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 3,799,916 United States Patent Office Patented Mar. 26, 1974 1. 2 with the alkyl haloformate present, which necessitates 3,799,916 using at least a stoichiometrically equivalent amount of WNYTL CHLORDE BASED POLYMERS PREPARED hydrogen peroxide amounting to not less than 1 mole BY N-STUNITATORS IN ACD MEDUM Michael Langsam, Allentown, Pa., assignor to Air of hydrogen peroxide for each two moles of alkyl halo Products and Chemicals, Inc., Allentown, Pa. formate. No Drawing. Filed June 19, 1972, Ser. No. 264,044 Although the process described in U.S. 3,022,281 did Int. C. C08f3/30, 15/06, 15/30 provide a solution to the problems of special storage and U.S. C. 260-87.1 10 Claims uncontrolled reaction rate, by eliminating the use of pre-manufactured peroxydicarbonates, other difficulties arose making the process less than satisfactory. It was ABSTRACT OF THE DISCLOSURE 10 found that polymers manufactured accordingly were not Granular vinyl chloride based polymers are manu in the desired granular form, but instead were of a fibrous factured in the presence of a peroxydicarbonate free consistency. Furthermore, it was discovered that other radical catalyst, which is prepared in-situ in an acid re commercially important resins, such as vinyl chloride action mixture. By initiating and maintaining polymeriza 5 vinyl acetate copolymers could not be successfully pre tion at a pH constantly maintained below 7 the need for pared in commercially acceptable quality, apparently due excess haloformate may be avoided without sacrificing to alkaline hydrolysis. product quality. Another approach to the problem is described in U.S. Pat. 3,575,945, which suggests using a stoichiometric ex BACKGROUND OF THE INVENTION cess of alkyl haloformate over hydrogen peroxide in order 20 to ensure preparation of the more commercially desirable The invention relates to a process for preparing com polymer granules. Here, as with the earlier described mercially desirable vinyl chloride based polymers, such process, the initial pH of the aqueous phase of the re as vinyl chloride homopolymers (PVC) and copolymers action mixture is always above 7. However, this more containing vinyl chloride and other comonomers, where recent process, though specifying an initial pH of 8.5 to in a peroxydicarbonate free-radical initiator is formed 25 11.7, gradually drifts to a pH below 7 as polymeriza in-situ while the reaction mixture is maintained at a pH tion proceeds, due to the generation of hydrogen halide below 7. The peroxydicarbonates prepared in the polym and the absence of an alkaline buffering agent. In spite erization process may be identified by the formula: of generally improved product quality, this later process 30 (U.S. 3,575,945) lacked desired flexibility, in terms of proportional ranges of reactants needed for in-situ prepa Ro-5-oo--or, ration of the peroxydicarbonate initiator. Here, as with wherein R1 and R2 are alkyl or alkenyl radicals. the earlier in-situ process, certain vinyl chloride based By constantly maintaining the pH of the reaction mix copolymers could not be readily prepared with acceptable ture in the acidic range from the time polymerization 35 quality. commences the ratio of organic haloformate to aqueous British Pat. 1,262,706, as in the case of the later U.S. soluble peroxide needed to prepare the catalyst can be patent, also provides for a process of manufacturing vinyl varied considerably without adversely affecting quality chloride polymers by in-situ mechanism using peroxydi of the resulting polymer. carbonate free-radical catalysts. Polymerization is also Polymerization of vinyl based monomers, such as vinyl 40 initiated in alkaline medium and subsequently falls to an chloride may be accomplished by means of a free-radical acid pH as the reaction progresses. polymerization initiator in a suspension, emulsion or bulk It has now been discovered that high quality granular polymerization system. Polymerization, itself, is initiated vinyl chloride based polymers can be prepared by means by the generation of free-radicals arising from the de which entail conducting polymerization at an initial pH composition of various organic peroxides, such as benzoyl 45 below 7 and maintaining it in the acid range throughout peroxide, lauroyl peroxide and the like. Peroxydicar the cycle. Furthermore, a broad, flexible range of re bonate type free-radical catalysts, as with other organic actants can be successfully employed for the in situ manu peroxy catalysts, if not given special handling by storing facture of the catayst without adversely affecting poly at sufficiently low temperatures or... if not metered into mer quality. The vinyl chloride based polymers are pre the reactor under carefully controlled conditions, can 50 pared by manufacturing peroxydicarbonate free-radical result in an uncontrollable rate of reaction endangering catalysts in the presence of at least one monomer, said both operators and equipment as well as adversely affect catalyst having the formula: ing the final product. Because peroxydicarbonate free-radical initiators stand O O out as a