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WO1996010443A1 - Agents a nitrures de phosphore pour la protection contre les incendies et les explosions - Google Patents

Agents a nitrures de phosphore pour la protection contre les incendies et les explosions Download PDF

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Publication number
WO1996010443A1
WO1996010443A1 PCT/US1995/012602 US9512602W WO9610443A1 WO 1996010443 A1 WO1996010443 A1 WO 1996010443A1 US 9512602 W US9512602 W US 9512602W WO 9610443 A1 WO9610443 A1 WO 9610443A1
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WIPO (PCT)
Prior art keywords
agent
chf
group
substituted
fire
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Ceased
Application number
PCT/US1995/012602
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English (en)
Inventor
Douglas S. Dierdorf
Stephanie R. Skaggs
Robert E. Tapscott
Jacob Kaizermann
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University of New Mexico UNM
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University of New Mexico UNM
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Application filed by University of New Mexico UNM filed Critical University of New Mexico UNM
Publication of WO1996010443A1 publication Critical patent/WO1996010443A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires

Definitions

  • the invention described and claimed herein is generally related to chemical agents used for fire extinguishment, explosion suppression, explosion inertion, and fire inertion and more particularly, to extinguishing, suppressing, and inerting phosphorus nitride agents that are replacements for halon fire and explosion suppressants and extinguishants.
  • the production of halons has been eliminated or curtailed in many nations due to their impact on stratospheric ozone.
  • halocarbons consist of all molecules containing carbon and one or more of the following halogen atoms: fluorine, chlorine, bromine, and/or iodine.
  • Halocarbons may also contain other chemical features such as hydrogen atoms, carbon-to-carbon multiple bonds, or aromatic rings.
  • Haloalkanes, a subset of halocarbons contain only single bonds between the carbon atoms.
  • the use of certain haloalkanes as fire extinguishing agents has been known for many years. For example, fire extinguishers containing carbon tetrachloride and methyl bromide were used in aircraft applications as early as the 1920s.
  • Haloalkanes used for fire protection are often designated by the "halon numbering system.” This system gives in order the number of atoms of carbon, fluorine, chlorine, and bromine in the molecule. Thus, for example, CBrClF2, whose chemical name is bromochlorodifluoromethane, is often referred to as Halon 1211.
  • extinguishment is usually used to denote complete elimination of a fire; whereas, “suppression” is often used to denote reduction, but not necessarily total elimination, of a fire or explosion. These two terms are sometimes used interchangeably.
  • halocarbon fire and explosion protection applications There are four general types of halocarbon fire and explosion protection applications.
  • Total flooding use includes protection of enclosed, potentially occupied spaces such as computer rooms as well as specialized, often unoccupied spaces such as aircraft engine nacelles and engine compartments in vehicles. Note that the term “total flood” does not necessarily mean that the extinguishing or suppressing agent is uniformly dispersed throughout the space protected.
  • the agent In streaming applications, the agent is applied directly onto a fire or into the region of a fire. This is usually accomplished using manually operated wheeled or portable units.
  • a second method which we have chosen to include as a streaming application, uses a "localized" system, which discharges agent toward a fire from one or more fixed nozzles. Localized systems may be activated either manually or automatically.
  • explosion suppression a halocarbon is discharged to suppress an explosion that has already been initiated.
  • suppression is normally used in this application since the explosion is usually self-limiting. However, the use of this term does not necessarily imply that the explosion is not extinguished by the agent.
  • a detector is usually used to detect an expanding fireball from an explosion, and the agent is discharged rapidly to suppress the explosion. Explosion suppression is used primarily, but not solely, in defense applications.
  • a halocarbon is discharged into a space to prevent an explosion or a fire from being initiated. Often, a system similar or identical to that used for total-flood fire extinguishment or suppression is used.
  • Inertion is widely used for protection of oil production facilities at the North Slope of Alaska and in other areas where flammable gases or explosive dusts may build up.
