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    • 专利摘要:
    COMPOSITION FOR EXTINGUISHING FERROCENE-BASED FIRE The present invention relates to a composition to extinguish fire based on ferrocene. The ferrocene-based fire-extinguishing composition comprises ferrocene, a derivative or a combination thereof in a content of 25 percent weight or more; when in use, a pyrotechnic agent is used as a heat source and as a heat source and as a power source, the pyrotechnic agent is fired and the high temperature generated by the combustion of the pyrotechnic agent is used to make the composition to extinguish fire produce a large amount of substance to extinguish fire, which is sprayed out together with the pyrotechnic agent in such a way as to achieve the purpose of extinguishing a fire. Compared to a conventional fire-extinguishing composition, a more efficient and safer fire-extinguishing composition is thus provided.
    公开号:BR112013006255B1
    申请号:R112013006255-0
    申请日:2011-09-07
    公开日:2021-01-19
    发明作者:Hongbao Guo；Honghong Liu
    申请人:Xi'an Westpeace Fire Technology Co., Ltd.；
    IPC主号:
    专利说明:

    Technical Field
    [001] The present invention relates to the field of fire protection and refers to a composition for extinguishing fire that is innovative and efficient, and more specifically to a composition for extinguishing fire based on ferrocene using ferrocene and its derivatives with the main materials to extinguish the fire. Background of the Invention
    [002] Since the Montreal Protocol, Canada (1987) presented a specific goal to replace the halon agent to extinguish fire, several countries around the world have committed themselves to researching a new technology to extinguish fire. The targeting of peoples' efforts is to acquire a technology to extinguish fire that is highly efficient with regard to extinguishing fire and that is free from contamination of the environment.
    [003] Because they are environmentally and environmentally friendly, gas fire extinguishing systems, dry powder fire extinguishing systems and water-based extinguishing systems have been widely used as an alternative to the halon agent to extinguish fire. Fire extinguishing systems for inert gases such as carbon dioxide, IG541 etc., physically extinguish the fire due to suffocation by reducing the oxygen concentration of the burned area. This way of extinguishing a fire easily poses a threat with regard to personal safety. Systems for extinguishing dry powder fire eject a dry powder using pressurized gas in such a way that the powder comes into contact with the flames and extinguishes the flames due to a physical and chemical inhibiting action. The system for extinguishing fire by spraying water performs a triple function, cooling, suffocating and isolating thermal radiation by means of a mist or water mist to control the fire, suppress the fire and extinguish the fire.
    [004] However, all of these fire extinguishing systems require high pressure storage in addition to a large volume and hence there is a risk of a physical explosion during storage. A document entitled “Security Analysis of Gas Fire Extinguishing System” (Fire Protection Science and Technology 2002 21 (5)) reports the analysis of the existing risks in the system to extinguish gas fire and produces a list of safety-related accidents triggered through the use of systems to extinguish pressurized and stored gas fires.
    [005] The data shows that foreign research institutions have conducted a lot of research looking for substances to extinguish fire. The next generation of the Fire and Extinguishing Technology (NGP) project team at the Building and Fire Research Center of the National Institute of Standards and Technology of America has already done a great deal of experimental work in the search for substances to extinguish fire to replace halon. In their studies, they found that ferrocene is a fire-extinguishing substance with a strong fire-extinguishing ability. Ferrocene was heated with nitrogen at a high temperature, carbon dioxide or CF3H as a carrier gas and was sublimated to gas. The test to extinguish fire was carried out by applying the gas together with ferrocene vapor over a flame. It has been found that the addition of ferrocene can significantly reduce the concentration to extinguish the carrier gas, thus proving that ferrocene has a strong ability to suppress flames (please refer to Halon Options Technical Working Conference 2-4May 2000, Flame Inhibition by ferrocene, alone and with CO2 and CF3H; Proceedings of the Combustion Institute, Volume 28.2000 / pp 965-2972, Flame inhibition by ferrocene and blends of inert and catalytic agents; Flame inhibition by ferrocene, Carbon Dioxide, and Trifluotomethane Blends Synergistic and Antagonistic Effects).
    [006] Henan Polytechnic University has also carried out research regarding ferrocene flame suppression and has published relevant articles such as Study of Characteristics of Heat Release Rate of Pool Fire under Action of Ferrocene, Journal of Henan Polytechnic University, 2008, Vol .27, No.6, Study of Characteristics of the Extinguishment of Alcohol Fire, Journal of China University of Mining Technology, 2008, Vol.37, No.2, Analysis of Effectiveness of Gas-phase Ferrocene in Suppressing Pool Fire, Journal of Safety and Environment, 2008, Vol.8, No.2, Experimental Research of Gas phase Ferrocene in Suppressing Alcohol Pool Fire, Thermal Science and Technology, 2007, Vol.6, No.3, Development of a Ferrocene Fire extinguishing Experimental Platform and Experimental Study on Fire extinguishing Effectiveness, Fire Science, 2007, Vol.16, No.2. In addition, Chinese patent CN 101327364A discloses an experimental system for extinguishing fire with ferrocene.
    [007] However, these studies on performance to extinguish fire with ferrocene have only been carried out and tested on laboratory research bases, but have not been applied practically. Although the Chinese patent CN 1238226a discloses an innovative aerosol fire extinguishing agent in which ferrocene is used in the formulation of the aerosol fire extinguishing agent, ferrocene is used as a catalyst and its flame inhibiting property is not used.
    [008] Existing aerosol fire extinguishing agents mainly include type S and type K extinguishing agents. In view of a comprehensive analysis of their performance characteristics, aerosol extinguishing agents mainly have the following disadvantages: due to the occurrence of a redox reaction of the agent to extinguish fire, a large amount of gas and active particles is generated and hence, the agents to extinguish fire in aerosol achieve the purpose of extinguishing fire through the combination of chemical and physical methods through the chain fission reaction of the active particles and the coverage and suffocation by the large amount of gas. The aerosol fire extinguishing agent undergoes a combustion reaction and releases a large amount of heat while releasing the aerosol. Therefore, it is necessary to add a cooling system to effectively reduce the temperature of the device and the aerosol and avoid outbreaks of secondary fires. As a result, the structure of the device is complex and bulky, and the process is complicated and expensive. Furthermore, many of the active particles lose their activity due to the presence of the cooling system, resulting in a great reduction in performance to extinguish fire. Summary of the Invention
    [009] Considering the state of the devices for extinguishing existing fire, especially the inherent disadvantages with regard to aerosol fire extinguishing agents, the objective of the invention is to provide a composition to extinguish fire based on ferrocene that does not need pressurized storage that is safer and more environmentally friendly, as well as efficient.