particularly preferred group of polymerization 55 R10-0-00--or, catalysts, one approach taken in correcting the foregoing wherein R1 and R2 are alkyl or alkenyl groups having problems was to produce such initiators in-situ rather from 1 to 7 carbon atoms. than by adding the pre-manufactured catalyst to the re Accordingly, it is a principal object of the present in actor. This process is described in U.S. Pat. 3,002,281, vention to provide a process for manufacturing high qual which provides for conducting the process in an alkaline 60 ity granular vinyl chloride based polymers wherein the medium above a pH 7 for binding the hydrogen halide polymerization initiator is prepared in-situ in a reaction liberated from the reaction of the peroxide and an alkyl mixture constantly maintained at a pH below 7. haloformate. The basic medium is maintained by use of It is a further object of the instant invention to provide an alkaline buffering agent suitable for producing and a flexible process allowing wide variation of proportional sustaining the pH above 7. This proces further provides 65 amounts of reactants for preparing in-situ peroxydicar for a sufficient amount of hydrogen peroxide to react bonate free-radical catalysts for polymerizing vinyl chlo 3,799,916 3 4. ride based monomers, without adversely affecting prod formate. The aqueous soluble peroxide may be, for exam uct quality. ple, hydrogen peroxide, alkali metal peroxides like so A still further object is to provide a process for manu dium and potassium or acid peroxides e.g. peracetic facturing vinyl chloride based copolymers by employing acid, performic acid, etc. The requirements in selecting a peroxydicarbonate free-radical catalyst, which catalyst, an appropriate peroxide are not critical, however, they itself, can be prepared in the reaction mixture. must, nevertheless, be miscible with the aqueous phase These and other objects, features and advantages of of the polymerization system. this invention will become apparent to those skilled in The haloformates may be represented by the formula: the art after a reading of the following more detailed description. O PREFERRED EMBODIMENTS OF O THE INVENTON Ro-5-x Broadly, the invention is directed to a process for pre paring vinyl chloride based polymers with a dialkyl or wherein R is alkyl or alkenyl and X is halogen, such dialkenyl peroxydicarbonate free-radical initiator, which as fluorine, chlorine, bromine or iodine. Alkyl and alkenyl, is prepared in-situ during polymerization of the mon in most instances, refer to radicals having from 1 to about omers. The process is adaptable to polymerization sys 7 carbon atoms, which may be both branched and straight tems having a water phase and a monomer phase in which chained groups, like methyl, ethyl, propyl, isopropyl, n each of the reactants required for preparing the catalyst 20 butyl, t-butyl, penty1, hexyl, allyl, propenyl and the like. is soluble in one of the two mentioned phases. However, higher radicals such as nonyl and lauryl are In carrying out the process, the peroxydicarbonate cat also included in this group. alyst is formed during the polymerization of one or more The following table illustrates but a few of the halo monomers by reacting a water soluble peroxide with an formates falling within the purview of the above formula: alkyl or alkenyl haloformate. The peroxide reactant is 25 soluble in the water phase and the haloformate is soluble TABLE I in the monomer phase. Included in the reaction mixture, R: X before polymerization commences, is an acidifier which CH3 - ----------------------------------- C maintains the aqueous phase of the mixture at a pH be C2H5 ---------------------------------- C low 7. The pH of the mixture remains acidic throughout 30 CH- was so wa way war mem.8 m me it mix a m i r vro - r * - we we I the reaction cycle. Because hydrogen halide is generated i-Cahi - --------------------------------- Br during the formation of the catalyst, additional acidifier t-C4Hg ----------------------------------- C is not needed to maintain the pH constantly below 7. CoH13 ----------------------------------- C However, most conveniently, an acid buffering agent can CH3- saw a sers w is a wers as alia a was a sm am am a mm ame a mass am no or rid no to row C be employed. 35 C2H5- ---------------------------------- F The peroxydicarbonate initiator decomposes after being Cahs ---------------------------------- Cl formed in the presence of the monomers, thus providing the necessary free-radicals to bring about polymerization C oH21 aws - a - - - - - A was a was sea a nea at am more mix mm ami me mi mum am-www. C of the monomers. The reaction commences by elevating In-situ preparation of the peroxydicarbonate catalysts the mixture to above ambient temperatures. 40 may be accomplished by incorporating the peroxide re As previously indictaed, the instant process finds wide actant into the aqueous phase of the reaction mixture spread use in polymerization systems containing both and the particular haloformate into the oil or monomer water and oil or monomer phases wherein vinyl based phase of the polymerization system.
