FR2766725A1 - STABILIZED DECONTAMINANT COMPOSITIONS - Google Patents

Abstract

The invention relates to stabilized decontaminating compositions containing an organic or inorganic peroxidizing agent and at least one organic stabilizing sequestering agent of the citrate, gluconate or phosphonate type. These compositions are useful for the decontamination of toxic agents and / or organophosphate or organosulfur pollutants.

Description

The invention relates to non-aggressive decontaminant compositions

  Stabilized agents which can be used for the destruction of toxic agents and / or organophosphorus or organosulfur pollutants, especially in the field of chemical warfare agents or in the field of agriculture, for example for the decontamination of insecticides. There are currently many 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.

  These compounds exhibit significant neurotoxicity because of their phosphorylating power with respect to cholinesterase whose inhibition leads to death.

  by accumulation of acetylcholine in the body.

  In addition, there are also toxic organosulfur products such as industrial sulphides or war agents of the family of vesicants, such as

I'ypérite.

  The existence of large stocks of these toxic chemicals and bacteriological is a problem whose solution includes the use of detoxicants to apply to equipment or people infected. Detoxifying solutions can be used in substitution or in combination with

  physical processes of displacement of toxic.

  A number of current decontaminant formulations are essentially based on highly alkaline formulas (solutions of soda, alkanolamines, or amines) and / or hypochlorite (calcium hypochlorite

  especially). These formulas have the main disadvantage of being very aggressive vis-à-

screw hardware.

  The object of the invention is therefore the development of highly effective decontaminating compositions vis-à-vis organophosphorus or organosulfur products, stable, low aggressiveness vis-à-vis equipment and personnel and

  having a great speed of action.

  The decontaminant solutions obtained by dissolving these compositions exhibit exceptional stability both from the point of view of the concentration of oxidizing species and especially in terms of decontamination efficiency. They have the advantage of being usable both on hardened vehicles covered with polyurethane paints, and on uncured vehicles (glycerophthalic paints, high porosity surfaces, presence of elastomers) and

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  only on delicate equipment (interior of vehicles, radios, electronic equipment). Because of their low aggressiveness, these compositions are also usable

  for the decontamination of people by contact with the skin.

  It has now been found that compositions comprising an organic or inorganic peroxidizing agent and at least one organic stabilizing sequestering agent of the citrate, gluconate or phosphonate type have very interesting properties both in terms of stability over time and efficiency.

  decontaminant on toxic agents, possibly in thickened form.

  The solutions obtained from the decontaminant compositions described in the literature are unstable over time, which renders them unsuitable for use under the normal conditions of use during which it may flow.

  an interval of 30 minutes to a few hours between their preparation and their use.

  Decontaminating compositions containing magnesium monoperoxyphthalate (MPPM) and a surfactant, preferably cationic, are described in patent FR 2,676,368. Various decontamination processes, some of which make use of peroxides or MPPM, combined with surfactants cationic, are described in the publication B. Séguès et al., Bull. Soc. Chim. Fr., 1996, 133, 925-937. The publication of S. Batthacharya, J. Org. Chem. 1997, 62, 2198-2204 reports a micellar catalytic decomposition reaction of phosphorus derivatives via microemulsions of MPPM in the presence of an agent

  cationic surfactant. Various publications by C. Lion et al. (eg Bull.

  Soc. Chim., Belg., 1991, 100, 555) relate to the decontaminant efficiency of

  combinations of different peracids and cationic surfactants.

  Nevertheless, the use of sequestering agents to stabilize the solutions

  decontaminants has never been mentioned in the literature.

  The subject of the invention is therefore stabilized decontaminant compositions comprising at least one organic or inorganic peroxidizing agent and at least one

  organic stabilizing sequestering agent of citrate, gluconate or phosphonate type.

  By "stabilizing sequestering agent" is meant in the rest of the

  description both a single stabilizing sequestering agent and a mixture of agents

sequestering stabilizers.

  The stabilizing sequestering agent is advantageously chosen from the

  sodium gluconate, sodium citrate, diethylenetriaminepentamethylene-

  sodium phosphonate (DETPM), ethylenediaminetetramethylenephosphonate

  sodium (EDTMP) and sodium hydroxyethyldiethylphosphonate (HEDP).