    [010] The ferrocene-based fire extinguishing composition of the present invention comprises ferrocene, ferrocene derivatives or a combination thereof, in a content of 25 weight percent or more.
    [011] In addition to ferrocene or ferrocene derivatives as the main material for extinguishing fire, a variety of flame retardants, additives, etc. commonly used in the art can be suitably added to the ferrocene-based fire extinguishing composition of the present invention.
    [012] The ferrocene-based fire extinguishing composition of the present invention can simultaneously achieve the following effects. Firstly, the composition to extinguish fire based on ferrocene when heated, instantly releases a large amount of an efficient fire extinguishing substance which is mainly in the form of liquid particles or solid particles. Due to the synergistic effect of a variety of micro particles, the time to extinguish the fire is greatly reduced. Second, the flame retardant effect of the decomposition product further enhances the fire extinguishing efficiency of the fire extinguishing agent while at the same time reducing the possibility of re-occurrence of the combustion source. Third, the ferrocene-based fire extinguishing composition being heated to a high temperature can rapidly undergo endothermic decomposition, hence, efficiently and quickly reducing the heat released by the combustion of a pyrotechnic agent and greatly reducing the temperature of the nozzle of the fire extinguisher and the substance being sprayed out. Therefore, the complicated cooling system of the fire extinguishing device is eliminated, and the risk of outbreaks of secondary fires is also eliminated. Fourth, the fire-extinguishing composition can be easily processed and molded and can be used alone or used in combination with a physical refrigerant. Fifth, it has a stable performance and is easy to store in the long term. Sixth, it has a low toxicity or it is non-toxic and it is environmentally and ecologically correct and it performs well.
    [013] Hereinafter the ferrocene-based fire-extinguishing composition of the present invention will be described in more detail.
    [014] The ferrocene-based fire extinguishing composition of the present invention comprises ferrocene, ferrocene derivatives or a combination thereof with a content of 25 weight percent or more.
    [015] It has been revealed in the prior art that ferrocene is added to the composition to extinguish fire. However, it is added as an additive and the amount of addition is very small, about 5 percent by weight or less. Through a large number of experiments, the present inventors have found that when ferrocene or ferrocene derivatives are used as the material to extinguish a main fire (at a content of 25 percent by weight or more), an excellent effect for extinguishing fire can be achieved and it is something environmentally and ecologically correct.
    [016] The flame-inhibiting mechanism of ferrocene or ferrocene derivatives is as follows: ferrocene in the gas phase or its derivatives under a high temperature decomposes to produce gaseous iron atoms that react with oxygen to generate FeO2; FeO2 can capture oxygen radicals during the chain combustion reaction to generate FeO; FeO, which is an unstable active substance, enters a catalytic circulation of the hydrogen atom recombination together with Fe (OH) 2 and FeOH; Fe (OH) 2 can capture hydrogen radicals during the combustion chain reaction to generate FeOH; FeOH can continue to consume hydrogen radicals during the chain combustion reaction to generate FeO, hence, forming a circulation that FeO consumes hydrogen radicals to block the chain combustion reaction.
    [017]

    [018]

    [019]

    [020] While a large number of radicals block the chain combustion reaction, iron particles or other active particles released during the decomposition process have a synergistic effect with the substance to extinguish fire released from pyrotechnic agents and components auxiliaries of the fire-extinguishing composition in such a way that the fire-extinguishing efficiency of the fire-extinguishing agent is further enhanced and the time to extinguish effective fire is greatly reduced.
    [021] In order to obtain a good fire-extinguishing effect, the content of ferrocene or a ferrocene derivative contained in the ferrocene-based fire extinguishing composition of the present invention is at least 25 by mass percentage, preferably 40 percentage mass or more. Although the objective of the present invention can be achieved when the content of ferrocene or ferrocene derivative is 100 percent by mass, when this content reaches a certain level, the effect to extinguish fire of ferrocene or the ferrocene derivative will not change considerably in the regards the increase in its content. From this point of view, it is preferable that the content of ferrocene or the ferrocene derivative be 80 weight percent or less.
    [022] In order to ensure that the fire extinguishing composition has a stable performance under a normal temperature condition and is conveniently stored for a long time, preferably the ferrocene derivative has a melting point of 100 ° C or more high. In addition, a volatile ferrocene derivative is additionally appreciated in such a way that the fire-extinguishing composition being heated can rapidly decompose, volatize and release a large amount of substance to extinguish fire and quickly consume the heat generated by the combustion of the agent to extinguish fire. .
