JP5437363B2 - Compositions and processes for destroying organophosphorus and / or organosulfur contaminants - Google Patents

Abstract

The invention relates to a decontaminating composition comprising: (i) perpropionic acid, (ii) dipicolinic acid, (iii) a salt of hydroxyethyldiethylphosphonic acid, (iv) a surface-active agent, and (v) an alkalinizing agent. The decontaminating compositions that are the subject of the invention have a high stability and high effectiveness, enabling a rapid destruction of the toxic organophosphorus or organosulphur agents.

Description

  The present invention relates to the decontamination of organophosphorus or organosulfur pollutants and / or poisons, for example the decontamination of pesticides, especially in the field of chemical weapons or agriculture. The present invention particularly relates to a novel decontamination composition comprising two specific stabilizers, and further to a process for the destruction of these organophosphorus and / or organosulfur contaminants.

  In the field of chemical weapons, there are currently many organophosphorus esters derived from phosphoric acid and phosphinic acid, such as Tabun, Sarin or Soman. These compounds have high neurotoxicity due to their phosphorylation ability with respect to cholinesterase, and inhibition of cholinesterase results in accumulation of acetylcholine in the organism leading to death.

  In addition, there are toxic organosulfur products, such as industrial sulfide or blister family weapons, such as yperit.

  Used in the agricultural field as pesticides and herbicides, organophosphate toxic compounds such as organophosphates, amidophosphates, organoamidophosphates, phosphoro-thionates, phosphonothionates and phosphonoamidothionates, and also R There are -S-R 'type organic sulfur compounds, and R and R' represent in particular hydrocarbon radicals or halogenated hydrocarbon radicals.

  Of the best known organophosphorus compounds, O, O-diethyl-Op-nitrophenyl phosphate (Paraoxon), O, O-diethyl-Op-nitrophenylphosphonothioate (Parathion) and O , O-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidyl) phosphorothioate (Diazinon) plays an important role in agriculture as an insecticide or herbicide.

  In addition, toxic organosulfur compounds such as dichloro-2,2′-diethyl sulfide or 2-phenyl-2-chlorodiethyl sulfide are also very powerful chemical agents, and this stability substantially reduces toxicity. Can stay in a contaminated area for several years without seeing it.

  The existence of a large stockpile of the products listed above is a problem. These removals include the use of decontaminating compositions to be applied to the product itself or to contaminated materials or individuals. The decontamination composition can be used as a replacement for a poison or in combination with a physical method for replacing a poison.

  Therefore, it is possible to have a decontamination composition capable of degrading toxic products themselves and decontaminating materials contaminated with poisons quickly and effectively, especially in the intended use or accidental use of such compounds. is important.

  The most effective compositions currently available are sodium hydroxide solutions in the presence of amines or calcium perchlorate in aqueous media or methyl glycol (1,2-propanediol); however, such solutions Is corrosive with respect to brittle materials, in particular light metal alloys.

  It is well known that nucleophilic compounds are effective products for removing organophosphorus and organosulfur-based poisons. Thus, hydroxyl anions in strongly basic media can neutralize these toxicants. However, the effectiveness obtained is achieved by a strong aggressiveness with respect to the material to be decontaminated.

  Another approach is that due to both this nucleophilic and oxidative properties, basic media that are not very strong or even near neutral, peroxygenated compounds such as aqueous hydrogen peroxide, tert-butyl hydroperoxide, perborate And using a peracid.

  Various peroxygenated compounds are most commonly used in solutions containing surfactants of the quaternary ammonium type that improve the contact between the peroxygenation reactant and the poison during decontamination.

  Peracids currently proposed in the decontamination of materials contaminated with various families of poisons, in particular Paraoxon® and sulfur-containing compounds, are linear chains containing long carbon chains and having a pH of 6-8. In the form of aqueous solutions of aqueous peracids or aqueous solutions based on industrial peracids such as magnesium monoperoxyphthalate or phthalimidoperhexanoic acid, which in both cases are in particular quaternary ammonium salt type interfaces. Combined with an active agent.

  However, the first peracid is rarely commercially available at the industrial level and has moderate stability and moderate solubility, while the second peracid is commercially available but is solid at ambient temperature. It is a form, has the same level of stability at high temperatures, and is not easy to handle during use.

Aqueous compositions based on C ₂ -C ₄ percarboxylic acids and dipicolinic acid are described in international application WO 01/30452 as decontamination agents. However, such compositions have stability problems and use percarboxylic acid anhydrides obtained by an expensive process of azeotropic distillation.