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  Surprisingly, it has been found that organic sequestering agents such as ethylenediaminetetraacetate (EDTA) and diethylenetriaminepentaacetate (DTPA) do not provide any advantage in decomposition efficiency (measured in

  percentage residual of toxic), but on the contrary tend to inhibit it.

  In the remainder of the description, the quantities are expressed in percentages

weight.

  The compositions according to the invention may comprise an alkaline buffer.

  By "an alkaline buffer" is meant in the following description also

  well a single alkaline buffer that a mixture of alkaline buffers.

  They may also comprise at least one constituent chosen from

  a hydrotropic agent, a viscosing agent and an antifoaming agent.

  They may optionally comprise at least one surfactant

  cationic, nonionic and / or amine oxide.

  The peroxidizing agent used in the compositions according to the invention

  can be an organic or mineral peroxidizing agent.

  By "a peroxidizing agent" is meant in the following description also

  a single peroxidizing agent that a mixture of peroxidizing agents.

  In an advantageous aspect, the peroxidizing agent is an organic peroxidizing agent such as peracid or peroxide, for example magnesium monoperoxy phthalate hexahydrate (MPPM); Diperoxydodecanediolic 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 peroxide

  diphtaloyl. MPPM is a particularly advantageous peroxidizing agent.

  In another aspect of the invention there will be used a mineral peroxidizing agent, such as, for example:

- H2O2;

  adducts of H 2 O 2 such as percarbonates, in particular sodium percarbonate; 1,4-diazabicyclo [2.2.2] octane (H2O2) 2; phosphate peroxohydrates such as sodium peroxypyrophosphate; the periureum; persalts such as sodium perborate tetrahydrate or monohydrate; potassium monopersulfate, Curox and Caro acid salts, ammonium persulfate, sodium persulfate or potassium persulfate; potassium permanganate; peroxymonophosphates; peroxydiphosphates;

  alkaline peroxides such as sodium peroxide or magnesium.

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  In an advantageous aspect, a mineral peroxidizing agent will be used in the presence of an oxidation activator, that is to say a molecule capable of

generate in situ a peracid.

  In this case, use may in particular be made of an activator without interfacial properties such as those which generate: peracetic acid, for example tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG), tetraacetylglucoluryl (TAGU), tetraacetylcyanuric acid ( TACA), α-acetoxy-co-methyl N-N '(diacetyl) malonamide, acetylsalicylic acid (ASA), sodium paraacetoxybenzenesulfonate (AOBS), diacetyl dimethylglyoxin (DDG) and ethylidene benzoateacetate (EBA) ; Perphthalic acid such as phthalic anhydride (PAN); or - perbenzoic acid such as benzoylimidazole (BID),

  sodium parabenzoxybenzenesulfonate (BOBS).

  Activators with interfacial properties such as nonanoyloxybenzenesulfonate (NOBS), which generates pernonanoic acid or isononanoyloxybenzenesulfonate (ISONOBS), which generates perisononanoic acid, can also be used.

  A preferred organic peroxidizing agent is MPPM.

  A preferred combination is sodium percarbonate or peroxide as inorganic peroxidizing agents and TAED as a peroxidation activator. By "a cationic surfactant" is meant in the following the

  description both a single type of cationic surfactant that a mixture

cationic surfactants.

  As a cationic surfactant, it is possible, for example, to use the

  chloride or cocoyltrimethylammonium bromide, didecyldimethyl chloride

  ammonium, benzalkonium chloride, mixtures of benzalkonium chlorides and alkyldimethylethylbenzylammonium chlorides, and quaternary or polyquaternary ammonium-derived surfactants, optionally partially ethoxylated or whose alkyl chain is optionally interrupted by a grouping

ester or amide.

  In general, it is possible to use cationic surfactants represented by the formulas

A A

R-N-B Xe or R'-N-B X (

C R "

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  in which - R is C8-C22 alkyl or alkenyl - R 'and R ", independently, represent C8-C12 alkyl or alkenyl - C is A-CH2; - (CH2) 2 CH3 or - (CH2) ) NB XB '-A, B and B' independently represent CH3, CH2CH3, C (CH3) 3 or [(CH2) mO; H, m being 2 or 3 and n being an integer of 1 to 3,

  X represents a halogen or a methosulphate group.

  Polycationic surfactants such as N, N, N ', N', N'-pentamethyl-N-tallow-1,3-propane diammonium dichloride may also be used.

