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
  • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
  • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
  • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
• • 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
  • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
  • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
• • 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
  • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
  • A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
• • 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
  • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
  • A62D2101/20—Organic substances
  • A62D2101/26—Organic substances containing nitrogen or phosphorus
• • 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
  • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
  • A62D2101/20—Organic substances
  • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

Definitions

• the invention relates to the use of non-decontaminating compositions aggressive stabilizers usable for the decontamination of toxic agents and / or organophosphorus or organosulfur pollutants, especially in the field of agents of chemical warfare or in the field of agriculture, for example for the insecticide decontamination.
• organophosphorus esters derived from phosphoric and phosphonic acids used as chemical warfare agents such as Tabun, Sarin or Soman, or as insecticides in agriculture, such as paraoxon or diazinon.
• organosulfurous toxic products such as industrial sulfides or warfare agents of the vesicant family, such as mustard.
• a number of current decontaminating formulations are essentially based on very alkaline formulas (soda solutions, alkanolamines, or amines) and / or hypochlorite (calcium hypochlorite especially).
• the main drawback of these formulas is that they are very aggressive towards equipment.
• the object of the invention is therefore the development of compositions very effective decontaminants vis-à-vis organophosphorus products or organosulphurous, stable, of low aggressiveness towards the material and the personnel and having a great speed of action.
• the decontaminating solutions obtained by dissolving these compositions exhibit exceptional stability both from the point of view of concentration of oxidizing species that especially in terms of the effectiveness of decontamination.
• compositions can also be used for decontamination of people by contact with the skin.
• compositions comprising an agent organic or mineral peroxidant and at least one stabilizing sequestering agent organic citrate, gluconate or phosphonate type exhibited very interesting both in terms of stability over time and efficiency decontaminating on toxic agents, possibly in thickened form.
• the subject of the invention is therefore the use of decontaminating compositions stabilized comprising at least one organic or mineral peroxidizing agent and at at least one organic stabilizing sequestering agent such as citrate, gluconate or phosphonate for the decontamination of toxic and / or polluting agents organophosphorus or organosulfur, in particular warfare agents oganophosphorus or organosulfur, or in the field of agriculture for the decontamination of organophosphorus or organosulfur phytosanitary agents, particularly insecticides, or for the decontamination of industrial pollutants.
• organophosphorus or organosulfur in particular warfare agents oganophosphorus or organosulfur
• in the field of agriculture for the decontamination of organophosphorus or organosulfur phytosanitary agents, particularly insecticides, or for the decontamination of industrial pollutants.
• a stabilizing sequestering agent is meant in the remainder of the description of a single stabilizing sequestering agent as well as a mixture of agents sequestering stabilizers.
• the stabilizing sequestering agent is advantageously chosen from sodium gluconate or polyphosphonates such as for example citrate sodium, sodium diethylenetriaminepentamethylene phosphonate (DETPM), sodium ethylene diaminetetramethylene phosphonate (EDTMP) and sodium hydroxyethyldiethylphosphonate (HEDP).
• sodium gluconate or polyphosphonates such as for example citrate sodium, sodium diethylenetriaminepentamethylene phosphonate (DETPM), sodium ethylene diaminetetramethylene phosphonate (EDTMP) and sodium hydroxyethyldiethylphosphonate (HEDP).
• organic sequestrants such as ethylenediaminetetraacetate (EDTA) and diethylenetriaminepentaacetate (DTPA), traditionally used as stabilizers of H 2 O 2 , do not confer any advantage in decomposition efficiency (measured as a residual percentage of toxic), but on the contrary tend to inhibit it.
• EDTA ethylenediaminetetraacetate
• DTPA diethylenetriaminepentaacetate
• compositions used according to the invention can comprise a buffer alkaline.
• an alkaline buffer is meant in the following description also just one alkaline buffer than a mixture of alkaline buffers.
• They can also include at least one constituent chosen from a hydrotropic agent, a viscosity agent and an anti-foaming agent.
• They can optionally include at least one surfactant cationic, nonionic and / or an amine oxide.