    [023] The ferrocene derivatives used in the present invention can be ferrocene aldehydes or ketones such as 1,2-diformyl ferrocene, 3-ferrocenyl acryldehyde, (4-formylphenyl) ferrocene, octamethylformylferrocene, chloroacetyl ferrocene, 1-acetyl-1 ' ferrocene cyano, α-oxo-1,1'-trimethylene ferrocene, β-oxo-1,1'-tetramethylene ferrocene, 1,1'-diacetyl ferrocene, (1,3-dioxobutyl) ferrocene, 1-acetyl-1 '- acetylamino ferrocene, (2-chlorobenzoyl) ferrocene, benzoyl ferrocene, 1,1'-di (3-cyanopropionyl) ferrocene, phenylacetyl ferrocene, (2-methoxybenzoyl) ferrocene, 1,1'- di (acetoacetyl) ferrocene , 1-acetyl-1'-p-chlorobenzoyl ferrocene, 1-ferrocenyl-3-phenyl-2-propen-1-one, 3-ferrocenyl-1-phenyl-2-propen-1-one, (2,4- dimethoxy benzoyl) ferrocene, 1,1'-di (propionoacetyl) ferrocene, bisferrocenyl methyl ketone, 2-acetyl-biferrocene, 1,1'- di (pentafluorobenzoyl) ferrocene, 1,2-bisferrocenyl acyl ethane, 1,3-bis (ferrocenyl methylidene) acetone, 1'-acetyl-2,2-bisf errocenyl propane, 1,1'-di (benzoylacetyl) ferrocene
    [024] The ferrocene derivatives used in the present invention can also be composed of ferrocene carboxylic acid and its derivatives, such as carboxylic acid, 2-hydroxy ferrocene carboxylic acid, ferrocene acetic acid, ferrocene thioacetic acid, 3- acrylic acid ferrocenyl, ferrocene propionic acid, methylatio ferrocene acetic acid, 1,1'-ferrocene diacetic acid, ferrocene butyric acid, ferrocene pentanoic acid, 2,2-dimethyl-3-ferrocenyl propionic acid, 1,1'- dipropionic ferrocene, hexanoic ferrocene acid, 1,1'-dibutyric ferrocene acid, 4,4'-bisferrocenyl pentanoic acid, diformyl 1,1'-ferrocene chloride, 1,2-ferrocene dicarboxylic anhydride, 1,1'-diacetic ferrocene anhydride , 2- (1'-carboxymethyl ferrocene) benzoic anhydride, ferrocene formic anhydride, ferrocene-1,1'-dicarboxylate dimethyl, 3-ferrocenyl ethyl acrylate, 1.1 '' '- di (methoxycarbonyl) -biferrocene, 4 , 4'- bisferrocenyl methyl pentanoate, ferroc formamide eno ferrocene, formyl hydroxylamino, ferrocene formil hydrazide, acetamido ferrocene, ferrocene formyl azirdine, 1'-vinyl ferrocene formamide, N- (2-cyanoethyl) ferrocene formamide, N-acetyl-2-ferrocenyl ethyl, N-butyl ferrocene formamide, 1 , 1'-ferrocene diformila azirdino, N, N, N ', N'- tetramethyl-1,1'-ferrocene diformamido, N-phenyl ferrocene forms hydroxylamino, N-ferrocenyl phthalimido, N-benzoyl-2-ferrocenyl ethyl, 4 , 4-bisferrocenyl valeramido, ferrocene cyan, 1,1'-ferrocene cyano.
    [025] The ferrocene derivatives used in the present invention can also be composed of ferrocene alcohols, phenols or ethers such as α-hydroxy ferrocene acetonitrile, ferrocene dimethanol, ferrocene 1,2-dimethanol, 1,1'-di ( 1- ethoxy) ferrocene, octamethyl ferrocene methanol, ferrocenyl- (2,4,6-trimethoxyphenyl) methanol, bisferrocenyl methanol, α, α-diphenyl ferrocene methanol, 4- (2-ferrocenyl-2-ethoxy) - 4'-methyl -2,2'-bipyridine, 2-methyl-α, α-diphenyl ferrocene methanol, 1,4-bisferrocenyl-1,4-butanediol, 4,4-bisferrocenyl-1-pentanol, 4,4'-di (2 -ferrocenyl-2-ethoxy) -2,2'-bipyridine, 1,1'-di (diphenylhydroxymethyl) ferrocene, (4-hydroxyphenyl) ferrocene, 2-oxa-1,1'-trimethylene ferrocene, 1,3-dimethyl -2-oxa-1,1'-trimethylene ferrocene, bis (ferrocenyl methyl) ether, 1,1-bisferrocenyl methyl tert-butyl ether.
    [026] The ferrocene derivatives used in the present invention can also be ferrocene hydrocarbon compounds such as 1,1'-trimethylene ferrocene, 1,1'-diethyl ferrocene, 1-vinyl1'-chloroferrocene, 1,1'-di (α-cyclopentadienyl ethylidene) ferrocene, phenylethynyl ferrocene, bisferrocenyl acetylene, 1,1'-di (phenylethynyl) ferrocene, 1,1'-bis (ethinyl ferrocenyl) ferrocene, 1,1 ', 2,2'-tetrachlorous ferrocene, fluoroferrocene, biferrocene, 2,2-bisferrocenyl propane, 1,1-bisferrocenyl pentane, 1 ', 1' '' - di (triphenyl methyl) biferrocene.
    [027] The ferrocene derivatives used in the present invention can also be nitrogen-containing ferrocene compounds such as (2-nitrovinyl) ferrocene, (4-nitrophenyl) ferrocene, ethylamino 2-hydroxy-2-ferrocenyl, N, N'-bisferrocenyl ethylenediamino, N, N'-bisferrocenyl methyl ethylenediamino, N, N'-di (bisferrocenyl methyl) ethylenediamine, 2-hydroxy-5-nitrobenzylimino ferrocene, benzoyl ferrocene oxime, ferrocene methyl diazomethyl ketone, 1,1'-diphenyl azene, 1,1'-diphenyl azene phenyl methylimino benzene, 1,6-differenocenyl-2,5-diaza-1,5-hexadiene.
    [028] The ferrocene derivatives used in the present invention can also be sulfur-containing or phosphorus-containing ferrocene compounds such as disulfonyl 1,1'-ferrocene chloride, disulfonyl 1,1'-ferrocene azide, sulfonyl ferrocene chloride, acid sulfinic ferrocene, sulfonic acid ferrocene, (diethyldithiocarbamate) -ferrocene, 1,1'-di (dimethyl-dithiocarbamate) -ferrocene, ferrocene methyl phenyl sulfone, thiolferrocenyl-ferrocene sulfonate, bisferrocenyl disulfide, N, N'-dicylic -1,1'-disulfonamido ferrocene, (diphenylphosphine) -ferrocene; and silicone-containing ferrocene compounds such as 1,1'-dichloro-2-trichlorosylanylferrocene, bis (1,1'-dichloro-2,2'-ferrocenylean) -silane, (1,1'-octamethyl-ferrocenyl) -dimethylasilane , (1,1'-dichloro-2,2'-ferrocenilean) -diphenylasilane, 1,1'-di [α-hydroxy-α- (trisylylpropyl) ethyl] ferrocene, 1,1'-di (phthalimido methyladisylyl) ferrocene .
    [029] The ferrocene derivatives used in the present invention can also be heterocyclic ferreocene compounds such as 2-ferrocenyl-1,3-dithian, 5-ferrocenyl-methylidene-1-aza-3-oxa-4-oxo-2- phenyl-1-cyclopentene, 1,3-bisferrocenyl imidazoline, 2,5-bisferrocenyl tetrahydrofuran.
    [030] The ferrocene derivatives used in the present invention can also be, for example, 1,1'-dic copper ferrocene, chlorine mercury ferrocene, boric acid ferrocene, acetylated ferrocenyl cuprous, titanocene bisferrocenyl.