Load more

Recommended publications
  • Peroxysalts of the Alkali Metals and Related Species
    PEROXYSALTS OF THE ALKALI METALS AND RELATED SPECIES. A Thesis Submitted for the Degree of DOCTOR OF PHILOSOPHY of the University of London BY DAVID PHILIP JONES, B.SC., A,R,C.S, Department of Chemistry, Imperial College of Science and Technology, London, SW7 2AY August, 1979. 2 ABSTRACT Peroxysalts of the Alkali Metals and Related Species. David Philip Jones The work described in this thesis is concerned mainly with the preparation, characterisation and physicochemical properties of a series of different inorganic peroxysalts, in particular the alkali metal percarbonates. Extensive use has been made of vibrational spectroscopy as a tool for obtaining structural information, with both 2H and 13C isotopic substitutions helping in the assignments of vibrational modes. All of the peroxysalts studied fall into either of two categories. The first are perhydrates, which contain hydrogen peroxide of crystallisation, such as sodium oxalate monoperhydrate, Na2C204.H202 and " sodium percarbonate", Na2CO3.11H2O2. The second group contain peroxo moieties bound to atoms other than hydrogen, e.g., boron in " sodium perborate" , Na2B2(02)2(OH)4.6H20 or carbon in potassium peroxydicarbonate, K2C206, these types of compounds being referred to as " true" peroxysalts. The structures of both of the commonly used bleaching agents " sodium percarbonate" and " sodium perborate" are described, full X-ray structural determinations having been carried out in the Chemical Crystallography Laboratories during the course of this work. 3 Due to particular interest in percarbonates, one of the very few known transition metal peroxycarbonato complexes, bistriphenyl- phosphine peroxycarbonato platinum(II) has been prepared and its structure also determined by X-ray crystallography.
    [Show full text]
  • United States Patent Office Patented Sept
    3,692,599 United States Patent Office Patented Sept. 19, 1972 2 tend to undergo decomposition at temperatures in the 3,692,599 PROCESS OF FORMINGHGH-ENERGY range of 10° to 60° C. and even the decomposition prod PROPELLANT BNDERS ucts, such as isopropyl alcohol, formed from the diiso John B. Gardiner, Mountainside, and Herschel T. White, propyl peroxydicarbonate promote violent decomposition Montclair, N.J., assignors to Esso Research and Engi of the ester. Thus, it can be seen that it is important in neering Company using a peroxydicarbonate in admixture with other sub No Drawing. Fied Feb. 28, 1963, Ser. No. 262,296 stances that the other substances should not cause ex Int, C. C06d 5/06 plosive decomposition. U.S. C. 49-9 4. Claims The high-energy polyether acrylates containing NF2 This invention relates to a method of forming stronger 0 groups to be used in forming the cured binders are vis high-energy binders, particularly polyacrylate binders con cous liquid polymers having molecular weights in the taining NF2 oxidizing groups, by using esters of peroxy range of about 500 to about 5,000. The starting materials carbonic acid as initiators in curing acrylates of NF for these polymers are polyethers having a suitable high containing polymers. content of NF groups attached to carbon atoms and As described in U.S. application Ser. No. 224,885, 5 OH functionality. Some of the NF2-containing polyethers filed Sept. 11, 1962 by John B. Gardiner and Anthony may be made by expoxidizing an NF-containing olefin J. Passannate, high-energy oxidizer binders obtained from and polymerizing the resulting NF-containing epoxide.