• the peroxidizing agent used in the compositions according to the invention can be an organic or mineral peroxidizing agent.
• a peroxidizing agent is meant in the following description also just one peroxidizing agent than a mixture of peroxidizing agents.
• the peroxidizing agent is peroxidizing agent organic such as a peracid or a peroxide, for example monoperoxyphthalate magnesium hexahydrate (MPPM); diperoxydodecanedioic acid (DPDA); acid perbenzoic acid, perphthalic acid, perlauric acid, perazelaic acid, acid persalicylic acid, diperadipic acid, peracetic acid, diperoxytererephthalic acid and their salts; dicumyl peroxide, tert-butylcumyl peroxide and peroxide diphtaloyl.
• MPPM is a particularly advantageous peroxidizing agent.
• an inorganic peroxidizing agent will be used in the presence of an oxidation activator, that is to say a molecule capable of generating a peracid in situ .
• compositions comprising a mineral peroxidizing agent in presence of an oxidation activator and at least one organic sequestering agent citrate, gluconate or phosphonate type for the decontamination of toxic agents and / or organophosphorus or organosulfur pollutants represents an aspect advantageous of the invention.
• activators with interfacial properties such as than nonanoyloxybenzenesulfonate (NOBS), which generates pemonanoic acid or isononanoyloxybenzenesulfonate (ISONOBS), which generates acid Perisononanoic.
• NOBS nonanoyloxybenzenesulfonate
• ISONOBS isononanoyloxybenzenesulfonate
• a preferred organic peroxidizing agent is MPPM.
• a preferred combination is sodium percarbonate or perurated as mineral peroxidants and TAED as an activator of peroxidation.
• a cationic surfactant is meant in the remainder of the description of a single type of cationic surfactant as well as a mixture cationic surfactants.
• cationic surfactant for example, cocoyltrimethylammonium chloride or bromide, didecyldimethylammonium chloride, benzalkonium chloride, mixtures of benzalkonium chlorides and alkyldimethylethylbenzylammonium chlorides, and surfactants quaternary or polyquaternary ammonium derivatives, possibly partially ethoxylated or whose alkyl chain is optionally interrupted by a group ester or amide.
• Polycationic surfactants such as N, N, N ', N' dichloride, N'-pentamethyl-N-tallow-1,3-propane diammonium and the N, N, N ', N', N ', N ", N" -heptamethyl-N-tallow-dipropylene triammonium trichloride.
• nonionic surfactant in the remainder of the description of a single type of nonionic surfactant as well as a mixture nonionic surfactants.
• Preferred nonionic surfactants are oxide of lauryldimethylamine and octylpyrrolidone.
• An advantageous alkaline buffer in the compositions used according to the invention is for example a carbonate or an alkali silicate, in particular the sodium carbonate.
• the solutions containing the compositions according to the invention have a pH greater than 6.5, preferably between 8.5 and 12, especially between 9 and 11. If necessary, the pH can be adjusted using an agent basifying such as sodium, potassium, ammonium hydroxide; silicates or sodium, potassium, ammonium borates etc ...
• hydrotropic agent it is possible to use, for example, urea, cumenesulfonates, toluenesulfonates or xylenesulfonates of sodium, potassium or ammonium; phenols ethoxylated with 4 ethylene oxides (such as the product marketed under the name Ethylan HB4 ® by Diamond Shamrock).
• viscosity agent is meant in the following description as well a single type of viscosity agent than a mixture of viscosity agents.
• the viscosity agent is preferably chosen from polymers giving the solution a thixotropic or shear thinning character. These features allow increase the contact time of the decontaminating solution with any surface non-horizontal such as those that can be found on vehicles (tank, plane, etc ). It is generally considered that an average viscosity under low stress of 60 to 300 mPa.s ensures sufficient contact for efficiency optimal decontaminant.
• Another advantage of the viscosity agent is that it makes it possible to maintain in suspension of a certain number of materials participating in the effectiveness of the solution but whose solubility is sometimes reduced.
• the viscosity agent can be, for example, modified corn starch or hydroxyethylcellulose.