  An aqueous composition comprising a peroxidant which may be a peracid as a decontamination agent is described in patent application EP 0894512. Nevertheless, this type of composition has a relatively weak decontamination effect.

International Publication No. 01/30452 EP 0894512

  Therefore, there is a real need for new decontamination compositions that are much more stable, more effective than those described above, and that allow rapid destruction of organophosphorus or organosulfur poisons.

  The present application has developed a composition that can solve the above-mentioned problems, and in particular, has developed a composition that has excellent stability and excellent effectiveness and that causes rapid destruction of poisons.

The subject of the present invention is therefore first of all:
(I) perpropionic acid,
(Ii) dipicolinic acid,
(Iii) Hydroxyethylidene diphosphonic acid (HEDP or a salt thereof)
A decontamination composition comprising (iv) a surfactant and (v) a basifying agent.

  Surprisingly, the composition as defined above is stable enough to obtain sustained decontamination effectiveness.

  Surprisingly, it is also noted that the compositions that are the subject of the present invention containing perpropionic acid show greater decontamination effectiveness than compositions containing peracetic acid (Examples 2 and 3).

  Preferably, the hydroxyethylidene diphosphonate is sodium hydroxyethylidene diphosphonate (HEDP).

  For the purposes of the present invention, the term “decontamination composition” means a composition that can be used for decontamination of materials contaminated with organophosphorus and / or organosulfur compounds, or degradation of the toxic product itself. With the goal.

  Advantageously, the perpropionic acid used is in particular in the form of an aqueous solution obtained by reaction of an aqueous hydrogen peroxide solution with propionic acid in the presence of a catalyst such as sulfuric acid or boric acid. Such a preparation process is described, for example, in French patent application FR 2462425. Unlike the no aqueous solution of perpropionic acid described in French patent application numbers FR2464947 and FR2519634, the aqueous solution does not undergo an azeotropic distillation step with a toxic or flammable organic solvent such as 1,2-dichloroethane or cyclohexane. Can be obtained by a simple method.

  Thus, the perpropionic acid used is perpropionic acid as product, propionic acid as unreacted reactant, aqueous hydrogen peroxide solution as unreacted reactant, and sulfuric acid or boric acid as catalyst. It is the form of the aqueous solution containing.

Accordingly, the decontamination composition as defined above, in addition to compounds (i) to (v):
Propionic acid,
An aqueous hydrogen peroxide solution and sulfuric acid and / or boric acid can be included.

  Such compositions are water-soluble liquids, which facilitates the use of decontamination compositions that are the subject of the present invention.

  In one particular embodiment of the invention, the composition defined above is in the form of an aqueous solution. The subject of the present invention is therefore also an aqueous solution comprising a decontamination composition as defined above.

  The composition that is the subject of the present invention comprises a basifying agent. Preferably, the basifying agent is sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, ammonium phosphate, silicic acid. Selected from sodium, potassium silicate, ammonium silicate, sodium borate, potassium borate and ammonium borate, and mixtures thereof. The basifying agent can adjust the pH of the composition that is the subject of the present invention. Advantageously, the composition that is the subject of the present invention has a pH of greater than 7, preferably 8 to 12, in particular 8.5 to 9.5.

  The composition according to the invention can be buffered to a pH of 7 to 10. If the composition that is the subject of the present invention is a basic composition, dipicolinic acid, perpropionic acid and HEDP can be in the form of their corresponding salts.

  The composition that is the subject of the present invention may also contain an alkaline buffer. For the purposes of the present invention, the term “alkaline buffer” is intended to mean both a single type of alkaline buffer and a mixture of alkaline buffers. The composition according to the invention comprises an alkaline buffer such as an alkaline carbonate or alkaline silicate, in particular potassium carbonate or sodium carbonate.

  For the purpose of the present invention, the term “surfactant” is used in the proportion of 0 to 25% by weight, preferably 5 to 20% by weight, based on the total weight of the composition. It is intended to mean a cationic, nonionic or zwitterionic surfactant.

Cationic surfactants can include those of the quaternary ammonium type, for example:
Cetyltrimethylammonium bromide,
Cetyltrimethylammonium chloride,
Cetyldimethyl (2-hydroxyethyl) ammonium bromide,
Cetylmethylbis (2-hydroxyethyl) ammonium bromide,
Mention may be made of benzyltrimethylammonium bromide and cetyldiaza-1,4-bicyclo [2.2.2] octylammonium bromide.