    [Show full text]
  • Potentially Explosive Chemicals: Safe Storage and Handling
    Guidelines for Explosive and Potentially Explosive Chemicals: Safe Storage and Handling Guidelines for Explosive and Potentially Explosive Chemicals Safe Storage and Handling TABLE OF CONTENTS 1. Introduction ............................................................................................ 1 2. Common Laboratory PECs ................................................................... 2 3. General Storage Precautions ................................................................. 3 4. Sample Label ........................................................................................... 4 5. Specific Storage and Testing Guidelines for Peroxide Forming Chemicals ................................................................................................ 5 5.1 About Peroxide Forming Chemicals ..................................... 5 5.2. Testing Schedule for Peroxide Forming Chemicals ............ 6 Disposal or Testing Recommendations ................................ 6 5.3 An Analysis of Common Detection Procedures from R.J. Kelly’s article, ”Review of Safety Guidelines for Peroxidizable Organic Chemicals“ Peroxide Detection Methods ....................................... 7 Ferrous Thiocyanate Method ...................................... 7 Iodide Tests ................................................................... 8 Dip Strips ....................................................................... 9 Titanium Sulfate ........................................................... 9 Summary ....................................................................
    [Show full text]
  • Hazardous Waste List (California Code of Regulations, Title 22 Section 66261.126)
    Hazardous Waste List (California Code of Regulations, Title 22 Section 66261.126) Appendix X - List of Chemical Names and Common Names for Hazardous Wastes and Hazardous Materials (a) This subdivision sets forth a list of chemicals which create a presumption that a waste is a hazardous waste. If a waste consists of or contains a chemical listed in this subdivision, the waste is presumed to be a hazardous waste Environmental Regulations of CALIFORNIA unless it is determined that the waste is not a hazardous waste pursuant to the procedures set forth in section 66262.11. The hazardous characteristics which serve as a basis for listing the chemicals are indicated in the list as follows: (X) toxic (C) corrosive (I) ignitable (R) reactive * =Extremely Hazardous A chemical denoted with an asterisk is presumed to be an extremely hazardous waste unless it does not exhibit any of the criteria set forth in section 66261.110 and section 66261.113. Trademark chemical names are indicated by all capital letters. 1. Acetaldehyde (X,I) 2. Acetic acid (X,C,I) 3. Acetone, Propanone (I) 4. *Acetone cyanohydrin (X) 5. Acetonitrile (X,I) 6. *2-Acetylaminofluorene, 2-AAF (X) 7. Acetyl benzoyl peroxide (X,I,R) 8. *Acetyl chloride (X,C,R) 9. Acetyl peroxide (X,I,R) 10. Acridine (X) 11. *Acrolein, Aqualin (X,I) 12. *Acrylonitrile (X,I) 13. *Adiponitrile (X) 14. *Aldrin; 1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-1,4,5,8-endo-exodimethanonaphthlene (X) 15. *Alkyl aluminum chloride (C,I,R) 16. *Alkyl aluminum compounds (C,I,R) 17.
    [Show full text]
  • New York City Department of Environmental Protection Community Right-To-Know: List of Hazardous Substances
    New York City Department of Environmental Protection Community Right-to-Know: List of Hazardous Substances Updated: 12/2015 Definitions SARA = The federal Superfund Amendments and Reauthorization Act (enacted in 1986). Title III of SARA, known as the Emergency Planning and Community Right-to-Act, sets requirements for hazardous chemicals, improves the public’s access to information on chemical hazards in their community, and establishes reporting responsibilities for facilities that store, use, and/or release hazardous chemicals. RQ = Reportable Quantity. An amount entered in this column indicates the substance may be reportable under §304 of SARA Title III. Amount is in pounds, a "K" represents 1,000 pounds. An asterisk following the Reporting Quantity (i.e. 5000*) will indicate that reporting of releases is not required if the diameter of the pieces of the solid metal released is equal to or exceeds 100 micrometers (0.004 inches). TPQ = Threshold Planning Quantity. An amount entered in this column reads in pounds and indicates the substance is an Extremely Hazardous Substance (EHS), and may require reporting under sections 302, 304 & 312 of SARA Title III. A TPQ with a slash (/) indicates a "split" TPQ. The number to the left of the slash is the substance's TPQ only if the substance is present in the form of a fine powder (particle size less than 100 microns), molten or in solution, or reacts with water (NFPA rating = 2, 3 or 4). The TPQ is 10,000 lb if the substance is present in other forms. A star (*) in the 313 column= The substance is reportable under §313 of SARA Title III.