    [031] For individuals with expertise versed in the technique, it should be understood that the present invention aims to find a main and innovative material for extinguishing fire and its content in the composition for extinguishing fire, which can be used by those individuals with expertise versed in the technique optionally in combination with cooperating substances commonly used in the art such as flame retardants, additives or other fire-extinguishing substances, etc., as long as the fire-extinguishing composition is not impaired.
    [032] The addition of these coordination substances aims to prevent the material to extinguish a main fire from burning before reaching the flames and, therefore, lose the ability to extinguish fire.
    [033] The flame retardants which can preferably be used in the present invention are compounds which have a decomposition temperature of 100 ° C or more, which are able to decompose when heated and which can release particles of gas, liquid or solid or compounds in which thermal decomposition products have a flame retardant effect. Specifically, as flame retardants brominated flame retardants such as etrabromobisphenol A, tetrabromobisphenol A ether, 1,2-bis (tribromophenoxy) ethane, 2,4,6-tribromophenyl glycidyl ether, tetrabromic phthalic anhydride, 1,2- bis (tetrabromo phthalimido) ethane, tetrabromo dimethyl phthalate, tetrabromo disodium phthalate, decabromodiphenyl ether, tetradecabromodi (phenoxy) benzene, 1,2-bis (pentabromophenyl) ethane, pentabromophenyl-hydroxybromethylene, pentabyl acrylate, pentabromethyl acrylate , hexabromobenzene, pentabromotoluene, 2,4,6-tribromophenyl maleimido, hexabromo cyclododecane, N, N'-1,2-bis (dibromonorbornyl dicarbimido) ethane, pentabromochloro-cyclohexane, tri (2,3-dibromopropyl) isocyanurate, bromine copolymer - styrene, tetrabromobisphenol A-carbonate oligomer, polypentabromobenzyl acrylate, polydibromophenyl ether; chlorinated flame retardants such as declorane plus, HET anhydride (hydrochloric anhydride), pentacyclodecane perchlorine, tetrachloro bisphenol A, tetrachlorophthalic anhydride, hexachlorobenzene, chlorinated polypropylene, chlorinated polyvinyl chloride, vinyl chloride chloride and vinyl chloride chloride , hexachloroethane; organic phosphorus flame arresters such as 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosfabicyclo [2,2,2] octane, 2,2-dimethyl-1,3-propanediol-di ( neopentyl glycol) diphosphate, 9,10-dihydro-9-oxa-10-phosphatenatrene phosphathenthene-10 oxide, bis (4-carboxyphenyl) -phosphine oxide, phosphine bis (4-hydroxyphenyl) -phenyl oxide, phosphine oligomer phenyl (diphenyl sulfone) phosphate; halogenated phosphorus flame arresters such as tris (2,2-di (bromomethyl) -3-bromopropyl) phosphate, tris phosphate (dibromophenyl), 3,9-bis (tribromophenoxy) -2,4,8,10-tetraoxa- 3,9- diphosphospiro [5.5] -3,9-dioxo-undecane, 3,9-bis (pentabromophenoxy) -2,4,8,10-tetraoxa-3,9-diphosphospiro [5.5] -3 , 9-dioxo-undecane, 1-oxo-4-tribromophenoxycarbonyl-2,6,7-trioxa-1-fosfabicyclo [2,2,2] octane, p-phenylean-tetrakis (2,4,6-tribromophenyl) - diphosphate, 2,2-di (chloromethyl) -1,3-propanediol-di (neopentyl glycol) diphosphate, 2,9-di (tribromo-neopentyloxy) -2,4,8,10-tetraoxa-3,9-diphosphospiro [5.5] -3,9-dioxo-undecane; nitrogen-based flame retardants or nitrogen phosphorus-based flame retardants such as melamine, melamine cyanide, melamine orthophosphate, dimelamine orthophosphate, melamine polyphosphate, melamine borate, melamine octamolibate, cyanuric acid, isocyanuric acid, cyanuric acid, isocyanuric acid, cyanuric acid, isocyanuric acid. (hydroxyethyl), 2,4-diamino-6- (3,3,3-trichloropropyl) -1,3,5-triazine, 2,4-di (N-hydroxymethyl-amino) -6- (3, 3,3-trichloro-propyl-1,3,5-triazine), diguanidine hydrophosphate, hydrogen guanidine phosphate, guanidine carbonate, guanidine sulfamate, urea, urea dihydrogen phosphate, dicyandiamide, melamine bis (2,6,7 -trioxa-phosfa-bicyclo [2.2.2] octane-1-oxo-4-methyl) -hydroxy-phosphate, 3,9-dihydroxy-3,9-dioxo-2,4,8,10-tetraoxa-3, 9-diphosphospiro [5.5] undecane-3,9-dimelamino, 1,2-di (2-oxo-5,5-dimethyl-1,3-dioxa-2-phosfacyclohexyl-2-amino) ethane, N, N ' -bis (2-oxo-5,5-dimethyl-1,3-dioxa-2-phosfacyclohexyl) -2,2'-m-phenylanediamino, tri (2-oxo-5,5-dimethyl-1,3-dioxa -2-phosphacyclohexyl -2-methyl) amino, hexachlorocyclotriphosphazene; and inorganic flame retardants such as red phosphorus, ammonium polyphosphate, diamonium hydrophosphate, dihydrogen ammonium phosphate, zinc phosphate, aluminum phosphate, boron phosphate, antimony trioxide, aluminum hydroxide, aluminum hydroxide, hydromagnesite, alkaline aluminum oxalate, zinc borate, barium metaborate, zinc oxide, zinc sulfide, zinc heptahydrate, aluminum borate rod, ammonium octamolybdate, ammonium heptamolybdate, zinc stannate, stannous oxide, stanic oxide, ferrocene, ferric acetone, ferric oxide, ferric iron oxide, ammonium bromide, sodium tungstate, potassium hexafluorotitanate, potassium hexafluorozirconate, titanium dioxide, calcium carbonate, barium sulfate.
