EP0060532A1 - Additif anti-catalytique pour poudres extinctrices ou retardatrices de flamme, ces poudres et leur méthode de préparation - Google Patents

Additif anti-catalytique pour poudres extinctrices ou retardatrices de flamme, ces poudres et leur méthode de préparation Download PDF

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Publication number
EP0060532A1
EP0060532A1 EP82102013A EP82102013A EP0060532A1 EP 0060532 A1 EP0060532 A1 EP 0060532A1 EP 82102013 A EP82102013 A EP 82102013A EP 82102013 A EP82102013 A EP 82102013A EP 0060532 A1 EP0060532 A1 EP 0060532A1
Authority
EP
European Patent Office
Prior art keywords
acid
cyclodextrin
salt
catalytic additives
fire
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP82102013A
Other languages
German (de)
English (en)
Other versions
EP0060532B1 (fr
Inventor
András Kerekes
Geb. Dargay Ilona Dr. Teke
József Dr. Szejtli
Zsuzsanna Dr. Budai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koeporc Elektronikai Alkatresz Es Mueszaki Keramia
Original Assignee
KOPORC ELEKTRONIKAI ALKATRESZ ES MUSZAKI KERAMIAGYARTO VALLALAT
KOEPORC ELEKT ALKATR MUESZAKI
Koporc Elektronikai Alkatresz Es Mueszaki Keramiagyarto Vallalat
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by KOPORC ELEKTRONIKAI ALKATRESZ ES MUSZAKI KERAMIAGYARTO VALLALAT, KOEPORC ELEKT ALKATR MUESZAKI, Koporc Elektronikai Alkatresz Es Mueszaki Keramiagyarto Vallalat filed Critical KOPORC ELEKTRONIKAI ALKATRESZ ES MUSZAKI KERAMIAGYARTO VALLALAT
Priority to AT82102013T priority Critical patent/ATE20521T1/de
Publication of EP0060532A1 publication Critical patent/EP0060532A1/fr
Application granted granted Critical
Publication of EP0060532B1 publication Critical patent/EP0060532B1/fr
Expired 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
    • A62D1/0007—Solid extinguishing substances
    • A62D1/0014—Powders; Granules