  N, N, N ', N', N ', N ", N" -heptamethyl-N-tallow-dipropylene triammonium trichloride.

  By "a nonionic surfactant" is meant in the following the

  description both a single type of nonionic surfactant that a mixture

nonionic surfactants.

  As optional nonionic surfactant, especially in the range of 0 to 25%, preferably 5 to 20%, mention may be made, for example, of alkoxylated fatty alcohols of formula R - [(CH 2) 2 O] n - [(CH2) 30] mH wherein R is as defined above; n and m, independently, represent an integer from 0 to 50, the sum of which n + m> 1; alkylpolyglucosides of formula R '"- [glucose] n- in which R"' is C8-C16 alkyl and n is an integer of 1 to 3; reduced sugar esters, polyol esters and their ethoxylated derivatives, such as, for example, sorbitan monostearate, glycerol or ethylene glycol, or ethoxylated ethoxylated sorbitan monostearate; ethoxylated alkylamides of formula: ## STR2 ##

O (CH2CH20) SH

  o R is as defined above and r and s are integers from 0 to 15, whose sum + s> I;

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  alkylpyrrolidones, the alkyl group of which is C6-C20; the alkylamine oxides of general formula: A B or R, A and B are as defined above;

and their mixtures.

  Preferred nonionic surfactants are

  lauryldimethylamine and octylpyrrolidone.

  An alkaline buffer which can be used in the compositions according to the invention is

  an alkali carbonate or silicate, especially sodium carbonate.

  Advantageously, the solutions containing the compositions according to the invention have a

  pH greater than 6.5, preferably between 8.5 and 12, in particular between 9 and 11.

  If necessary, the pH can be adjusted using an alkalizing agent such as sodium hydroxide, potassium hydroxide, ammonium hydroxide; silicates or borates of

  sodium, potassium, ammonium etc.

  "By" a hydrotrope agent "means in the following description

  both a single type of hydrotrope and a mixture of hydrotropic agents.

  As hydrotropic agent, it is possible to use, for example, urea, cumene sulphonates, toluenesulphonates or xylenesulphonates of sodium, potassium or ammonium; ethoxylated phenols with 4 ethylene oxides (such as the product

  marketed under the name Ethylan HB4 by Diamond Shamrock).

  By "viscosifying agent" is meant in the following description as well

  a single type of viscosity agent that a mixture of viscosizing agents.

  The viscosing agent is preferably chosen from polymers conferring on the solution a thixotropic or rheofluidifying character. These characteristics make it possible to increase the contact time of the decontaminating solution with any non-horizontal surface such as those that can be found on vehicles (tank, airplane, etc.). It is generally considered that an average viscosity under low stress of 300 mPa.s allows to ensure sufficient contact for efficiency

optimal decontaminant.

  Another advantage of the viscosifying agent is that it makes it possible to maintain in suspension a certain number of materials which contribute to the effectiveness of the solution but

  whose solubility is sometimes reduced.

  The viscosing agent may be, for example, modified corn starch or

Hydroxyethyl cellulose.

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  The aqueous solutions of the compositions according to the invention in the final formulation may also contain antifreezes, in a proportion of 5 to 40%, preferably 15 to 25%, such as for example propylene glycol, ethylene glycol or

diethylene glycol.

  In a preferred aspect, the compositions according to the invention comprise: 1 to 95%, preferably 10 to 70%, of a peroxidizing agent, 1 to 35%, preferably 15 to 20%, of a stabilizing sequestering agent organic, 0 to 25%, preferably 5 to 15%, a peroxidation activating agent, 0.5 to 90%, preferably 2 to 30%, an alkaline buffer, 0 to 30%, preferably 5 to 20%, a cationic surfactant and / or an amine oxide and / or a nonionic surfactant, 0 to 50%, preferably 2 to 30%, hydrotropic agent, - 0 to 20%, preferably 5 to 15%, of a viscosifying agent, and - 0 to 5%, preferably 0.05 to 1%, antifoam, the various constituents of said compositions being such that defined above and the

  sum of said constituents being equal to 100%.

  Advantageously, the compositions according to the invention comprise: 10 to 70% of a peroxidizing agent, 15 to 20% of an organic stabilizing sequestering agent, 0 to 15% of a peroxidation-activating agent, 30% of an alkaline buffer, 5 to 20% of a cationic surfactant, 0 to 20% of an amine oxide and / or a nonionic surfactant, 0 to 30% of a hydrotropic agent, 0 to 15% of a viscosifying agent, and 0 to 1% of antifoam,

  the sum of the constituents being equal to 100%.