  • a dangerous condition for example, dangerous concentrations of flammable or explosive gases
  • the halocarbon is then discharged to prevent the explosion or fire from occurring until the condition can be remedied.
  • the halogenated chemical agents currently in use for fire extinguishment are generally bromine-containing haloalkanes.
  • Such chemicals contain bromine, fluorine, and carbon (and, in at least one case, chlorine), contain no hydrogen atoms, and have only single bonds between atoms.
  • These chemicals include Halon 1202 (CBr 2 F 2 ), Halon 1211 (CBrClF 2 ), Halon 1301 (CBrF 3 ), and Halon 2402 (CBrF 2 CBrF 2 ).
  • Information on the most important of the existing halons are shown in Table I.
  • Halon 1301 bromotrifluoromethane
  • Halon 1211 bromochlorodifluoromethane
  • Halon 1301 is widely used for total-flood fire extinguishment, explosion suppression, and inertion. Due to its higher boiling point and higher toxicity, Halon 1211 is usually not used in total-flood applications, but, it is widely used in streaming. TABLE I. EXISTING HALONS.
  • Bromine-containing haloalkanes such as the existing halons operate as fire extinguishing agents by a complex chemical reaction mechanism involving the disruption of free-radical chain reactions, which are essential for continuing combustion.
  • the existing halons are desirable as fire extinguishing agents because they are effective, because they leave no residue (i.e., they are liquids that evaporate completely or they are gases), and because they do not damage equipment or facilities to which they are applied.
  • halons have come to be recognized as serious environmental threats due to their ability to cause stratospheric ozone depletion.
  • production of the existing halons (Halon 1201, Halon 1301, Halon 1211, and Halon 2402) stopped at the end of 1993.
  • HCFCs hydrochlorofluorocarbons
  • HFCs hydrofluorocarbons
  • FCs or PFCs perfluorocarbons
  • HCFCs, HFCs, and FCs have a significantly decreased effectiveness compared to the halons now used for fire and explosion protection in most applications.
  • the HCFCs have a sufficiently large ODP that their production is restricted and will eventually be phased out under both the Montreal Protocol and the U.S. Clean Air Act.
  • the HFCs and, in particular, the FCs have significant atmospheric lifetimes (usually on the order of years or even hundreds of years) and are believed to cause global warming. This may cause eventual restrictions on the HFCs and FCs.
  • agent here means either a single compound or mixtures of two or more compounds and may include mixtures of phosphorus nitride compounds with other materials.
  • phosphorus nitride compounds for use as agents for fire extinguishing and suppression (in either total-flooding or streaming application), explosion suppression, and explosion and fire inertion.
  • phosphorus nitride compounds are any compounds containing a direct (covalent) bond between a nitrogen atom and a phosphorus atom. Thus, they do not include such ionic compounds as ammonium phosphate (NH 4 PO 4 ), where their is no direct bonding between nitrogen and phosphorus other than ionic attraction.
  • Phosphorus nitride compounds include two groups: cyclic compounds containing a cyclic backbone (usually containing alternating phosphorus and nitrogen atoms) and compounds having a backbone containing linear chains (but which also may contain cyclic substituents along the chain). The latter are often polymers whose exact structures have not been fully characterized. Examples are shown below for a six-member cyclic ring and for a four-member chain.
  • Alkyl groups are groups containing only carbon and hydrogen atoms such as methyl (-CH 3 ), ethyl (-CH 2 CH 3 ), n-propyl (-CH 2 CH 2 CH 3 ), and is ⁇ -propyl (CH(CH 3 ) 2 ).
  • Substituted alkyl groups are alkyl groups in which one or more of the hydrogen (H) atoms have been replaced by other atoms or groups.
  • Aryl groups are groups containing only carbon and hydrogen atoms in "aromatic" rings. The most common of these is the phenyl group, -C 6 H5. Substituted aryl groups have one or more of the hydrogen atoms replaced by some other substituent. An example is perfluorophenyl, -C 6 F 5 .
  • Alkoxide groups have the structure -OR, where R is an alkyl or a substituted alkyl group.
  • Agents include the cyclic phosporus fluoronitride compounds P 3 N 3 F 6 , P 4 N 4 F 8 , and, in general, cyclic compounds having a formula (PNF 2 ) n , where "n" is 2 or greater. These compounds have the cyclic PN backbone with fluorine atoms as substituents. For example, the structures of the "trimer” P 3 N 3 F 6 and "tetramer” P 4 N 4 F 8 are shown below.