Definitions

  • the invention relates to anti-catalytic additives for fire retardant and fire extinguishing powder and highly effective fire retardant and fire extinguishing powder containing them based on 1 or more salt (s), primarily acid salt (s), especially the alkali and alkaline earth metals and / or corresponding Ammonium salt (s), and / or their mixed crystals with urea, and process for their preparation.
  • salt primarily acid salt (s), especially the alkali and alkaline earth metals and / or corresponding Ammonium salt (s), and / or their mixed crystals with urea, and process for their preparation.
  • bicarbonates are particularly suitable from these three aspects. Potassium bicarbonate, sodium bicarbonate and ammonium bicarbonate are most widely used, but also disodium hydrogen phosphate and diammonium hydrogen phosphate.
  • the extinguishing effect of the fire extinguishing powder depends on the type of manufacture, for example on the raw materials and the process technology or technology used to produce the salt. This particularly affects the crystal size and the particle size distribution. By reducing the particle size, the specific surface area is increased and thus the extinguishing effect is increased. However, this is only possible up to a certain limit, since below a certain particle size the ballistic properties of the powder deteriorate to such an extent that it can only be goal-locked or sprayed together with carriers.
  • the mode of action of the fire-extinguishing powder had to be considered first.
  • the flames that burn with flames are essentially gas fires.
  • the acidic salts get into the flame, are decomposed by the heat and the acid radicals released act as "radical scavengers" for the initiating radicals and thereby break the chain.
  • the weaker acids are displaced from their salts by the stronger acids. The decomposition of the. acidic salts and thus the speed of their action could therefore be increased by letting them have a strong acid in the flame.
  • the invention is therefore based on the object, while eliminating the disadvantages of the prior art additives to increase de.
  • the invention also relates to fire retardant and fire extinguishing powder based on 1 or more salt (s), primarily acid salt (s), especially the alkali and alkaline earth metals and / or corresponding ammonium salt (s), and / or their Mixed crystals with urea, optionally containing 1 or more adsorbent (s) and / or other inert material (s), which are characterized in that they contain inventive anti-catalytic additives in such amounts that a) and / or b ) and / or c) in amounts of 2 to 20% by weight and / or d) and / or e) and / or f) in amounts of 0.5 to 25% by weight.
  • inventive anti-catalytic additives in such amounts that a) and / or b ) and / or c) in amounts of 2 to 20% by weight and / or d) and / or e) and / or f) in amounts of 0.5 to 25% by weight.
  • the invention further relates to a process for the preparation of the anti-catalytic additives according to the invention, which is characterized in that a) and / or b) and / or c) and / or d) and / or e) and / or f) to an average Particle size set below 10 microns and, optionally together with 1 or more adsorbent (s) and / or other inert material (s), is mixed.
  • adsorbent (s) and / or other inert material (s) are used, these are preferably used in an amount (s) of 75 to 25% by weight, in particular 35 to 25 % By weight, and a) and / or b) and / or c) and / or d) and / or e) and / or f) preferably used in an amount (s) of 25 to 75% by weight, in particular 65 to 75% by weight.
  • the invention furthermore relates to a process for the preparation of the fire retardant and fire-extinguishing powders according to the invention, which is characterized in that the salt (s) and / or its or their mixed crystals with urea, optionally together with 1 or more adsorbent (s) and / or other inert material (s), with the anti-catalytic additives according to the invention in 2 to 20% by weight a) and / or b) and / or c) and / or 0.5 to 25% by weight d) and / or e) and / or f) appropriate amounts are mixed.
  • the salt (s) and / or its or their mixed crystals with urea optionally together with 1 or more adsorbent (s) and / or other inert material (s)
  • the anti-catalytic additives according to the invention in 2 to 20% by weight a) and / or b) and / or c) and / or 0.5 to 25% by weight d) and
  • adsorbents and / or other inert material (s) is or are used together with the salt (s) and / or their mixed crystals, these will be mostly in a small proportion (s), namely from 0.5 to 20.0% by weight, in particular 0.5 to 10.0% by weight. very particularly 0.5 to 2.0% by weight, based on the amount of basic fire retardant or basic fire extinguishing powder ⁇ amount (s) of the salt (s) and / or its or their mixed crystals with urea + any amount present (n ) of the adsorbent and / or other material or materials ⁇ used.
  • the cyclodextrins with which inclusion complexes of mineral acids and / or organic halides and / or their organic acid complexes ⁇ a) and / or b) and / or c) ⁇ can be present in the anticatalytic additives or fire retardant and fire extinguishing powders according to the invention are cyclic oligosaccharides .
  • the ring comprising 6, 7 or 8 glucopyranose units systems are called ⁇ -, B- or ⁇ -cyclodextrins.
  • the diameter of the cavity formed by the ring is approximately 6, 8 and 10 A. With suitable size and polarity, the cyclodextrins form crystalline inclusion complexes.
  • the anti-catalytic additives or fire retardant and fire-extinguishing powder according to the invention preferably contain as inclusion complex (s) with 1 or more cyclodextrin (s) and / or organic acid complex (s) of cyclodextrins ⁇ a) and / or b) and / or c) [a] such [n] with ⁇ - and / or ⁇ -cyclodextrin.
  • the anti-catalytic additives or fire retardant and fire extinguishing powder according to the invention as inclusion complex (s) of 1 or more mineral acid (s) with 1 or more cyclodextrin (s) ⁇ a) ⁇ [such] such as phosphoric acid and / or contain [a] hydrohalic acid (s).
  • the inclusion complex (s) of 1 or more mineral acid (s) with 1 or more cyclodextrin (s), in particular ⁇ -cyclodextrin and / or ⁇ -cyclodextrin is or are particularly suitable in the anti-catalytic additives or fire retardant and fire-extinguishing powders according to the invention , [such] of phosphoric acid and / or 1 or more hydrohalic acid (s), especially hydrochloric acid and / or hydrobromic acid, as mineral acid (s).
  • the fire extinguishing effect of the inclusion complexes of mineral acids with cyclodextrins increases in the order - from those with ⁇ -cyclodextrin to those with ⁇ -cyclodextrin to those with ⁇ -cyclodextrin as cyclodextrin.
  • the fire extinguishing effect of their inclusion complexes with cyclodextrins decreases in the order of hydroiodic acid, hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid.
  • the inclusion complexes of ⁇ -cyclodextrin are generally most preferred because of their best accessibility.
  • the anti-catalytic additives or fire retardant and fire-extinguishing powder according to the invention preferably contain as inclusion complex (s) of 1 or more organic halide (s) with 1 or more cyclodextrin (s) ⁇ b) ⁇ [one] such [s] of [one] aliphatic halogenated hydrocarbon (s), especially Chlorkoh - lenwasserstoff (s), particularly carbon tetrachloride, chloroform and / or trichlorethylene, and / or bromohydrocarbons hydrogen (s), especially methylbro- mide.