  A preferred composition according to the invention comprises: -30 to 70% of MPPM, 10 to 30% of sodium gluconate or sodium citrate, 10 to 30% of sodium carbonate, 0 to 5% of sodium hydroxide, and sodium, 5 to 10% benzalkonium chloride, 5% hydroxyethylcellulose, and 0 to 1% antifoam,

  the sum of the constituents being equal to 100%.

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  Another preferred composition according to the invention comprises 10 to 40% of sodium percarbonate, 5 to 15% of TAED, 2 to 20% of sodium carbonate, 10 to 30% of mixture of benzalkonium chlorides, and 30% urea, 2 to 20% DETPM or sodium gluconate, 5 to 15% modified corn starch, and 0 to 1% antifoam,

  the sum of the constituents being equal to 100%.

  Phosphonates of the DETPM or EDTMP type not only have a beneficial effect on the stability and the effectiveness of the decontaminating solutions, but also a peptizing or redispersant action on the flocculates or "creaming" that may occur during the dilution of the compositions comprising agents cationic surfactants and / or activated mineral persalt. In the composition mentioned above, it is for example advantageous to combine an organic sequestering agent such as guconate or sodium citrate with a

  phosphonate such as DETPM or EDTMP.

  The invention also relates to the use of the compositions as defined above for the decontamination of toxic agents and / or organophosphorus or organosulfur pollutants, in particular organophosphorus or organosulfur warfare agents, or in the field of agriculture for the decontamination of organophosphorus or organosulfur phytosanitary agents, in

  insecticides, or for the decontamination of industrial pollutants.

  The compositions may be in the form of a powder, a liquid, a

gel or suspension.

  The components of the final formulation in liquid form at room temperature can be either sprayed on the powder constituting the remainder of the formulation, or incorporated separately in liquid form into the solution.

decontaminant.

  The compositions according to the invention are preferably used in aqueous solution at a concentration of 2 to 50%, preferably 8 to 25% by weight. They can also be used in the form of emulsions or microemulsions after dispersion in a water-immiscible organic solvent such as, for example, aliphatic or aromatic hydrocarbons, optionally

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  chlorinated, for example toluene, xylene, methylene chloride and tetrachlorethylene. They can be used manually or mechanically by sprinkling, washing, spraying, soaking, impregnation or any other operation allowing the contact of said compositions with contaminated material or persons. The stability of the solutions is measured by assaying the active oxygen after a given storage time (1 h 30) at room temperature or at 40 C, according to the

nature of the oxidizing agent.

  Decontaminant efficiency measures are performed by analysis of the

  residual toxic by gas chromatography.

  The invention is illustrated by the following nonlimiting examples:

Example 1

  Different compositions according to the invention are summarized in Table 1 below.

O1 CO (> 1 O - - 1 O.-3

Cn 0 Ln 0 cn 0 0n

Table 1

A B C D E F G H

  Magnesium monoperoxyphtallate 60.00 50.00 Sodium percarbonate 35.00 Peruvian 45.00 70.00 1,4-diazabicyclo [2.2. 2] octane (H 2 O 2) 70.00 Curox 55.00 sodium perborate tetrahydrate 30.00 tetraacetyl ethylenediamine 6.00 4.00 tetraacetyl glycoluryl 10.00 sodium isononanoyloxybenzene sulfonate 10.00 lauryl dimethylamine oxide 10 00 N-octyl pyrrolidone 8.50 Didecyl ammonium chloride 9.00 Cetyl trimethyl ammonium methosulfate 9.00 Duoquad T50 25.00

  Benzalkonium Chloride 10.00 4.00 -

  Hyamine 15.00 10.00 Hydrogenated fatty tallow alcohol ethoxylated with 25 moles of EO 5.00 10.00 Condensate of ethylene oxide and propylene oxide (DEHYPON LS 54) 10.00 Polyethylene glycol of molecular weight 1500 5, 00 Sodium carbonate 15.00 14.00 14.95 7.00 17.00 17.50 6.00 Urea 16.00 5.00 Sodium bicarbonate

  3.93 Sodium ethylenediamine-tetramethylenephosphonate 4.00 10.00 Sodium diethylenetriamine-pentamethylenephosphonate 4.00 Sodium citrate 13.00 Sodium gluconate 10.90 10.00 21.00 9.90 Sodium cumene sulphonate., 3 00 Silicone oil DB 100 (Dow Coming) 0.10 0.05 0.07 0.10 Hydroxyethyl cellulose 4.00 2.00 Modified corn starch 10.00 5.00 xanthan gum 1.00 Total 100, 00 100,00 100,00 100,00 100,00 100,00 100, 00 100,00

O0 N. -. - -

  Table 2 <CD, CD

Table 2 (>.