    [034] The flame retardants used in the present invention can also be other chemical substances which have a decomposition temperature of 100 ° C or higher and can decompose substances to extinguish fire, for example, sodium bicarbonate, potassium bicarbonate, cobalt carbonate, zinc carbonate, basic zinc carbonate, heavy magnesium carbonate, basic magnesium carbonate, manganese carbonate, ferrous carbonate, strontium carbonate, sodium potassium hexahydrate carbonate, magnesium carbonate, calcium carbonate, dolomite, basic copper carbonate, zirconia carbonate, beryllium carbonate, sodium sesquicarbonate, cerium carbonate, lanthanum carbonate, guanidine carbonate, lithium carbonate, scandium carbonate, vanadium carbonate, chromium carbonate, nickel carbonate, carbonate yttrium, silver carbonate, praseodymium carbonate, neodymium carbonate, samarium carbonate, europium carbonate, gadolinium carbonate, terbium carbonate, thulium carbonate, ytterbium carbonate, lutetium carbonate, aluminum diacetate, calcium acetate, sodium bitrate, sodium acetate, potassium acetate, zinc acetate, strontium acetate, nickel acetate, acetate copper, sodium oxalate, potassium oxalate, ammonium oxalate, nickel oxalate, manganese oxalate dihydrate, iron nitride, sodium nitrate, magnesium nitrate, potassium nitrate, zirconia nitrate, dihydrogen calcium phosphate, dihydrate phosphate sodium dihydrogen, potassium dihydrogen phosphate, aluminum dihydrogen phosphate, dihydrogen ammonium phosphate, dihydrogen zinc phosphate, dihydrogen manganese phosphate, dihydrogen magnesium phosphate, hydrogen sodium phosphate, hydrogen hydrogen phosphate, calcium phosphate hydrogen, ammonium phosphate, mannium ammonium phosphate, ammonium polyphosphate, potassium metaphosphate, potassium tripolyphosphate, trimetaphosphate d and sodium, ammonium hypophosphite, dihydrogen ammonium phosphite, manganese phosphate, hydrogen dioxide phosphate, hydrogen dimanganese phosphate, guanidine phosphate, melamine phosphate, urea phosphate, strontium phosphate, hydrogen dimetaborate, boron acid, ammonium pentateate potassium tetraborate, magnesium metaborate octahydrate, ammonium tetraborate tetrahydrate, strontium metaborate, strontium tetraborate, strontium tetraborate tetrahydrate, sodium tetraborate decahydrate, manganese borate, zinc borate, ammonium sulfate, ammonium fluoride aluminum, aluminum potassium sulfate, aluminum ammonium sulfate, ammonium sulfate, magnesium hydrogen sulfate, aluminum hydroxide, aluminum hydroxide, iron hydroxide, cobalt hydroxide, bismuth hydroxide, strontium hydroxide, cerium hydroxide, lanthanum hydroxide, molybdenum hydroxide, ammonium molybdate, zinc stannate, magn trisilicate osesium, telluric acid, manganese tungstate, manganite, cobaltocene, 5-aminotetrazole, guanidine nitrate, azobisformamide, powdered nylon, oxamido, biuret, pentaerythritol, decabromodiphenyl ether, tetrahydrate, citrate, tetrahydrate, citrate, tetrahydrate, citrate sodium, manganese citrate, magnesium citrate, copper citrate, ammonium citrate, nitroguanidine.
    [035] From the view of sufficiently exerting the effect to extinguish fire from ferrocene and its derivatives which is current as well as the main extinguishing material, the content of the aforementioned flame retardants is not greater than 75 in mass percentage, preferably 60 in percent weight or less, and in addition preferably 50 percent weight or less and 20 percent weight or more.
    [036] The ferrocene-based fire extinguishing composition of the present invention can also be added, when necessary, with various additives such as a complex solution of stearate, graphite and a water-soluble polymer or a mixture thereof. The content of the additive is preferably from 0.5 to 10 percent by weight.
    [037] Each of the preferred components of the ferrocene-based fire extinguishing composition of the present invention and its content are:
    [038] ferrocene, a derivative of ferrocene or a combination thereof from 30 percent mass to 80 percent mass
    [039] a flame retardant from 20 weight percent to 60 weight percent
    [040] an additive from 5 percentage mass to 8 percentage mass.
    [041] Each of the most preferred components of the ferrocene-based fire extinguishing composition of the present invention and its content are:
    [042] ferrocene, a derivative of ferrocene or a combination thereof from 40 percent weight to 70 percent weight
    [043] a flame retardant from 30 percent mass to 50 percent mass
    [044] an additive from 5 percentage mass to 8 percentage mass.
    [045] The ferrocene-based fire extinguishing composition of the present invention can be molded using processes such as granulating, molding, raw extrusion, foliage, spheres, strips and hives and can be subjected to a coating treatment of surface. When the surface coating treatment is carried out, methyl hydroxypropyl cellulose or hydroxy ethyl cellulose is preferably added as a surface coating agent. The surface coating agent can improve the surface finish of the composition system and allow for an additional improvement in strength, abrasion resistance and vibration resistance, hence preventing the refrigerant from calcification, abrasion and spillage from the extinguisher. during transportation. Description of Preferred Achievements
    [046] The ferrocene-based fire extinguishing composition of the present invention is described in more detail by means of the examples below:
    [047] Example 1
    [048] Add 50 g of a prepared composition of ferrocene, ammonium phosphate dihydrogen and ferrous ammonium sulfate to a fire extinguisher device in which 50 g of a type K thermal aerosol generating agent is filled. Then perform a test to extinguish a fire caused by oil (or gasoline) in a 0.1 m2 oil pan. The test result is shown in Table 1.
    [049] Example 2
    [050] The prepared composition of ferrocene and ammonium polyphosphate is tested in accordance with Example 1. The test result is shown in Table 1.
    [051] Example 3
    [052] The prepared composition of ferrocene and zinc carbonate is tested in accordance with Example 1. The test result is shown in Table 1.
    [053] Example 4
    [054] The prepared composition of ferrocene, potassium chloride, zinc oxide, iron oxide and basic magnesium carbonate is tested in accordance with Example 1. The test result is shown in Table 1.
    [055] Example 5
    [056] The prepared composition of ferrocene, potassium chloride, zinc oxide, manganese carbonate and sodium silicate is tested in accordance with Example 1. The test result is shown in Table 1.
    [057] Example 6
    [058] The prepared composition of ferrocene, melamine and aluminum hydroxide is tested in accordance with Example 1. The test result is shown in Table 1.
    [059] Example 7
    [060] The prepared composition of ferrocene and ammonium oxalate is tested in accordance with Example 1. The test result is shown in Table 1.