  • the compounds also include the cyclic phosphorus chloronitride compounds P3N3CI6, P4N4CI8, and, in general, cyclic compounds having a formula (PNCl 2 ) n . where "n" is 2 or greater. Cyclic phosphorus nitrides containing both fluorine and chlorine in the same molecule are also included. Examples of trimers are P3N3CIF5, P 3 N 3 C1 2 F 4 , P 3 N 3 C1 3 F 3 , P 3 N 3 C1 4 F 2 , and P 3 N 3 C1 5 F. These include all isomers of the compounds. Isomers are different arrangements of the atoms on the same molecule. For example, three isomers available for P3N 3 CI3F 3 are shown below.
  • Cis-2,4-dibromo-2,4,6,6- tetrafluoro-l,3,5,2,4,6-triazaphosphorine is an example of a mixed fluorine/bromine substituted 6-membered ring:
  • phosphorus nitrogen compounds also form chains.
  • the cup burner is a widely accepted laboratory test apparatus for determining the fire extinguishing and suppressing effectiveness of agents.
  • an agent is introduced into a stream of air which passes around a cup of burning liquid fuel, and the concentration of gaseous agent needed to extinguish the flame is determined.
  • any agent that is normally a liquid is allowed to become a gas before being mixed into the stream of air and passed by the burning liquid fuel.
  • halocarbon carrier may be added to one or more of the phosphorus nitride compounds to aid in distribution of the agent, to modify the physical properties, or to provide other benefits.
  • Mixtures of halocarbon carriers with phosphorus nitride compounds may be either azeotropes, which do not change in composition as they evaporate, or zeotropes, which do change in composition during evaporation (more volatile components tend to evaporate preferentially).
  • azeotropes Mixtures that change only slightly in composition during evaporation are sometimes termed "near azeotropes.” In some cases, there are advantages to azeotropes and near azeotropes. Mixtures covered by this application include azeotropes, near azeotropes, and zeotropes.
  • Carriers can be materials such as hydrochlorofluorocarbons, hydrofluorocarbons, or perfluorocarbons.
  • Hydrochlorofluorocarbons are chemicals containing only hydrogen, chlorine, fluorine, and carbon. Examples of
  • HCFCs that could be used as carriers are 2,2-dichloro-l,l,l-trifluoroethane
  • HFCs are chemicals containing only hydrogen, fluorine, and carbon.
  • Examples of potential HFC carriers are trifluoromethane (CHF 3 ), difluoromethane (CH 2 F 2 ), 1,1- difluoroethane (CH 3 CHF 2 ), pentafluoroethane (CHF 2 CF 3 ), 1,1,1,2-tetrafluoroethane (CH 2 FCF 3 ), l,l,l,2,2-pentafluoropropane (CF 3 CF 2 CH 3 ), 1,1,1,2,3,3- hexafluoropropane (CF 3 CHFCHF 2 ), 1,1,1,3,3,3-hexafluoropropane (CF 3 CH 2 CF 3 ), 1,1,1 ,2,2,3,3-heptafluoropro ⁇ ane (CF 3 CF 2 CF 2 H), 1,1,1 ,2,3,3,3-heptafluoropropane (CF 3 CHFCF 3 ), and 1,1,1,4,4,4
  • Perfluorocarbons which contain only fluorine and carbon, are characterized by very low toxicities.
  • Examples of perfluorocarbons that could be used as carriers are tetrafluoromethane (CF ), hexafluoroethane (CF 3 CF 3 ), octafluoropropane (CF 3 CF 2 CF 3 ), decafluorobutane (CF 3 CF 2 CF 2 CF 3 ), dodecafluoropentane (CF 3 CF 2 CF 2 CF 2 CF 3 ), tetradecafluorohexane (CF 3 CF 2 CF 2 CF 2 CF 2 CF 3 ), perfluoromethylcyclohexane (C 6 F ⁇ i CF 3 ), perfluorodimethylcyclohexane (CeF ⁇ o(CF 3 ) 2 ), and perfluoromethyldecalin (C ⁇ oF ⁇ CF 3 ).
  • the embodiments include the use of agents comprised of cyclic and/or linear (polymeric) phosphorus nitrides, with or without carriers, for the four applications of fire extinguishment or suppression using a total-flood application, fire extinguishment or suppression using a streaming application, explosion suppression, and inertion against fires and explosions.
  • agents comprised of cyclic and/or linear (polymeric) phosphorus nitrides, with or without carriers, for the four applications of fire extinguishment or suppression using a total-flood application, fire extinguishment or suppression using a streaming application, explosion suppression, and inertion against fires and explosions.
  • the following examples illustrate the fire and explosion protection in accordance with the invention.
  • Example 1 Into a flowing air stream in which a cup of burning n-heptane fuel is contained was introduced a mixture of N 3 P 3 F6, N 3 P 3 FsCl, N 3 P 3 F 4 C1 2 , and N 3 P 3 F 3 C1 3 sufficient to raise the concentration to 0.28 percent agent by gas volume.
  • This concentration of agent was less than one-tenth as much as required to extinguish the same fire using Halon 1211 (which required a concentration of 3.2 percent) or using Halon 1301 (which required a concentration of 2.9 percent).
  • Example 2 Onto a 1.5-inch diameter cup containing 1 /4-inch of burning ⁇ - heptane fuel, a stream of a mixture of N 3 P 3 F 6 , N 3 P 3 F 5 C1, N 3 P 3 F 4 C1 2 , and N 3 P 3 F 3 C1 3 was discharged. The fire was immediately extinguished.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fireproofing Substances (AREA)