  A0 A1 A2 A3 A4 A5 A6 A7 A8 s x Magnesium monoperoxyphtallate _. Sodium percarbonate 4.40 4.40 4.40 4.40 4.40 4.40 4.40 4.40 4.40 cD Tetraacetylethylenediamine 2.40 2.40 2.40 2.40 2 40 2.40 2.40 2.40 2.40 - C Benzalkonium chloride

  CD Sodium carbonate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 8 O Urea 4,30 4,30 4,30 4,30 4,30 4 , 4.30 4.30 4.30 3 - o Sodium hydroxide o

  Sodium ethylenediamine-tetramethylenephosphonate 4.00 o.

  Diethylenetriamine-sodium pentamethylenephosphonate 4, 00 o

Sodium citrate 4.00

  Sodium Gluconate 4.00.oo Sodium ethylenediamine tetraacetate 4.00 4.00 8 C3 D Sodium diethylenediamine pentaacetate 4.00 Q Magnesium sulphate 1.00 3 Silicone oil DB 100 (Dow Corning) 0.01 0.01 0.01 0.01 0.01 0.01 0, 01 0.01 0.01 _.D CD Hydroxyethyl cellulose _ CD Modified corn starch 3.00 3.00 3.00 3.00 3, 00 3.00 3.00 3.00 3.00 <n (D

CD (O

  Total Powder 15,11 15,11 19, 11 19,11 19,11 19,11 19,11 20,11 19,11 o Water at 28 HF (temp = 20 C) _ o _ <- Water at 28 HF (temp = 40 C) 84.89 84.89 80.89 80.89 80.89 80.89 80.89 79.89 80.89 OD <O, Total 100.00 100.00 100.00 100, 00 100.00 100.00 100.00 100.00 100.00 oO - - 1? (D _. CD <n

t "M -

  tn 1 0o 0o n0 o 0n Table 2 (continued)

B0 B1 B2 B3 B4 B5 B6 B7 B8

  Magnesium monoperoxyphtallate 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Sodium percarbonate Tetraacetyl ethylenediamine 4.00 Benzalkonium chloride 1.30 1, 30 1, 30 1.30 1.30 1.30 1.30 1.30 1.30 Sodium carbonate 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Urea Sodium hydroxide 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 Sodium ethylenediamine-tetramethylenephosphonate 4.00 Sodium diethylenetriamine-pentamethylenephosphonate 4.00 Sodium citrate 4 , 00 Sodium gluconate 4.00 Sodium ethylenediamine tetraacetate 4.00 4.00 Sodium diethylenediamine pentaacetate 4.00 Magnesium sulphate 1.00 Silicone oil DB 100 (Dow Corning) 0.01 0.01 0, 01 0.01 0.01 0, 01 0.01 0.01 0.01 Hydroxyethyl cellulose 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Starch modified corn _ Total Powder 13.41 13.41 17.41 17.41 17, 41 17.41 17.41 18.41 17.41 Water at 28 HF (temp = 20 C) 86.59 86.59 82 , 59 82.59 82.59 82.59 82.59 81.59 82.59 Water at 28 HF (temp. = 400C) Pi -.j Total 100,00100,00000 100, 00 100,00 100,00 100,00 100,00 100,00 100,00 Plj ro,

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Example 3

  The effectiveness of the decontaminant solutions containing compositions of Table 2 above was measured by residual toxicity analysis by

  gas chromatography (GC).

  The measure of effectiveness was performed on paraoxon and diethylsulfide at a concentration of 50 mg of toxic substance / 5 ml of decontaminant solution min after dissolution and with a contact time of the decontaminant solution and the substance. 10 min. Two types of decontaminant compositions containing respectively as oxidizing agent, either sodium percarbonate with TAED as an activator, or MPPM, were used.

  presence or absence of stabilizing sequestering agent.