    [061] Example 8
    [062] The prepared composition of ferrocene styrene, dihydrogen ammonium phosphate and ferrous ammonium sulphate is tested in accordance with Example 1. The test result is shown in Table 1.
    [063] Example 9
    [064] The prepared composition of biferrocene and ammonium polyphosphate is tested in accordance with Example 1. The test result is shown in Table 1.
    [065] Example 10
    [066] The prepared composition of ferrocene sulfonyl chloride, potassium chloride, zinc oxide, manganese carbonate and sodium silicate is tested in accordance with Example 1. The test result is shown in Table 1.
    [067] Comparative Example 1
    [068] Perform a test to extinguish a fire caused by oil (or gasoline) in a 0.1 m2 oil pan using a sample of a fire extinguishing device in which only 100 g of a fire extinguishing agent in a thermal aerosol type S is full. The test result is shown in Table 1.
    [069] Comparative Example 2
    [070] Perform a test to extinguish a fire caused by oil (or gasoline) in a 0.1 m2 oil pan using a sample of a fire extinguishing device in which only 100 g of a fire extinguishing agent in a thermal aerosol type K is full. The test result is shown in Table 1.
    [071] Comparative Example 3
    [072] Prepare a fire-extinguishing composition merely by adding manganese carbonate, which is a material to extinguish refrigerant and auxiliary and magnesium stearate and hydroxypropyl methyl cellulose as process aids, without adding ferrocene as the main fire-extinguishing substance. The prepared composition is tested in accordance with example 1. The test result is shown in Table 1. Table 1: comparison of the ingredients of the various components and the contrast of the test results



    [073] Type S and K fire extinguishing agents used in Comparative examples 1 and 2 in the above mentioned tables are commercially available. From Table 1, it is clear that the composition for extinguishing fire based on ferrocene in examples 1 to 10 of the present invention not only shows a much higher efficiency for extinguishing fire than Comparative examples 1 to 3, but it is also obviously superior Comparative Examples 1 to 3 with respect to the time required to extinguish the fire and with respect to the temperature at the generator nozzle. In addition, the ferrocene-based fire extinguishing compositions used in examples 4, 5, 6 and 10, in which a surface coating agent is added, perform a significant improvement with respect to strength, abrasion resistance and resistance to vibration when compared to other compositions to extinguish fire.
    [074] The specific Examples mentioned above are merely exemplary and the various modifications and variations carried out by individuals with expertise in the art based on the teachings of these examples of the present invention fall within the scope of protection of the present invention. Those individuals skilled in the art should understand that the above-mentioned description is only for the purpose of explaining the present invention and is not intended to limit the present invention in its scope.
    权利要求:
    Claims (20)
    [0001]
    1. Ferrocene-based fire-extinguishing composition comprising: ferrocene, a ferrocene derivative, or a combination thereof at a content of 40% by weight or more, characterized by the fact that: the ferrocene derivative is a compound of aldehydes or ferrocene ketones, or a compound of ferrocene carboxylic acid and its derivative, or a compound of ferrocene alcohols, phenols or ethers, or a ferrocene hydrocarbon compound, or a nitrogen-containing ferrocene compound, or a ferrocene compound containing sulfur or phosphorus-containing, or a silicon-containing ferrocene compound, or a heterocyclic ferrocene compound, or a compound selected from the group consisting of 1,1'-dichroic ferrocene, ferrocene chloromercurium, boric ferrocene acid, cupric ferrocenyl acetylide , or bisferrocenyl titanocene; the composition additionally comprises a flame retardant, the flame retardant is a brominated flame retardant, a chlorinated flame retardant, an organic phosphorus flame retardant, a halogenated phosphorus flame retardant, a nitrogen based flame retardant or phosphorus-nitrogen based flame retardant, or inorganic flame retardant; wherein the content of the flame retardant is not more than 75% by weight; and the composition additionally comprises an additive, the additive is a complex solution of stearate, graphite and water-soluble polymer, or a mixture thereof, wherein the content of the additive is 0.5 to 10% by weight.
    [0002]
    2. Composition according to claim 1, characterized by the fact that the melting point of the ferrocene derivative is 100 ° C or higher.
    [0003]
    Composition according to claim 2, characterized by the fact that the ferrocene derivative is a volatile compound.
    [0004]
    4. Composition according to claim 1, characterized by the fact that the compound of ferrocene aldehydes or ketones is 1,2-diformyl ferrocene, 3-ferrocenyl acryldehyde, (4-formylphenyl) ferrocene, octamethylformyl ferrocene, chloroacetyl ferrocene, 1- acetyl-l'-cyano ferrocene, α-oxo-1,1'-trimethylene ferrocene, .beta.-oxo-1,1'-tetramethylene ferrocene, 1,1'-diacetyl ferrocene, (1,3-dioxobutyl) ferrocene , 1-acetyl-1'-acetylamino ferrocene, (2-chlorobenzoyl) ferrocene, benzoyl ferrocene, 1,1'-di (3-cyano-propionyl) ferrocene, phenylacetyl ferrocene, (2-methoxybenzoyl) ferrocene, 1.1 ' -di (acetoacetyl) ferrocene, 1-acetyl-1'-p-chlorobenzoyl ferrocene, 1-ferrocenyl-3-phenyl-2-propen-1-one, 3-ferrocenyl-1-phenyl-2-propen-1-one , (2,4-dimethoxy benzoyl) ferrocene, 1,1'-di (propionoacetyl) ferrocene, bisferrocenyl methyl ketone, 2-acetyl-biferrocene, 1,1'-di (pentafluorobenzoyl) ferrocene, 1,2-bisferrocenyl acyl ethane , 1,3-bis (ferrocenyl methylidene) acetone, 1'-acetyl-2,2-bisferrocenyl propane, or 1,1 ' -di (benzoylacetyl) ferrocene.