  These surfactants are known and most of these are commercially available. These are C.I. A. Bunton et al. , J .; Am. Chem. Soc. 95, 2912 (1973) and L.M. Horner et al. , Phosphorus and Sulfur, 11, 339 (1981).

Nonionic surfactants that can optionally be used include, for example:
Alkoxylated aliphatic alcohols of the formula R — [(CH ₂ ) ₂ O] _m — [CH ₂ CH (CH ₃ ) O] _n —H where R is 8 to 22 carbon atoms, preferably 12 to 14 Alkyl or alkenyl containing 1 carbon atom; n and m independently represent an integer from 0 to 50 and the sum of n + m is>1;
An alkylpolyglucoside of the formula R ′ ″-[glucose] _n —, where R ′ ″ is C ₈ -C ₁₆ alkyl and n is an integer from 1 to 3;
Esters of reducing sugars, polyol esters and ethoxylated derivatives thereof, such as sorbitan monostearate, glycerol monostearate or ethylene glycol monostearate, or ethoxylated sorbitan monostearate containing 20 ethylene oxides;
formula

のエトキシル化アルキルアミド、
式中、Ｒは上記で定義された通りであり、ｒおよびｓは０から１５の整数であり、ｒ＋ｓの合計は＞１である；
アルキルピロリドンであって、このアルキル基がＣ_６−Ｃ_２０アルキルであるアルキルピロリドン；
およびこれらの混合物
を挙げることができる。

Ethoxylated alkylamides of
Where R is as defined above, r and s are integers from 0 to 15, and the sum of r + s is>1;
An alkyl pyrrolidone, alkylpyrrolidones the alkyl group is a C ₆ -C ₂₀ alkyl;
And mixtures thereof.

  Preferably, perpropionic acid is present in the aqueous solution at a concentration of, for example, 0.05 to 4.5 mol / l.

In one preferred embodiment, the composition that is the subject of the present invention is based on the total weight of the composition:
4 to 16% by weight of perpropionic acid,
0.1% to 2% by weight dipicolinic acid,
0.5% to 5% by weight sodium hydroxyethyl diethylphosphonate,
5 wt% to 20 wt% surfactant,
2% to 20% by weight of basifying agent, and 5% to 15% by weight of alkaline buffer.

  The solution that is the subject of the present invention also comprises at least one component selected from hydrophobic agents, such as urea or sodium cumene sulfonate, thickeners, such as xanthan gum, modified corn starch or hydroxyethyl cellulose, or else antifoam agents Can be included.

  The composition may be in the form of a powder, liquid, gel or suspension.

  The composition according to the invention is preferably used in an aqueous solution at a perpropionic acid concentration of 0.5% to 40% by weight, based on the total weight of the solution. They can also be in the form of emulsions or microemulsions after dispersion in water-immiscible organic solvents such as, for example, optionally chlorinated aliphatic or aromatic hydrocarbons such as toluene, xylene, methylene chloride, and tetrachloroethylene. Can be used.

  They can be used manually or mechanically by spraying, coating, spraying, dipping, impregnation or any other operation that can bring the composition into contact with the mixed materials or individuals.

  The subject of the invention is also a process for decontaminating organophosphorus or organosulfur toxicants and / or pollutants, which contacts the toxicants and / or pollutants with a composition as defined above. including.

  Said organophosphorus or organosulfur poison and / or pollutant are, for example, organophosphorus or organosulfur weapons in the military field, or organophosphorus or organosulfur plant protection agents, in particular insecticides or industrial pollutants in the agricultural sector. May be.

  The subject of the present invention is also a process for decontaminating materials contaminated with organophosphorus and / or organosulfur compounds, and projecting, spraying or simplifying a composition as defined above on the contaminated material. Or by applying the contaminated material by dipping into a container containing the composition as defined above.

  When the contaminated material is decontaminated due to the pH of the composition that is the subject of the present invention, the material may be a reinforced vehicle coated with polyurethane paint, a non-reinforced vehicle (glycerophthalic paint, porous High surface, presence of elastomer), and high sensitivity devices (vehicle interior, radio, electronic devices) can be selected.

  Due to their low aggressiveness, these compounds can also be used to decontaminate individuals by contact with the skin.

  The molar ratio of perpropionic acid to contaminants is generally 5 to 10 for organophosphorus contaminants (hydrolyzed to phosphate) or 3 to 5 for organic sulfur contaminants (oxidized to sulfones).