• compositions according to the above invention can also contain antifreeze agents, at a rate of 5 to 40%, preferably 15 to 25%, such as for example propylene glycol, ethylene glycol or diethylene glycol.
• DETPM or EDTMP phosphonates not only have an effect beneficial for the stability and effectiveness of decontaminating solutions, but also a peptizing or redispersing action on flocculates or "creaming" which may occur during the dilution of the compositions comprising agents cationic surfactants and / or activated mineral persalts.
• an agent organic sequestrant such as guconate or sodium citrate
• a phosphonate such as DETPM or EDTMP.
• compositions used according to the invention can be in the form powder, liquid, gel or suspension.
• the components of the final formulation are in liquid form at room temperature can be either sprayed on the powder making up the rest of the formulation, or incorporated separately in liquid form in the solution decontaminating.
• compositions which can be used according to the invention are preferably used. works in aqueous solution at a concentration of 2 to 50%, preferably 8 to 25% by weight, having a pH greater than 6.5, preferably between 8.5 and 12.
• emulsions or microemulsions after dispersion in an organic solvent immiscible with water such as as for example aliphatic or aromatic hydrocarbons, possibly chlorinated, for example toluene, xylene, methylene chloride and tetrachlorethylene.
• organic solvent immiscible with water such as as for example aliphatic or aromatic hydrocarbons, possibly chlorinated, for example toluene, xylene, methylene chloride and tetrachlorethylene.
• compositions can be used manually or mechanically by sprinkling, whitewashing, spraying, soaking, impregnating or any other operation allowing the contact of said compositions with equipment or persons contaminated.
• the invention also relates to stabilized decontaminant compositions which can be used for the decontamination of toxic organophosphorus or organosulfur agents, comprising at least one organic peroxidizing agent or one inorganic peroxidizing agent chosen from H 2 O 2 adducts, persalts and alkaline peroxides, and at least one organic stabilizing sequestering agent of the citrate, gluconate or phosphonate type.
• compositions preferably comprise a sequestering agent organic stabilizer which is a polyphosphonate which can be chosen from DETPM, EDTMP and HEDP.
• They can also include at least one constituent chosen from an alkaline buffer, a hydrotropic agent, a viscosity agent, an anti-foaming agent, a cationic surfactant, a nonionic surfactant and an amine oxide.
• compositions comprise an organic peroxidizing agent chosen from magnesium monoperoxyphthalate hexahydrate (MPPM); diperoxydodecanedioic acid (DPDA); perbenzoic acid, perphthalic acid, perlauric acid, perazelaic acid, persalicylic acid, diperadipic acid, peracetic acid, diperoxyterephthalic acid and their salts; dicumyl peroxide, tert-butylcumyl peroxide and diphtaloyl peroxide, or an inorganic peroxidizing agent selected from sodium percarbonate; 1,4-diazabicyclo [2.2.2] octane (H 2 O 2 ) 2 ; phosphate peroxyhydrates such as sodium peroxypyrophosphate; the per negligence; sodium perborate tetrahydrate or monohydrate; potassium monopersulfate, Curox ® and Caro acid salts, ammonium persulfate, sodium persulfate or potassium persulfate;
• compositions comprising a mineral peroxidizing agent in combination with an activator of peroxidation, said peroxidation activator being able to be chosen from tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG), tetraacetylglucoluryl (TAGU), tetraacetylcyanuric acid (TACA), ⁇ -acetoxy- ⁇ -methyl N-N '(diacetyl) malonamide, acetylsalicylic acid (ASA), sodium paraacetoxybenzenesulfonate (AOBS), diacetyldimethylglyoxin (DDG) and ethylidene benzoateacetate (EBA); phthalic anhydride (PAN); the benzoylimidazole (BID), sodium parabenzoxy benzenesulfonate (BOBS); the nonanoyloxybenzènesulfonate (NOBS) and
• Particularly advantageous decontaminating compositions include sodium percarbonate or perurea as agents peroxidants and TAED as a peroxidation activator.
• sodium carbonate will be used as a buffer. alkaline.
• compositions according to the invention may also contain oxide of lauryldimethylamine or octylpyrrolidone as a nonionic surfactant.