    [0005]
    5. Composition according to claim 1, characterized in that the compound of ferrocene carboxylic acid and its derivative is ferrocene carboxylic acid, 2-hydroxy ferrocene carboxylic acid, ferrocene acetic acid, ferrocene thioacetic acid, 3-ferrocenyl acrylic acid, propionic ferrocene acid, methylthio acetic ferrocene acid, 1,1'-ferrocene diacetic acid, ferrocene butyric acid, ferrocene pentanoic acid, 2,2-dimethyl-3-ferrocenyl propionic acid, 1,1'-ferrocene dipropionic acid, hexanoic ferrocene acid , 1,1'-ferrocene dibutyric acid, 4,4'-bisferrocenyl pentanoic acid, 1,1'-ferrocene chloride diformila, 1,2-ferrocene dicarboxylic anhydride, 1,1'-ferrocene diacetic anhydride, 2- anhydride (1'-carboxymethyl ferrocene) benzoic, formic ferrocene anhydride, dimethyl ferrocene-1,1'-dicarboxylate, ethyl 3-ferrocenyl acrylate, 1,1 '' - di (methoxycarbonyl) -biferrocene, 4.4 pentanoate -bisferrocenyl methyl, ferrocene formamide, formyl hydroxide ferrocene ylamine, ferrocene formyl hydrazide, acetamido ferrocene, ferrocene formyl azirdine, 1'-vinyl ferrocene formamide, N- (2-cyanoethyl) ferrocene formamide, N-acetyl-2-ferrocenyl ethylamine, N-butyl ferrocene formamide, 1,1'- diformil azirdine ferrocene, N, N, N, N'-tetramethyl-1,1'-ferrocene diformamide, N-phenyl ferrocene formyl hydroxylamine, N-ferrocenyl phthalimide, N-benzoyl-2-ferrocenyl ethylamine, 4,4-bisferrocenyl valeramide , ferrocene cyan, or ferrocene 1,1'-dician.
    [0006]
    6. Composition according to claim 1, characterized by the fact that the compound of ferrocene alcohols, phenols, or ethers is α-hydroxy ferrocene acetonitrile, ferrocene dimethanol, 1,2-ferrocene dimethanol, 1,1'-di (1 -ethoxy) ferrocene, octamethyl ferrocene methanol, ferrocenyl- (2,4,6-trimethoxyphenyl) methanol, bisferrocenyl methanol, α, α-diphenyl ferrocene methanol, 4- (2-ferrocenyl-2-ethoxy) -4'-methyl- 2,2'-bipyridine, 2-methyl-α, α-diphenyl ferrocene methanol, 1,4-bisferrocenyl-1,4-butanediol, 4,4-bisferrocenyl-1-pentanol, 4,4'-di (2- ferrocenyl-2-ethoxy) -2,2'-bipyridine, 1,1'-di (diphenylhydroxymethyl) ferrocene, (4-hydroxyphenyl) ferrocene, 2-oxa-1,1'-trimethylene ferrocene, 1,3-dimethyl- 2-oxa-1,1'-trimethylene ferrocene, bis (methyl ferrocenyl) ether, or 1,1-bisferrocenyl methyl tert-butyl ether.
    [0007]
    Composition according to claim 1, characterized by the fact that the ferrocene hydrocarbon compound is 1,1'-trimethylene ferrocene, 1,1'-diethyl ferrocene, 1-vinyl-1'-chloroferrocene, 1,1 ' -di (α-cyclopentadienyl ethylidene) ferrocene, phenylethynyl ferrocene, bisferrocenyl acetylene, 1,1'-di (phenylethynyl) ferrocene, 1,1'-bis (ferrocenyl ethinyl) ferrocene, 1,1 ', 2,2'-tetrachlor ferrocene, fluoroferrocene, biferrocene, 2,2-bisferrocenyl propane, 1,1-bisferrocenyl pentane, or 1 ', 1' '' - di (triphenyl methyl) biferrocene.
    [0008]
    8. Composition according to claim 1, characterized by the fact that the nitrogen-containing ferrocene compound is (2-nitrovinyl) ferrocene, (4-nitrophenyl) ferrocene, 2-hydroxy-2-ferrocenyl ethylamine, N, N'-bisferrocenyl ethylenediamine, N, N'-bisferrocenyl methyl ethylenediamine, N, N'-di (bisferrocenyl methyl) ethylenediamine, 2-hydroxy-5-nitrobenzylimino ferrocene, benzoyl ferrocene oxime, ferrocene methyl diazomethyl ketone, 1,1'-diphenyl azoferryl azoferryl azoferril phenyl methylimino benzene, or 1,6-differenocenyl-2,5-diaza-1,5-hexadiene.
    [0009]
    Composition according to claim 1, characterized in that the sulfur-containing or phosphorus-containing ferrocene compound is 1,1'-ferrocene disulfonyl chloride, 1,1'-ferrocene disulfonyl sorrel, sulfonyl ferrocene chloride, acid sulfinic ferrocene, ferrocene sulfonic acid, (diethyl-dithiocarbamate) -ferrocene, 1,1'- di (dimethyl-dithiocarbamate) -ferrocene, ferrocene methyl phenyl sulfone, thiolferrocenyl-ferrocene sulfonate, bisferrocenyl disulfide, N, N'-dicyclo -1,1'-ferrocene disulfonamide, or (diphenylphosphino) -ferrocene.
    [0010]
    10. Composition according to claim 1, characterized by the fact that the ferrocene compound containing silicon is 1,1'-dichloro-2-trichlorosilanil-ferrocene, bis (1,1'-dichloro-2,2'-ferrocenylene) -silane, (1,1'-octamethyl-ferrocenylene) -dimethylsilane, (1,1'-dichloro-2,2'-ferrocenylene) -diphenylsilane, 1,1'-di [α-hydroxy-α- (trisilylpropyl) ethyl] ferrocene, or 1,1'-di (phyldimide methyldisylyl) ferrocene.
    [0011]
    11. Composition according to claim 1, characterized by the fact that the heterocyclic ferrocene compound is 2-ferrocenyl-1,3-dithian, 5-ferrocenyl-methylidene-1-aza-3-oxa-4-oxo-2- phenyl-1-cyclopentene, 1,3-bisferrocenyl imidazoline, or 2,5-bisferrocenyl tetrahydrofuran.
    [0012]
    12. Composition according to claim 1, characterized by the fact that the brominated flame retardant is tetrabromobisphenol A, tetrabromobisphenol A ether, 1,2-bis (tribromophenoxy) ethane, 2,4,6-tribromophenyl glycidyl ether, anhydride phthalic tetrabromo, 1,2-bis (tetrabromo phthalimide) ethane, tetrabromo dimethyl phthalate, disodium tetrabromo phthalate, decabromodiphenyl ether, tetradecabromodi (phenoxyl) benzene, 1,2-bis (pentabromophenyl) ethane, bromo-trimethyl-phenyl-phenethyl-phenethyl-phenyl , pentabromobenzyl acrylate, pentabromobenzyl bromide, hexabromobenzene, pentabromotoluene, 2,4,6-tribromophenyl maleimide, hexabromo cyclododecane, N, N'-1,2-bis (dibromonorbornyl dicarbimide) ethane, pentabromochloro-cyclohexane, 2,3 -dibromopropyl) isocyanurate, bromo-styrene copolymer, tetrabromobisphenol A-carbonate oligomer, polypentabromobenzyl acrylate, or polydibromophenylene ether.
