatic Polyurethanes? Patrick Tomkins, Carlot Valgaeren, Koen Adriaensen, Thomas Cuypers, Dirk E. De Vos* Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F – box 2461, 3001 Leuven, Belgium *Corresponding author: [email protected] Abstract: Cyclohexylamines are important intermediates for chemical industry are used for various applications and are currently synthesized by hydrogenation of anilines. However, the direct synthesis from bio-derived phenol using ammonia is an interesting alternative. We herein present the high-yield synthesis of cyclohexylamines using Rh/C, in contrast to Pd-based catalysts, which are the state-of-the-art materials for the formation of N-alkylated cyclohexylamines and resulted in poor yields for the reaction with ammonia. The hydrogen bonding of isopropanol as solvent allowed for excellent activity. These results will broaden the catalyst landscape for the direct amination of phenol and give new incentives to fellow researchers. Keywords: Phenol, amination, cyclohexylamine. 1. Introduction Cyclohexylamines have many applications. However, one of the most important examples is the fully hydrogenated 4,4’-methylenedianiline-derivative (H12-MDA). Currently this is synthesized by the reduction of methylenedianiline. With a potential change in feedstock from fossil sources to lignin-derived phenolics the traditional route is barely possible. Recently there were several reports describing the conversion of phenol to N-alkylated anilines using Pd/C.1, 2 In this reaction, a reductant is used to initially convert phenol to cyclohexanone, which then reacts with an amine to form an N-alkylated cyclohexylamine which is then hydrogenated towards the corresponding cyclohexylamine in one pot.
    [Show full text]
  • Intram Olecular Dipole R Eorientation of Am Ino Com Pounds And
    Intramolecular Dipole Reorientation of Amino Compounds and their Interaction with Solvent Molecules II Jaakko K. Eloranta* Institut für Physik der Johannes-Gutenberg-Universität Mainz, Abteilung Mikrowellenphysik (Z. Naturforsch. 28a, 82—88 [1973]; received 28 November 1972) The dielectric absorption of dilute solutions of chlorocyclohexane, cyclohexylamine, dicyclo- hexylamine, diphenylamine, N-methyldiphenylamine, and triphenylamine in various solvents has been measured between 0.3 and 135 GHz. The measurements have been carried out at 20 °C and for some solutions also at -30 and 60 °C. The previous measurements made for the compounds have been extended to higher frequencies and improved by a greater number of frequencies. The loss curves have been resolved into multiple absorption regions. A rather much contributing far infrared (FIR) term was necessary to be involved in each analysis. The intra­ molecular dipole reorientation process in cyclohexylamine is considerably slower than in aniline because of the lack of the mesomeric interaction. In dicyclohexylamine only the overall re­ laxation was observed at microwave frequencies. Two large regions were resolved for N-methyl­ diphenylamine at microwave frequencies whilst in diphenylamine the second region likely contributes to the very large FIR region. Evidences for weak association between diphenyl­ amine and the aromatic solvents were obtained. In the first part of this investigation1 indications cially the so called far infrared (FIR) absorption, were obtained, in accordance with previous results2-4, is considered, the significance of which was pointed that the mesomeric interaction between the lone pair out by Klages and Krauss5. The solvent dependence electrons in the nitrogen and the ^-electrons of the of the relaxation processes2 is reinvestigated using phenyl ring plays an important role in the intra­ aromatic and aliphatic solvents with varying visco­ molecular dipole reorientation process of aniline and sities.