  • inclusion complex of 1 or more organic halide (s) with 1 or more cyclodextrin (s) ⁇ b) ⁇ [one] such [s] of [one] aliphatic halogenated hydrocarbon (s), especially Chlorkoh - lenwasserstoff (s), particularly carbon tetrachloride, chloroform and / or trichlorethylene, and / or bromohydro
  • the internal salts of amino acids with strong mineral acids ⁇ d) ⁇ should be mentioned in particular.
  • the inner salt (s) of 1 or more amino acid (s) with 1 or more mineral acid (s) ⁇ d) ⁇ are those with [a] hydrohalic acid (n ), in particular hydrochloric acid, and / or phosphoric acid and / or sulfuric acid are preferred as mineral acid (s). Betaine is also preferred as the amino acid.
  • the amino acids form internal salts with stronger mineral acids, from which the mineral acid (s) only release well above 100 ° C will set or will.
  • the hydrogen chloride is only released above 140 ° C. from betacid (the hydrochloride of betaine), which is particularly preferred as the inner salt of an amino acid in the anti-catalytic additives or fire retardant and fire-extinguishing powders according to the invention.
  • halogen paraffins preferred as solid alkyl halides (e) ⁇ in the anti-catalytic additives or fire retardant and fire extinguishing powders according to the invention especially chlorine paraffins, the fire retardant and fire extinguishing powder improving effect of which is in no way inferior to that of the inclusion complexes with cyclodextrins.
  • the halogen paraffin (s), especially chloroparaffin (s) preferably contained as solid alkyl halide (s) ⁇ e) ⁇ in the anti-catalytic additives or fire retardant and fire-extinguishing powders according to the invention.
  • An example of such a mixture is a mixture consisting of 25% by weight chlorinated paraffins with 20 to 24 carbon atoms, 50% by weight chlorinated paraffins with 25 to 28 carbon atoms and 25% by weight chlorinated paraffins with 29 to 32 carbon atoms.
  • the organic acid complex (s) of 1 or more cyclodextrin (s) ⁇ c) ⁇ is or are preferably in the inventive anti-catalytic additives or fire-retardant and fire-extinguishing powders are [those] with [one], optionally halogen-substituted, aliphatic carboxylic acid (s) with 1 to 6, especially 1 to 3, carbon atom (s), as acid (s), in particular trichloroacetic acid, formic acid and / or propionic acid.
  • the co-desorption complex (s) of 1 or more acid (s) ⁇ f) ⁇ can be one of inorganic and / or organic acids, preferably phosphoric acid, sulfuric acid and / or [one], optionally halogen-substituted, especially chlorine-substituted, aliphatic 'carboxylic acid (s) with 1 to 6, especially 1 to 3, carbon atoms, in particular trichloroacetic acid, on 1 or more adsorbent (s).
  • the anti-catalytic additives or fire retardant and fire-extinguishing powder according to the invention as chemisorption complex (s) of 1 or more acid (s) ⁇ f) ⁇ [such] on [an] activated oxide (s), in particular Aluminum oxide, very particularly ⁇ -aluminum oxide, and / or [a] zeolite (s), in particular [a] sodium / aluminum zeolite (s), of type 4-a, for example with pore diameters of silicon atom% of about 10 A and a quotient of about 1 as an adsorbent.
  • chemisorption complex of 1 or more acid (s) ⁇ f) ⁇ [such] on [an] activated oxide (s), in particular Aluminum oxide, very particularly ⁇ -aluminum oxide, and / or [a] zeolite (s), in particular [a] sodium / aluminum zeolite (s), of type 4-a, for example with pore diameters of silicon atom% of about 10 A and a quotient of about 1 as
  • the anti-catalytic additives or fire retardant and fire-extinguishing powders according to the invention as salt (s) and / or their mixed crystals with urea 1 or more carbonate (s), bicarbonate (s), phosphate (s) and / or hydrogen phosphate (s) of alkali and / or alkaline earth metals and / or the corresponding ammonium salt (s) and / or their mixed crystals with urea.
  • the adsorbent which is or may be present in the anti-catalytic additives or fire retardant and fire-extinguishing powders according to the invention is, in particular, activated oxide (s) other aluminum oxide, very particularly ⁇ -aluminum oxide, and / or zeolite (s), in particular [a] sodium / aluminum zeolite (s) of type 4-a, for example with pore diameters of approximately 10 ⁇ and a quotient of silicon - atom % of about preferred.
  • adsorbents must be present only in the presence of chemisorption complexes of acids, specifically in the chemisorption complexes themselves.
  • the fire retardant or fire extinguishing powders according to the invention whereby they are preferably with the salt (s) and / or its or their mixed crystals with urea and the inert material (s) which may be present and which are different from the adsorbents ) mixed into the fire retardant or fire-extinguishing powder according to the invention, mostly only in small proportions, namely from 0.5 to 20.0% by weight, in particular 0.5 to 10.0% by weight, very particularly 0.5 to 2.0% by weight, based on the basic fire retardant or ground fire extinguishing powder, but the amount of which can also be substantially larger, for example in the case of 42.5% by weight sodium bicarbonate, 54.5% by weight boehmite [AlO (OH)] and 3 wt .-% calcium stearate existing fire extinguishing powder ["Antispiro 100"] ⁇ Hungarian Patent 171 098 ⁇ , which in the inventions Fire retard
  • the amount (s) of the former in the latter is selected such that the desired proportion (s) of the fire retardant or fire-extinguishing powder according to the invention (e) the former is obtained.
  • the fire retardant and fire extinguishing powders according to the invention although they contain relatively strong acids, do not cause any corrosion. Their effect is twice as great as that of the fire retardant and fire extinguishing powder, which does not contain any anti-catalytic additive. They are not restricted to individual classes of flammable substances, but can be used to extinguish the fires of all classes (A, B, C, D and E) of flammable substances. These powders can be safely stored below 100 ° C.
  • the fire-extinguishing powders according to the invention obtained in this way were subjected to the same quality test as that produced in the factory.
  • the in kg / m 2 . s measured extinguishing efficiency was converted into percentages and the relevant values are summarized in Table 1 below.
  • the extinguishing effect of the basic extinguishing powder containing no additive was taken as 100%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Fireproofing Substances (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Respiratory Apparatuses And Protective Means (AREA)
  • Slide Fasteners, Snap Fasteners, And Hook Fasteners (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
EP82102013A 1981-03-12 1982-03-12 Additif anti-catalytique pour poudres extinctrices ou retardatrices de flamme, ces poudres et leur méthode de préparation Expired EP0060532B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82102013T ATE20521T1 (de) 1981-03-12 1982-03-12 Antikatalytische zusaetze fuer brandverzoegerungsund feuerloeschpulver und diese enthaltende brandverzoegerungs- und feuerloeschpulver sowie verfahren zu ihrer herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU81623A HU202765B (en) 1981-03-12 1981-03-12 Burning-delaying and fire-powder preparation containing anticatalytic material
HU62381 1981-03-12