    [Show full text]
  • 4. Reactive and Explosive Materials
    Rubin’s group laboratory operating procedure series 4. Reactive and Explosive Materials REVISION RECORD Rev.# Date By Description 1 August 29, 2009 Robert Kennedy Initial release APPROVED (Signature and date on file) PI/date (Signature and date on file) Group Safety Manager/date Page 1 of 13 Contents 1. Scope 2. Definitions http://www.ehs.berkeley.edu/pubs/guidelines/pecguidelines.html 3. Personal Protective Equipment 4. Engineering/Ventilation Control 5. Special Handling Procedures 6. Labeling Requirements 7. Storage Requirements 8. Spill and Accident Procedures 9. Waste Disposal Page 2 of 13 1. SCOPE The purpose of this standard operating procedure is to provide guidelines for the safe handling of reactive and explosive materials. SPECIFIC SOPs ARE REQUIRED FOR INDIVIDUAL EXPLOSIVE OR REACTIVE MATERIALS. Consult the MSDS for specific information about a particular reactive or explosive material. Check the appendices at the end of this guide to identify potentially explosive compounds. 2. DEFINITIONS 2.1. Explosive Explosive materials are chemical compounds or mechanical mixtures that, when subjected to heat, impact, friction, detonation, or other suitable initiation, undergoes rapid chemical change. Large volumes of highly heated gases are evolved that exert pressure on the surrounding medium. The term applies to materials that either detonate or deflagrate. Heat, light, mechanical shock, and certain catalysts initiate explosive reactions. For a comprehensive list of potentially explosive compounds, visit the website: http://www.ehs.berkeley.edu/pubs/guidelines/pecguidelines.html The list is included in the Appendices. View this list VERY CAREFULLY. The following are some commonly used chemicals that can become an explosion hazard under certain conditions: • Organic chemicals that form PEROXIDES through exposure to air or light (see Appendix 2 - Peroxide Forming Chemicals) • Organic azides and the azide salts of heavy metals.
    [Show full text]
  • Peroxide Forming Compounds Safety Procedure
    Inventory Control, Safe Storage, Disposal and Handling of Explosive and Potentially Explosive Chemicals Table of Contents 1. Introduction ............................................................................................................................................. 1 2. Common Laboratory PECs ........................................................................................................................ 2 3. General Storage Precautions ................................................................................................................... 3 4. Specific Storage and Testing Guidelines for Peroxide Forming Chemicals ............................................... 4 4.1 About Peroxide Forming Chemicals ................................................................................................... 4 4.2 Storage of Peroxide Forming Chemicals ............................................................................................ 4 4.3 Hazardous Waste Disposal ................................................................................................................. 5 Appendix I: Explosive and Potentially Explosive Chemical Families ............................................................ 5 Appendix II: Common Peroxide Forming Chemicals ................................................................................... 13 Appendix III: Explosion Hazard Due to Container Over-pressurization ..................................................... 18 1. Introduction Explosive chemicals can release
    [Show full text]
  • View PDF Version