Abstract

L'invention concerne plusieurs types d'agents à nitrures de phosphore utilisés pour éteindre les incendies et empêcher les explosions, et pour limiter leurs effets. Dans ces agents, l'azote et le phosphore sont liés directement par des liaisons covalentes. L'invention concerne plus particulièrement des agents à base de composés cycliques de nitrures de phosphore et de composés linéaires de nitrures de phosphore et de polymères.
PCT/US1995/012602 1994-09-30 1995-09-29 Agents a nitrures de phosphore pour la protection contre les incendies et les explosions Ceased WO1996010443A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31640694A 1994-09-30 1994-09-30
US08/316,406 1994-09-30

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WO1996010443A1 true WO1996010443A1 (fr) 1996-04-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021276A1 (fr) 2003-08-01 2005-03-10 Man Roland Druckmaschine Ag Procede et dispositif permettant d'imprimer egalement la conductivite electrique
CN113113669A (zh) * 2021-04-09 2021-07-13 珠海市赛纬电子材料股份有限公司 电解液添加剂和含有该添加剂的非水电解液及锂离子电池

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867344A (en) * 1969-04-17 1975-02-18 Grace W R & Co Burn-resistant plastic compositions
US3974251A (en) * 1973-03-07 1976-08-10 Hoechst Aktiengesellschaft Production of flameproof fibers of regenerated cellulose
US4053560A (en) * 1974-07-22 1977-10-11 Monsanto Research Corporation Flame retardant
US4063883A (en) * 1974-08-20 1977-12-20 Hoechst Aktiengesellschaft Manufacture of flame-retardant regenerated cellulose fibres
US4722766A (en) * 1984-09-11 1988-02-02 Graviner Limited Extinguishing of fires and explosions
US4903573A (en) * 1987-03-11 1990-02-27 Imperial Chemical Industries Plc Explosion suppression system and composition for use therein
US5102557A (en) * 1990-10-05 1992-04-07 University Of New Mexico Fire extinguishing agents for streaming applications
US5135054A (en) * 1990-10-05 1992-08-04 University Of New Mexico Fire extinguishing agents for flooding applications

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867344A (en) * 1969-04-17 1975-02-18 Grace W R & Co Burn-resistant plastic compositions
US3974251A (en) * 1973-03-07 1976-08-10 Hoechst Aktiengesellschaft Production of flameproof fibers of regenerated cellulose
US4053560A (en) * 1974-07-22 1977-10-11 Monsanto Research Corporation Flame retardant
US4063883A (en) * 1974-08-20 1977-12-20 Hoechst Aktiengesellschaft Manufacture of flame-retardant regenerated cellulose fibres
US4722766A (en) * 1984-09-11 1988-02-02 Graviner Limited Extinguishing of fires and explosions
US4903573A (en) * 1987-03-11 1990-02-27 Imperial Chemical Industries Plc Explosion suppression system and composition for use therein
US5102557A (en) * 1990-10-05 1992-04-07 University Of New Mexico Fire extinguishing agents for streaming applications
US5135054A (en) * 1990-10-05 1992-08-04 University Of New Mexico Fire extinguishing agents for flooding applications

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005021276A1 (fr) 2003-08-01 2005-03-10 Man Roland Druckmaschine Ag Procede et dispositif permettant d'imprimer egalement la conductivite electrique
CN113113669A (zh) * 2021-04-09 2021-07-13 珠海市赛纬电子材料股份有限公司 电解液添加剂和含有该添加剂的非水电解液及锂离子电池
CN113113669B (zh) * 2021-04-09 2022-05-17 珠海市赛纬电子材料股份有限公司 电解液添加剂和含有该添加剂的非水电解液及锂离子电池

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