  In parallel with this efficiency measure, active oxygen is measured after

  min (without sequestrant) and 90 min (with and without sequestrant).

  The tests were carried out according to the following method: 1 / Preparation of the decontaminating solution The decontaminating powder is weighed in a 100 ml glass bottle with ground-glass stopper, then 50 ml of 28 HF water are introduced. Stirring is carried out

  manual until complete dissolution of the powder.

  The pH is measured, as is the number of mg of oxygen available.

  2 / Determination of Active Oxygen a / MPPM Formulas A weight, noted P1, of this solution is taken by syringe and deposited in ml of demineralized water, and then acidified with 5 ml of acetic acid. 15 ml of KI solution at 20% by weight are then added and the solution is immediately determined by 0.1 N Na thiosulfate. After passing from orange to yellow, a Thiodene spatula (poisoning) is added.

  starch) and dosed until complete discoloration.

  b / Na Percarbonate or Perure Formulas A weight, noted P1, of this solution is taken by syringe and deposited in ml of demineralised water, and then acidified with 20 ml of 20% sulfuric acid. 0.1 N KMnO 4 is used until the appearance of the color pink, persistent at least

1 minute.

  The number of mg of active oxygen is obtained by the formula: Vx4

  mg of active O2 in 5 ml of solution = -

  Where V is the volume of Na thiosulfate or KMnO4 added to the

  realization of the reaction (disappearance or appearance of the color, as the case may be).

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  3 / Measurement of the decontaminant efficiency Using a capillary 1 mm in diameter, the drops of toxic substance are deposited on the bottom of a 100 ml glass bottle with ground-glass stopper. We

  closes the bottle immediately and we note weight P of toxic deposited.

  After 90 minutes of dissolution, 5 ml of the decontaminant solution are

  taken by syringe and deposited on the toxic, (the bottle being closed soon).

  This decontaminant + toxic solution is placed on a shaking table, with maximum stirring for 10 min. In the flask, are introduced: - 40 ml of a saturated solution of NaCl, supplemented to 70 ml with deionized water; - 10.0 ml of internal standard solution;

  2 ml of xylene are added for the extraction of diethylsulphide.

  The internal standard solution for GC is a solution of 0.05% dibutylsébaçate in CH2CI2 for paraoxon, and a solution of 0.4% butyl acetate

  in CH2Cl2 for diethylsulfide.

  The bottle is capped and stirred manually for 30 s. Everything is placed

in a separating funnel.

  The organic phase is recovered in a 25 ml flask with ground stopper

on Na2SO4.

  If the decontaminant solution contains a cationic surfactant, extractable

  with methylene chloride it should be precipitated before GPC injection.

  For this, the recovered organic phase is added with 20 ml of a

  solution of an anionic surfactant in majority molar ratio.

  Gas chromatography (GC) is carried out with a VARIAN 3400 flame ionization detection device, with a 2.5% OV1 glass column on a 80/100 mesh gas chromium (length: 1.5 m; 1 / 8th) for the paraoxon, and a PORAPAK Q glass column (length: 1.5 m, diameter 1 / 8th)

for diethylsulfide.

  The percentage of decomposition of the toxic is given by the formula mg of residual toxic P (starting mg toxic)) The results are reported in tables 3 (active oxygen) and 4

  (decontaminant efficacy) below.

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Table 3 Stabilization of the oxidant (mg 02 1 5 ml solution) N "FORMULA A (base

  percarbonate + TAED) After 15 min after 90 min A0 Solution A without sequestering stabilizer at 15 '11.0 A1 Solution A without sequestering stabilizer 1.8

A2 A + 4% DETPMI 9.8

A3 A + 4% EDTMP 8.9

  A4 A + 4% sodium gluconate 11.0 A5 A + 4% sodium citrate 4.9 A6 A + 4% EDTA4Na 6.6 A7 A + 4% EDTA 2 Na + 1% MgSO4 6.8 A8 A + 4% DTPA 5 Na 10.2 NO FORMULA B (MPPM base) After 15 min after 90 min BO Solution B without stabilizing sequestrant at 15 '14.4 BI1 Solution B without stabilizing sequestrant 5.5