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue On the incompatibility of lithium–O2 battery technology with CO † Cite this: Chem. Sci.,2017,8,6117 2 Shiyu Zhang, ‡a Matthew J. Nava,‡a Gary K. Chow,b Nazario Lopez, §a Gang Wu, c David R. Britt,b Daniel G. Nocera *d and Christopher C. Cummins *a When solubilized in a hexacarboxamide cryptand anion receptor, the peroxide dianion reacts rapidly with À CO2 in polar aprotic organic media to produce hydroperoxycarbonate (HOOCO2 ) and À À peroxydicarbonate ( O2COOCO2 ). Peroxydicarbonate is subject to thermal fragmentation into two equivalents of the highly reactive carbonate radical anion, which promotes hydrogen atom abstraction reactions responsible for the oxidative degradation of organic solvents. The activation and conversion of the peroxide dianion by CO2 is general. Exposure of solid lithium peroxide (Li2O2)toCO2 in polar aprotic Received 17th March 2017 organic media results in aggressive oxidation. These findings indicate that CO must not be introduced Accepted 19th June 2017 2 À in conditions relevant to typical lithium–O2 cell configurations, as production of HOOCO2 and DOI: 10.1039/c7sc01230f À À O2COOCO2 during lithium–O2 cell cycling will lead to cell degradation via oxidation of organic Creative Commons Attribution 3.0 Unported Licence. rsc.li/chemical-science electrolytes and other vulnerable cell components. – Introduction carbonate-derived CO2 during the recharge cycle of lithium O2 batteries2 prompted us to consider the possibility that The two-electron reduction of molecular oxygen to the peroxide carbonate formation may be a consequence of peroxide dianion is an attractive cathode redox couple for developing combination with carbon dioxide; this would likely confer – 1 rechargeable lithium O2 batteries.
    [Show full text]
  • Laboratory Chemical Safety Manual 2002
    LABORATORY CHEMICAL SAFETY REFERENCE MANUAL 2013 Risk Management Services www.riskmanagement.ubc.ca Table of Contents Emergency Contact Numbers ............................................................................................ 5 Forward and Disclaimer .................................................................................................... 6 University of British Columbia Safety Policy ........................................................................ 7 1. Introduction ................................................................................................................ 9 1.1 Risk Management Services (RMS) ............................................................................ 9 1.2 Duties and Responsibilities ...................................................................................... 9 1.3 Incident/Accident Reporting ..................................................................................... 9 1.4 Chemical Safety Program ....................................................................................... 10 1.5 Environmental Services Facility (ESF)...................................................................... 10 2. Risk Assessment ........................................................................................................ 11 2.1 Safe Experiment Design ......................................................................................... 11 2.1.1 Introduction ..................................................................................................
    [Show full text]
  • By CAS Number
    RHODE ISLAND HAZARDOUS SUBSTANCE LIST Source: T - ACGIH F - NFPA49 C - IARC C. A. S. Order C.A.S. ACGIH NFPA IARC CHEMICAL NAME C 1,2-Dimethyl hydrazine - skin F Alkylaluminums C Benzo (j) fluoranthene F Bichromates F Butyllithium in hydrocarbon solvents F Calcium dichromates (see dichromates) C Chlorophenols T Coal dust T Cotten dust, raw T Diatomaceous earth, Natural C Dibenzo(a.j.)pyrene F Fuel oil T Iron salts (soluble) as Fe. F Lanolin F Lard oil (commercial or animal) F Lithium dichromate FMagnesium dichromate T Methyl acetylene-propadiene mixture C Methyl methanesulfonate T Mineral wool fiber C Mitomycin F Mono-(trichloro)4(Mono K dichloro)-penta-s-triazine-trione F Monochloro-s-triazinetrione acid F Motor fuel antiknock compounds C N-Methyl-N'-nitro-N-nitrosoguanidine C N-Nitrosopiperidine F NaK T Nickel sulfide roasting ( fume & dust ) C Nitrogen mustard N-oxide & its hydrochloride T Nuisance particulates F Oleo oil C Parachlorobiphenyls F Pentyl laurate F Pentylnaphthalene T Perlite dust C Phen F Quenching oil T Rosin core solder pyrolysis products as Formaldehyde) C Safrole T Soapstone dust C Soots, tars, and oils F Tallow oil C Thio urea F Transformer oil C Tris phosphate C Trypan blue F Uranium nitrate TF Vegetable oil-mist T Welding fumes (NOC) T Wood dust T l.p.g. 50-00-0 T F C formaldehyde solution 50-00-0 T F C formaldehyde, gas 50-00-0 T F C polyoxymethylene glycol 50-18-0 C cyclophosphamide 50-29-3 T ddt 50-32-8 T benzo[a]pyrene 50-76-0 C dactinomycin 50-78-2 T aspirin (acetylsalicylic acid) 51-52-5 C propylthiouracil