    [Show full text]
  • Raw Materials Supply Chain for Rubber Products
    John S. Dick Charles P. Rader Raw Materials Supply Chain for Rubber Products Overview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates Contents, Preface, Introduction, Chapter 4, Index Book ISBN HANSER 978-1-56990-537-1 Hanser Publishers, Munich • Hanser PublicaƟ ons, CincinnaƟ Contents Preface . V Acknowledgments . VI 1 Introduction . 1 1.1 Rubber Industry’s Place in the World Economy . 2 1.2 The Structure of the Tire Industry . 2 1.3 The Structure of the Nontire Industry . 5 1.4 Sectors of the Nontire Rubber Industry . 7 1.4.1 The Rubber Hose Industry ...................................... 7 1.4.2 The Belt Segment ............................................. 7 1.4.3 Seals and Gaskets ............................................. 7 1.4.4 Blowout Preventers and Packers ................................. 8 1.4.5 Single-Ply Roofing ............................................. 8 1.4.6 Bushings and Motor Mounts .................................... 8 1.4.7 Molded Rubber Goods ......................................... 8 1.4.8 Tank Lining .................................................. 8 1.4.9 Wire and Cable Insulation ...................................... 9 1.4.10 Shoe Heel and Sole Applications ................................. 9 1.4.11 Sponge Rubber Products ....................................... 9 1.4.12 Rubber Weatherstripping ....................................... 9 1.4.13 Rubber Latex Products ......................................... 9 1.4.14 Rubber Rollers ................................................ 9 1.4.15 Rubber Tiles ................................................. 10 1.4.16 Rubber Bands ................................................ 10 1.5 Market Forces . 10 2 Basic Raw Materials from Earth Extractions and Agriculture . 13 2.1 Vital Basic Raw Materials for Rubber . 14 2.1.1 Crude Petroleum Oil . 14 2.1.2 Natural Gas . 20 2.1.3 Natural Rubber . 23 2.1.4 Sulfur . 25 2.1.5 Zinc Ore .
    [Show full text]
  • One Pot Synthesis of Cyclohexanone Oxime from Nitrobenzene Using a Bifunctional Catalyst
    Document downloaded from: http://hdl.handle.net/10251/54629 This paper must be cited as: Rubio Marqués, P.; Hernández Garrido, JC.; Leyva Perez, A.; Corma Canós, A. (2014). One pot synthesis of cyclohexanone oxime from nitrobenzene using a bifunctional catalyst. Chemical Communications. 50(14):1645-1647. doi:10.1039/c3cc47693f. The final publication is available at Copyright Royal Society of Chemistry Additional Information Journal Name RSCPublishing COMMUNICATION One pot synthesis of cyclohexanone oxime from nitrobenzene with a bifunctional catalyst Cite this: DOI: 10.1039/x0xx00000x Paula Rubio-Marqués,a Juan Carlos Hernández-Garrido,b Antonio Leyva-Pérez,*a and Avelino Corma*a Received 00th January 2012, Accepted 00th January 2012 DOI: 10.1039/x0xx00000x www.rsc.org/ Cyclohexanone oxime is formed from nitrobenzene with 97% yield in a one-pot reaction catalysed by palladium and gold nanoparticles on carbon. The reaction is carried out under hydrogen at 60 ºC and the overall transformation involves a multi-step catalysed mechanism from which intermediates and catalytic active species have been identified. Figure 1. Hydrogenation of nitrobenzene to cyclohexanone oxime Cyclohexanone oxime is the key intermediate in the production of under static pressure catalysed by Au and/or Pd/C catalysts. The nylon 6 fibers and resins, and the worldwide market is one of the yield with Au/C + Pd/C is reproduced with semi-continuous 1 largest among chemical products. Manufacturing is typically carried dynamic pressure (see Suppo. Info. for details). out in a three-step procedure: a) synthesis of cyclohexane by metal- 2 catalysed hydrogenation of benzene; b) synthesis of cyclohexanone If Au/C is used alone under the same catalytic loading, 3-5 by oxidation of cyclohexane at low conversions per pass (<8%) or cyclohexanone oxime 2 is not obtained.