Publications (2)

Publication Number Publication Date
EP0060532A1 true EP0060532A1 (fr) 1982-09-22
EP0060532B1 EP0060532B1 (fr) 1986-06-25

Family

ID=10950510

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82102013A Expired EP0060532B1 (fr) 1981-03-12 1982-03-12 Additif anti-catalytique pour poudres extinctrices ou retardatrices de flamme, ces poudres et leur méthode de préparation

Country Status (8)

Country Link
EP (1) EP0060532B1 (fr)
AT (1) ATE20521T1 (fr)
CS (1) CS249121B2 (fr)
DE (1) DE3271817D1 (fr)
DK (1) DK155204C (fr)
FI (1) FI78239C (fr)
HU (1) HU202765B (fr)
NO (1) NO159240C (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITTO20100174A1 (it) * 2010-03-08 2011-09-09 Torino Politecnico Nanospugne ciclodestriniche per applicazione nel settore del ritardo alla fiamma di materiali polimerici
CN109329588A (zh) * 2018-10-24 2019-02-15 浙江海洋大学 深水网箱养殖用的海水鱼配合饲料
WO2020089245A1 (fr) * 2018-10-30 2020-05-07 Franz Wilhelm Cremer Agent de protection pour accumulateurs d'énergie électrochimiques, en particulier pour accumulateurs d'énergie contenant du lithium

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51140398A (en) * 1975-05-29 1976-12-03 Hochiki Corp Hydrophilic combustible liquid foam extinguishing agent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51140398A (en) * 1975-05-29 1976-12-03 Hochiki Corp Hydrophilic combustible liquid foam extinguishing agent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 86, 1977, Columbus, Ohio, US; abstract no. 123923M, page 154; *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITTO20100174A1 (it) * 2010-03-08 2011-09-09 Torino Politecnico Nanospugne ciclodestriniche per applicazione nel settore del ritardo alla fiamma di materiali polimerici
CN109329588A (zh) * 2018-10-24 2019-02-15 浙江海洋大学 深水网箱养殖用的海水鱼配合饲料
CN109329588B (zh) * 2018-10-24 2022-02-08 浙江海洋大学 深水网箱养殖用的海水鱼配合饲料
WO2020089245A1 (fr) * 2018-10-30 2020-05-07 Franz Wilhelm Cremer Agent de protection pour accumulateurs d'énergie électrochimiques, en particulier pour accumulateurs d'énergie contenant du lithium

Also Published As

Publication number Publication date
DK155204C (da) 1989-07-31
DK108182A (da) 1982-09-13
NO820799L (no) 1982-09-13
EP0060532B1 (fr) 1986-06-25
FI78239B (fi) 1989-03-31
NO159240B (no) 1988-09-05
HU202765B (en) 1991-04-29
DK155204B (da) 1989-03-06
ATE20521T1 (de) 1986-07-15
NO159240C (no) 1988-12-14
DE3271817D1 (en) 1986-07-31
FI820866L (fi) 1982-09-13
FI78239C (fi) 1989-07-10
CS249121B2 (en) 1987-03-12

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