    [Show full text]
  • United States Patent (19) 11 Patent Number: 5,548,046 Sanchez 45) Date of Patent: Aug
    US005548046A United States Patent (19) 11 Patent Number: 5,548,046 Sanchez 45) Date of Patent: Aug. 20, 1996 54). STABILIZED DIALKYL OTHER PUBLICATIONS PEROXYDICARBONATE COMPOSITIONS AND THEIR USES J. Am. Chem. Soc., 1950, 72, 1254-1263. 75) Inventor: Jose Sanchez, Erie, N.Y. Primary Examiner-Josepho L. Schofer (73) Assignee: Elf Atochem North America, Inc., Assistant Examiner-Wu C. Cheng Philadelphia, Pa. Attorney, Agent, or Firm-Stanley A. Marcus; Royal E. Bright (21) Appl. No.: 197,031 22 Filed: Feb. 16, 1994 57 ABSTRACT Thermally stabilized initiator compositions comprising: (51 Int. Cl. ............................ C08F 4/34; CO8F 120/20, C08F 14/06; CO8F 112/08; CO8F 110/02 (a) at least one dialkyl peroxydicarbonate, and 52 U.S. Cl. ....................... 526/230.5; 526/236; 526/328; (b) a stabilizing effective amount of a compound of 526/344; 526/346; 526/352; 526/217 Structure I: 58) Field of Search ................................. 526/230.5, 236, H Z I 526/328,344, 346, 352 N / C-C 56 References Cited R? Y, U.S. PATENT DOCUMENTS wherein R, R and Z are as defined in the summary of 3,413,277 11/1968 Crano et al. ......................... 526/230.5 the invention section, processes for their preparation 3,821,273 6/1974 D'Angelo ............................. 526/230.5 and use are disclosed. 5,155,192 10/1992 MacLeay ................................ 526/228 FOREIGN PATENT DOCUMENTS 56-167711 12/1981 Japan. 10 Claims, No Drawings 5,548,046 1 2 STABILIZED DIALKYL significant levels of hydroperoxides such as t-butyl hydro PEROXYDICARBONATE COMPOSTIONS peroxide and cumene hydroperoxide since these impurities AND THEIR USES are free-radical chain-transfer agents and can become incor porated into the resin molecular chains as peroxy end BACKGROUND OF THE INVENTION 5 groups.
    [Show full text]
  • Challenges and Opportunities for Electrochemical Processes As Next- Generation Technologies for the Treatment of Contaminated Water Jelena Radjenovic*,†,‡ and David L
    Critical Review pubs.acs.org/est Challenges and Opportunities for Electrochemical Processes as Next- Generation Technologies for the Treatment of Contaminated Water Jelena Radjenovic*,†,‡ and David L. Sedlak§ † Catalan Institute for Water Research (ICRA), Scientific and Technological Park of the University of Girona, 17003 Girona, Spain ‡ Advanced Water Management Centre, The University of Queensland, St Lucia, Queensland 4072, Australia § Department of Civil and Environmental Engineering, University of California, Berkeley, California 94720-1710, United States *S Supporting Information ABSTRACT: Electrochemical processes have been extensively investigated for the removal of a range of organic and inorganic contaminants. The great majority of these studies were conducted using nitrate-, perchlorate-, sulfate-, and chloride-based electrolyte solutions. In actual treatment applications, organic and inorganic constituents may have substantial effects on the performance of electrochemical treatment. In particular, the outcome of electrochemical oxidation will depend on the concentration of chloride and bromide. Formation of chlorate, perchlorate, chlorinated, and brominated organics may compromise the quality of the treated effluent. A critical review of recent research identifies future opportunities and research needed to overcome major challenges that currently limit the application of electro- chemical water treatment systems for industrial and municipal water and wastewater treatment. Given the increasing interest in decentralized wastewater
    [Show full text]