    [Show full text]
  • A Ruthenium Racemisation Catalyst for the Synthesis Of
    Erschienen in: Dalton Transactions ; 45 (2016), 29. - S. 11765-11771 https://dx.doi.org/10.1039/c6dt01525e Dalton Transactions View Article Online PAPER View Journal | View Issue A ruthenium racemisation catalyst for the synthesis of primary amines from secondary amines† Cite this: Dalton Trans., 2016, 45, 11765 Dennis Pingen,a Çiğdem Altıntaş,‡c Max Rudolf Schaller‡d and Dieter Vogt*b A Ru-based half sandwich complex used in amine and alcohol racemization reactions was found to be Received 20th April 2016, active in the splitting of secondary amines to primary amines using NH3. Conversions up to 80% along Accepted 10th June 2016 with very high selectivities were achieved. However, after about 80% conversion the catalyst lost activity. DOI: 10.1039/c6dt01525e Similar to Shvo’s catalyst, the complex might deactivate under the influence of ammonia. It was revealed www.rsc.org/dalton that not NH3 but mainly the primary amine is responsible for the deactivation. Introduction Primary amines are valuable building blocks in industrial Creative Commons Attribution 3.0 Unported Licence. chemistry; they are the main building blocks for a large variety of polymers, surfactants, corrosion inhibitors and fine-chemi- cals.1,2 For the production of primary amines, waste-free, selec- tive protocols are highly desired with special emphasis on renewable resources such as bio-alcohols.3 However, current industrial (heterogeneously catalysed) syntheses of amines from alcohols inevitably give mixtures of primary, secondary, and ter- tiary amines.4 Current homogeneously catalysed alcohol amin- This article is licensed under a ation reactions were shown to be very selective towards primary Scheme 1 ‘Hydrogen Shuttling’ in the splitting of secondary amines to amines, barely producing any secondary amines.
    [Show full text]
  • Use of High Throughput Assays and Computational Tools; Endocrine Disruptor Screening Program; Notice of Availability and Opportunity for Comment’’
    NRDC EPA-HQ-OPPT-2015-0305 August, 2015 Comments from the Natural Resources Defense Council On The Document Titled, ‘‘Use of High Throughput Assays and Computational Tools; Endocrine Disruptor Screening Program; Notice of Availability and Opportunity for Comment’’ To the U.S. Environmental Protection Agency Docket No. EPA-HQ-OPPT-2015-0305 August 18, 2015 Background The Natural Resources Defense Council ("NRDC") is a national, non-profit environmental organization of lawyers, scientists, and other professionals. NRDC presents these comments on behalf of our 1.4 million members and online activists. NRDC does not have any financial interest in the topic of these comments. The endocrine system utilizes highly complex, tightly controlled molecular processes for its optimal functioning in the body. The proper balance of hormones can be synchronized in a variety of ways (including direct protein binding, epigenetic alterations, gene activation and silencing), and is essential across the entirety of the life course. Small changes in the perfectly orchestrated symphony of hormone levels can severely disrupt the harmony necessary for critical windows of development (e.g., fetal development, infanthood, childhood, and adolescence), leaving the body vulnerable to a host of negative health outcomes (such as diabetes, cancer, obesity, and reproductive dysfunction). The last decade has seen an exponential increase in the development of computational, biological, and chemical tools capable of increasing both the number of chemicals analyzed and the pace of chemical toxicity evaluation. These tools, including the EPA Toxicity Forecaster (ToxCast™) and the National Institute of Environmental Health Sciences (NIEHS) Tox21 platforms, have the potential to rapidly generate molecular and cellular data for thousands of chemicals at once, and provide an additional stream of useful information that can aide in regulatory decision-making.
    [Show full text]
  • Våroćní Zpráva Za Rok 2016 the Company Report for The
    THE COMPANY 7Å30ė/¶;13«7"REPORT FOR THE;"30, YEAR 2016 CONTENTS 1| THE BASIC CHARACTERISTICS 6 2| The DEVELopment of SELected Indicators 9 3| The ManaGement Report 12 4| The Company’S Position; Research and DEVELopment 16 5| HUman ResoUrces and CommUnication 22 6| The InteGrated ManaGement System 27 7| ENVironmentaL Protection and Safety 29 8| The OWnership StrUctUre of BorsodChem Zrt. 33 ZÁKLADNÍ 1| CHARAKTERISTIKA THE BASIC 1|CHARACTERISTICS BorsodChem MCHZ, s.r.o., in its current form, continues hydrogenation lines for aniline production. Concurrently, in traditional chemical production that dates back to 1927. the company gradually discontinued the production At that time, the objective was to use the nearby source of sorbite, sulphuric acid, isopropylamine, nitrogen, oxygen, of coke gas to provide Czechoslovak production with argon, fertilisers and sodium nitrite, ammonia solution ammonia, nitric acid and artificial fertilisers before World and oxalic acid as a result of optimising the production War II, just like in surrounding European countries. portfolio. The production in a new plant started in 1928 with After 1990, the company underwent numerous the production of ammonia and ammonia sulphate. organisational and ownership changes. The joint-stock The production programme, originally focusing on the company “Moravské chemické závody” was formed production of fertilisers, was expanded and modernised in 1990 through the transformation of the state-owned after World War II. The production of formaldehyde plant. From 1 January 1999 to 26 April 2000, Moravské and urea-formaldehyde resins was launched and the chemické závody was a branch of Aliachem a.s. The processing of hydrogen for hydrogenation was expanded.