• decontaminating compositions according to the invention can be presented in the form of aqueous solutions preferably containing from 2 to 50%, preferably 8 to 25% by weight of decontaminating composition, having a higher pH to 6.5, preferably between 8.5 and 12.
• the stability of the solutions is measured by assaying the active oxygen after a given storage period (1 h 30) at room temperature or 40 ° C, depending on the nature of the oxidizing agent.
• Decontaminating efficacy measurements are carried out by analysis of the residual toxic by gas chromatography.
• the invention also relates to the use of above compositions as well as their aqueous solutions, as an agent with anti-bacterial, anti-viral, in particular anti-retroviral, anti-fungal activity and / or anti-algae.
• compositions according to the invention are collated in Table 1 below.
• Table 2 below reports different decontaminating solutions produced by diluting decontaminating compositions according to the invention.
• the effectiveness measurement was carried out on paraoxon and diethylsulfide at a concentration of 50 mg of toxic substance / 5 ml of decontaminating solution 90 min after dissolving and with a contact time of the solution decontaminant and toxic substance 10 min.
• active oxygen is measured after 15 min (without sequestering agent) and 90 min (with and without sequestering agent).
• the decontaminating powder is weighed in a 100 ml glass bottle to ground glass stopper, then 50 ml of water at 28 ° HF are introduced. We stir manual until complete dissolution of the powder.
• the pH is measured, as well as the number of mg of oxygen available.
• a weight, denoted P1 of this solution is withdrawn by syringe and deposited in 100 ml of demineralized water, then acidified with 5 ml of acetic acid. We then add 15 ml of solution of KI at 20% by weight and the dose is immediately determined with 0.1N Na thiosulfate. After changing from orange to yellow, add a spatula of Thiodene ® (poison starch) and dose until completely discolored.
• a weight, denoted P1 of this solution is taken with a syringe and deposited in 100 ml of demineralized water, then acidified with 20 ml of 20% sulfuric acid. We dose with KMnO 4 0.1 N until the appearance of the pink color, persistent at least 1 minute.
• This decontaminating + toxic solution is placed on a table shaking, with maximum agitation for 10 min.
• the internal standard solution for CPG is a 0.05% solution of dibutylsebacate in CH 2 Cl 2 for paraoxon, and a 0.4% butyl acetate solution in CH 2 Cl 2 for diethyl sulfide.
• the bottle is capped and shaken manually for 30 s. Everything is placed in a separating funnel.
• the organic phase is recovered in a 25 ml bottle with a stopper ground in Na 2 SO 4 .
• the decontaminating solution contains a cationic, extractable surfactant with methylene chloride, it should be precipitated before injecting CPG.
• the organic phase recovered is added with 20 ml of a solution of an anionic surfactant in majority molar ratio.
• GC Gas chromatography
• the percentage of decomposition of the toxic is given by the formula (1- mg of residual toxic P mg toxic starting ) ⁇ 100
• EDTA which ensures the stabilization of solutions, has an action inhibiting on the effectiveness of decontamination.
• a decontaminating solution B9 having the following weight composition was used: MPPM 5.14% Na gluconate 2.60% Na carbonate 1.95% Na hydroxide 0.39% Benzalkonium chloride 0.85% DB100 silicone oil (Dow Coming) 0.01% Sterile water at 20 ° C 89.06%
• the principle of the test consists in bringing different concentrations of the decontaminating solution to be tested into contact with a suspension of Staphylococcus Aureus ATCC 53-154.
• the tested product is neutralized by a broth with casein peptone, lecithin and polysorbate and there are survivors of the bacterial population according to standard NFT 72-150 (method by dilution / neutralization).
• sample 1 (99% v / v)
• sample 2 (50% v / v)
• sample 3 (10% v / v).

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Cited By (6)

Citations (6)

• 1997
  • 1997-07-31 FR FR9709783A patent/FR2766725A1/fr active Pending
• 1998
  • 1998-07-31 EP EP98401963A patent/EP0894512A1/de not_active Withdrawn

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