B2 B + 4% DETPMI 3.7

B4 B + 4% 6.7

  B5 B + 4% sodium citrate 4.4 B6 B + 4% EDTA4Na 1.7

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Table 4

  Efficiency I Efficiency / organophosphorus organosulfur N FORMULA A (percarbonate base + TAED)% decomposition% decomposition of PARAOXON DES A0 Solution A without sequestering stabilizer at 15 '81.8 98.0 A1 Solution A without stabilizing sequestrant 37.5 29.5

A2 A + 4% DETPM 63.0 74, 0

A3 A + 4% EDTMP 51.0 70, 0

  A4 A + 4% sodium gluconate 69.5 67, 5 A5 A + 4% sodium citrate 55.0 50.0 A6 A + 4% EDTA4 Na 15.0 27.0

A7 A + 4% EDTA2Na + 1% MgSO4 7.1 -

  A8 A + 4% DTPA 5 Na 39.2 51, 0 N FORMULA B (MPPM base) on PARAOXON on DES B0 Solution B without stabilizing sequestrant at 15 '63.2 97.9 B1 Solution B without stabilizing sequestrant 51.6 36 , 0

B2 B + 4% DETPM 71.0 33, 0

  B4 B + 4% sodium gluconate 76.0 61.0 B5 B + 4% sodium citrate 72.0 40.0 B6 B + 4% EDTA 4 Na 36.0 14.5 The results show that the addition of a stabilizing sequestering agent such as DETPM or DETMP make it possible both to stabilize the solutions

  decontaminant and maintain their decontaminating effectiveness.

  On the other hand, the EDTA, which ensures a stabilization of the solutions, has an action

  inhibitor on decontamination efficiency.

  Similarly, the addition of DTPA provides a stabilization of the oxidizing agent, but which does not result in any significant improvement in decontaminant efficiency on

  organophosphates and only a slight improvement on organosulfur.

  As a result, aminopolycarboxylate sequestering agents such as EDTA

  or DTPA are excluded from the scope of the invention.

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Claims (24)