    [Show full text]
  • United States Patent 0 " Cc Patented Sept
    3,206,510 United States Patent 0 " cc Patented Sept. 14, 1965 1 2 point, which is also variable with the wetness of the crys 3,206,510 tals, increases from 35° C. to 65° C. when the initial molar PROCESS FOR MAKING CYCLOHEXANONE ratio of dicyclohexylaminc/cyclohexylamine changes from OXIME' Francis Weiss, Pierre-Benite, and Marcel Thevenon, 0.05 to 0.66. La Mulatiere, France, assignors to Societe d’Electro According to the process of our invention, cyclohexyl Chimie d’Electro-Metallurgie et des Acieries Electri amine is treated with hydrogen peroxide in an aqueous ques d’Ugine, Paris, France, a corporation of France medium, in the presence of a catalyst and dicyclohex No Drawing. Filed May 9, 1963, Ser. No. 279,298 ylamine to oxidize cyclohexylamine into cyclohexanone Claims priority, application France, May 10, 1962, oxime. Then this cyclohexanone-oxime is separated from 8 6 10 the reaction medium as an addition compound with 7 Claims. (01. 260-566) dicyclohexylamine, and pure cyclohexanone-oxime is col This invention relates to a process for making cyclo lected from the addition compound by distillation. hexanone-oxime by oxidation of cyclohexylamine with The optimum conditions for performing the reaction hydrogen peroxide, in the presence of soluble salts of are as follows: tungstic, molybdic or uranic acids. (a) The hydrogen'peroxide is used in sensibly stoi The oxidation of cyclohexylamine into cyclohexanone chiometric quantities relating to cyclohexylamine, i.e. 2 oxime by hydrogen peroxide in the presence of catalysts, moles per mole, according to the formula: preferably soluble tungst-ic salts, is well known.
    [Show full text]
  • Title Studies on Catalytic Action, XIV : a Comparative Study of The
    Studies on Catalytic Action, XIV : A Comparative Study of the Title Catalytic Activity of Reduced Copper, Reduced Nickel and Thoria, II Author(s) Komatsu, Shigeru; Tanaka, Choji Memoirs of the College of Science, Kyoto Imperial University. Citation Series A (1925), 8(3): 135-145 Issue Date 1925-03-30 URL http://hdl.handle.net/2433/256705 Right Type Departmental Bulletin Paper Textversion publisher Kyoto University Studies on Catalytic Action, XIV. A Comparative Study of the Catalytic Activity of Reduced Copper, Reduced Nickel and Thoria, 11. Shigeru Komatsu and Choji rrana]rn. (Received November 22, 1924) I, THE CATALYTIC ACTION OF THE CATALYSTS ON CYCLOHEXYLAMINE, In the tenth paper of this series, 1 on the catalytic action of the divided metals and metallic oxide on cyclohexanol at 200° and 300°, it was shown that reduced nickel acts principally as oxidizing catalyst and thoria promotes mostly the dehydration of the alcohol, whilst reduced nickel performs the latter action in the least degree, and reduced copper stands as a catalyst between these catalysts in every respect. The authors have then extended . the study to cyclohexylamine and examined whether the catalytic activity of these catalysts would be changed when the amine comes into contact with them at high temperature, by the presence of the NH2 group combined with the carbon atom of heX'l.methylene ring instead of the OH group in cyclohexanol, since the varying absorptive capacity of the catalysts, with reactant or resultant, would account for such a specific activity of the catalyst. As to the reaction products from cyclohexylamine by the catalytic action of the metals at a high temperature, it \Vill be supposed to be the hydrocarbons2 (b~nzene, cyclohex.:ine and other hydrocarbons) derived from cyclohexene formed by the decomposition of the amine, aniline, dicyclohexylamine, cyclohexylphenylamine, diphenylamine and carbazol by I S.
    [Show full text]