    [0013]
    13. Composition according to claim 1, characterized by the fact that the chlorinated flame retardant is declorane plus, HET anhydride (chlorendric anhydride), pentacyclodecane perchlor, tetrachlorobisphenol A, tetrachlorophthalic anhydride, hexachlorobenzene, chlorinated polypropylene, chlorinated polyvinyl chloride, polyvinyl chloride chloride vinyl chloride - vinylidene chloride, chlorinated polyether, or hexachloroethane.
    [0014]
    14. Composition according to claim 1, characterized by the fact that the organic phosphorus flame retardant is 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosfabicyclo [2,2,2] octane, 2,2-dimethyl-1,3-propanediol-di (neopentyl glycol) diphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide, bis (4-carboxyphenyl) -phenyl phosphine oxide, oxide bis (4-hydroxyphenyl) -phenyl phosphine, or phenyl (diphenyl sulfone) phosphate oligomer.
    [0015]
    Composition according to claim 1, characterized in that the halogenated phosphorus flame retardant is tris (2,2-di (bromomethyl) -3-bromopropyl) phosphate, tris (dibromophenyl) phosphate, 3,9-bis (tribromophenoxy) -2,4,8,10-tetraoxa- 3,9-diphosphospiro [5.5] -3,9-dioxo-undecane, 3,9-bis (pentabromophenoxy) -2,4,8, 10-tetraoxa- 3,9-diphosphospiro [5.5] -3.9-- dioxo-undecane, 1-oxo-4-tribromophenoxycarbonyl-2,6,7-trioxa-1-phosphocycle [2,2,2] octane, p-phenylene-tetrakis (2,4,6-tribromophenyl) -diphosphate, 2,2-di (chloromethyl) -1,3-propanediol-di (neopentyl glycol) diphosphate, or 2,9-di (tribromoneopentyloxy) - 2,4,8,10-tetraoxa-3,9-diphosphospiro [5.5] -3, - 9-dioxo-undecane.
    [0016]
    16. Composition according to claim 1, characterized by the fact that the nitrogen-based flame retardant or nitrogen phosphorus-based flame retardant is melamine, melamine cyanurate, melamine orthophosphate, dimelamine orthophosphate, melamine polyphosphate, melamine borate, melamine octamolybdate, cyanuric acid, tris (hydroxyethyl) isocyanurate, 2,4-diamino-6- (3,3,3-trichloropropyl) -1,3,5-triazine, 2,4-di ( N-hydroxymethyl-amino) -6- (3,3,3-trichloropropyl-1,3,5-triazine), diguanidine hydrophosphate, guanidine dihydrogen phosphate, guanidine carbonate, guanidine sulfamate, urea, urea dihydrogen phosphate, diciandiamide , melamine bis (2,6,7-trioxa-1-phosfa-bicyclo [2.2.2] octane-1-oxo-4-methyl) -hydroxyphosphate, 3,9-dihydroxy-3,9-dioxo-2,4 , 8,10-tetraoxa-3,9-diphosphospiro [5.5] undecane-3,9-dimelamine, 1,2-di (2-oxo-5,5-dimethyl-1,3-dioxa-2-phosfacyclohexyl-2 -amino) ethane, N, N'-bis (2-oxo-5,5-dimethyl-1,3-dioxa-2-phosfacyclohexyl) -2,2'-m-phenylenediamine, tri (2-oxo-5,5-dimethyl-1,3-dioxa-2-phosphacyclohexyl-2-methyl) amine, or hexachlorocyclotriphosphazene.
    [0017]
    17. Composition according to claim 1, characterized by the fact that the inorganic flame retardant is red phosphorus, ammonium polyphosphate, diamonium hydrophosphate, ammonium dihydrogen phosphate, zinc phosphate, aluminum phosphate, boron phosphate, antimony trioxide , aluminum hydroxide, magnesium hydroxide, hydromagnesite, alkaline aluminum oxalate, zinc borate, barium metaborate, zinc oxide, zinc sulfide, zinc heptahydrate sulfate, aluminum borate whisker, ammonium octamolybdate, ammonium heptamolibdate , zinc stannate, stannous oxide, stannous oxide, ferrocene, ferric acetone, ferric oxide, ferro-ferric oxide, ammonium bromide, sodium tungstate, potassium hexafluorotitanate, potassium hexafluorozirconate, titanium dioxide, calcium sulfate, calcium carbonate of barium.
    [0018]
    18. Composition according to claim 1, characterized by the fact that each of the components of the composition and its content is: ferrocene, a derivative of ferrocene, or a combination thereof: from 40% by mass to 80% by mass a flame retardant: from 20% by mass to 60% by mass an additive: from 5% by mass to 8% by mass.
    [0019]
    19. Composition according to claim 1, characterized by the fact that each of the components of the composition and its content is: ferrocene, a derivative of ferrocene, or a combination thereof: from 40% by mass to 70% by mass a flame retardant: from 30% by mass to 50% by mass an additive: from 5% by mass to 8% by mass.
    [0020]
    20. Composition according to claim 1, characterized by the fact that the composition is subjected to a surface coating treatment.
    类似技术:
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    同族专利:
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    法律状态:
    2017-09-26| B25A| Requested transfer of rights approved|Owner name: XI'AN JANDR FIRE FIGHTING EQUIPMENT CO, LTD. (CN) |
    2017-10-10| B25A| Requested transfer of rights approved|Owner name: XI'AN WESTPEACE FIRE TECHNOLOGY CO., LTD. (CN) |
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-14| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-03-17| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-19| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CH201010285564.6|2010-09-16|
    CN2010102855646A|CN102179027B|2010-09-16|2010-09-16|Ferrocene extinguishing composition|
    PCT/CN2011/079426|WO2012034492A1|2010-09-16|2011-09-07|Ferrocene-based fire extinguishing composition|
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