  1. Stabilized decontaminant composition, characterized in that it comprises at least one organic or inorganic peroxidizing agent and at least one organic stabilizing sequestering agent of citrate, gluconate or phosphonate type. 2. Composition according to claim 1, characterized in that it comprises an organic stabilizing sequestering agent chosen from DETPM, EDTMP and HEDP.   3. Composition according to any one of claims I to 3,   characterized in that it also comprises at least one constituent selected from an alkaline buffer, a hydrotrope agent, a viscosifying agent, an antifoaming agent, a   cationic surfactant, a nonionic surfactant and an amine oxide.   4. Composition according to one of claims I to 3, characterized in that   it comprises, in weight percentages: 1 to 95%, preferably 10 to 70%, of a peroxidizing agent, 1 to 35%, preferably 15 to 20%, of an organic stabilizing sequestering agent, 0 to 25%, preferably 5 to 15%, of a peroxidation activating agent, 0.5 to 90%, preferably 2 to 30%, an alkaline buffer, 0 to 30%, preferably at 20%, a cationic surfactant and / or an amine oxide and / or a nonionic surfactant, 0 to 50%, preferably 2 to 30%, of a hydrotropic agent, 0 to 20%, preferably 5 to 15%, of a viscosing agent, and 0 to 5%, preferably 0.05 to 1%, of antifoam,   the sum of the constituents being equal to 100%.   5. Composition according to any one of claims 1 to 4,   characterized in that it comprises, in weight percentages: - 10 to 70% of a peroxidizing agent, - 15 to 20% of an organic stabilizing sequestering agent, - 0 to 15% of a peroxidation activating agent, - 2 to 30% of an alkaline buffer, 5 to 20% of a cationic surfactant, 0 to 20% of an amine oxide, 0 to 20% of a nonionic surfactant, 0 to 30% of a hydrotropic agent, 0 to 15% of a viscosing agent, and 0 to 1% of antifoam,   the sum of the constituents being equal to 100%. 18 2766725   6. Composition according to any one of claims 1 to 5,   characterized in that it comprises an organic peroxidizing agent selected from magnesium monoperoxy phthalate 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 diphenoyl peroxide.   7. Composition according to any one of claims 1 to 6,   characterized in that the peroxidizing agent is MPPM.   8. Composition according to any one of claims 1 to 5,   characterized in that it comprises a mineral peroxidizing agent selected from H2O2;   adducts of H2O2; persalts and alkaline peroxides.   9. Composition according to claim 8, characterized in that the agent   inorganic peroxidant is selected from H2O2; sodium percarbonate; the 1,4-   diazabicyclo [2.2.2] octane (H202) 2; phosphate peroxohydrates such as sodium peroxypyrophosphate; the periureum; sodium perborate tetrahydrate or monohydrate; potassium monopersulfate, Curox and Caro acid salts, ammonium persulfate, sodium persulfate or potassium persulfate; potassium permanganate; peroxymonophosphates; the   peroxydiphosphates; sodium peroxide or magnesium.   10. Composition according to any one of claims 1 to 5, 8 and 9,   characterized in that a mineral peroxidizing agent is used in combination with a peroxidation activator.   11. A composition according to claim 10, characterized in that the peroxidation activator is selected from tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG), tetraacetylglucoluryl (TAGU), tetraacetylcyanuric acid (TACA), and the like. acetoxy-α-methyl N-N '(diacetyl) malonamide, acetylsalicylic acid (ASA), sodium paraacetoxybenzenesulfonate (AOBS), diacetyl dimethylglyoxin (DDG) and ethylidene benzoateacetate (EBA); phthalic anhydride (PAN); benzoylimidazole (BID), sodium parabenzoxy benzenesulfonate (BOBS); nonanoyloxybenzenesulfonate (NOBS) and   isononanoyloxybenzenesulfonate (ISONOBS).   12. Composition according to any one of claims I to 11,   characterized in that it comprises sodium percarbonate or peroxide thereof   as peroxidants and TAED as a peroxidation activator.   13. Composition according to any one of claims I to 12,   characterized in that the alkaline buffer is sodium carbonate. 19 2766725   14. Composition according to any one of claims 1 to 13,   characterized in that it contains lauryldimethylamine oxide or octylpyrrolidone.   15. Composition according to any one of claims 1 to 14,   characterized in that it comprises a hydrotropic agent selected from urea, cumene sulfonates, toluenesulfonates or xylenesulphonates of sodium, potassium or   ammonium; ethoxylated phenols with 4 ethylene oxides.   16. Composition according to any one of claims 1 to 15,   characterized in that it comprises a viscosing agent selected from corn starch   modified and hydroxyethylcellulose.   17. Composition according to any one of claims I to 16,   characterized in that it comprises a cationic surfactant selected from cocoyltrimethylammonium chloride or bromide, didecyldimethylammonium chloride, benzalkonium chloride, mixtures of benzalkonium chlorides and alkyldimethylethylbenzylammonium chlorides, and surfactants derived from quaternary or polyquaternary ammonium, optionally partially ethoxylated or whose alkyl chain is optionally interrupted by an ester or amide group.   18. Composition according to any one of claims I to 7 and 13 to   17, characterized in that it comprises: - 30 to 70% of MPPM, - 10 to 30% of sodium gluconate or of sodium citrate, - 10 to 30% of sodium carbonate, - 0 to 5% of sodium hydroxide, 5 to 10% benzalkonium chloride, 5% hydroxyethylcellulose, and 0 to 1% antifoam   the sum of the constituents being equal to 100%.   19. Composition according to any one of claims 1 to 5 and 8 to 17,   characterized in that it comprises: - 10 to 40% of sodium percarbonate, - 5 to 15% of TAED, - 2 to 20% of sodium carbonate, - 10 to 30% of mixture of benzalkonium chlorides, - 30% urea, 2 to 20% DETPM or sodium gluconate, 5 to 15% modified corn starch, and 2766725 0 to 1% antifoam,   the sum of the constituents being equal to 100%.   20. Use of a composition according to any one of the claims   1 to 19 for the decontamination of toxic agents and / or organophosphorus or organosulfur pollutants.   21. Use of a composition according to any one of the claims   I to 19 for the decontamination of organophosphorus or organosulfur warfare agents.   22. Use of a composition according to any one of the claims   1 to 19 for the decontamination of organophosphorus or organosulfur phytosanitary agents, in particular insecticides or for the decontamination of agents industrial pollutants.   23. An aqueous solution containing from 2 to 50%, preferably from 8 to 25% by weight, of a decontaminant composition according to any one of Claims 1 to 19.   24. The solution of claim 23, characterized in that it has a pH   greater than 6.5, preferably between 8.5 and 12.