The subject of the invention is also a process for obtaining a decontamination composition according to the invention. This process includes the following sequential steps:
a) obtaining a composition comprising perpropionic acid, dipicolinic acid and hydroxyethylidene diphosphonic acid;
b) A step of dissolving the composition obtained in step a) in an aqueous composition containing a surfactant comprising an amine oxide and a basifying agent.

In another embodiment of the invention, the process for obtaining a decontamination composition comprises the following sequential steps:
a) obtaining a composition comprising perpropionic acid and dipicolinic acid;
b) dissolving the composition obtained in step a) in an aqueous composition comprising a surfactant, a basifying agent and a hydroxyethylidene diphosphonate, preferably sodium hydroxyethylidene diphosphonate.

  By way of example, the hydroxyethylidene diphosphonic acid of the composition that is the subject of the present invention can consist of a product sold by the company Solutia under the trade name Dequest 2010®, It can consist of products sold by Solutia under the Dequest 2016®.

  The following examples illustrate, but do not limit the scope of the invention. In these examples, percentages are by weight unless otherwise indicated.

  A perpropionic acid solution is prepared by mixing 1000 g of propionic acid, 500 g of aqueous hydrogen peroxide at 70%, 25 g of sulfuric acid, 7.5 g of dipicolinic acid and 15 g of hydroxyethylidene diphosphonic acid (Dequest 2010®). The mixture is kept stirring for 12 hours at ambient temperature in order to obtain an equilibrium concentration. The solution thus prepared contains:

＊過酸化水素水溶液は、硫酸セリウム（ＩＶ）で滴定される。
＊＊総活性酸素はヨード滴定で滴定される。

* The aqueous hydrogen peroxide solution is titrated with cerium (IV) sulfate.
** Total active oxygen is titrated by iodometric titration.

  Perpropionic acid is determined by the difference between total active oxygen and aqueous hydrogen peroxide.

370 g of the pre-prepared solution is then mixed with the following for decontamination application:
Barquat MS100 (Lonza) 70g
Glucopon (registered trademark) 100g
Potassium hydroxide 90g
190 g of potassium carbonate and 900 g of water.

  The reactivity as a function of time of the formulation prepared in Example 1 is tested for decontamination with Paraoxon®.

  In a stirred glass container, 1.8 g of the formulation prepared in Example 1 is added to 50 mg of Paraoxon®. Therefore, the initial decontamination / toxic agent molar ratio is 5.8. At T minutes after addition, the sample is removed and the reaction is stopped by adding excess sodium thiosulfate. 8 ml of water saturated with NaCl, 10 ml of 50/50 ethyl acetate / hexane and dibutyl sebacate 0.1% (internal standard) are then added to the sample. The organic phase is removed, dried over sodium sulfate and the remaining Paraoxon® is quantitatively measured by gas chromatography.

  This procedure is repeated after various time periods for the formulation prepared in Example 1.

  The results are summarized in the following table:

(Not according to the invention.)
The perpropionic acid-based formulation described in Example 1 was compared to a similar formulation based on peracetic acid. A 39% peracetic acid solution is prepared following the same procedure as in Example 1, replacing propionic acid with acetic acid, and then adding the same amount of the other components.

  The resulting formulation is tested with Paraoxon® according to the procedure described in Example 2. The initial decontamination / toxic agent molar ratio is 6.8. The results are shown in the following table:

  Thus, these examples show the advantages of perpropionic acid based formulations compared to peracetic acid based formulations for decontamination of organophosphate poisons.

Claims (13)

(I) perpropionic acid,
(Ii) dipicolinic acid,
(Iii) hydroxyethylidene diphosphonic acid or a salt thereof,
An organic phosphorus and / or organic sulfur compound decontamination composition comprising (iv) a surfactant and (v) a basifying agent.   The composition according to claim 1, wherein the hydroxyethylidene diphosphonate is sodium hydroxyethylidene diphosphonate.   The basifying agent is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium silicate, potassium silicate, ammonium silicate, sodium borate, potassium borate and ammonium borate, and mixtures thereof A composition according to any one of claims 1 and 2, characterized in that The composition according to any one of claims 1 to 3, further comprising an alkaline buffer. 5. A composition according to claim 4, wherein the alkaline buffer is selected from alkaline carbonates and alkaline silicates. Characterized in that it comprises a non-ionic surfactant addition, the compositions according to any one of claims 1 to 5. Characterized in that perpropionic acid is present in a concentration of 4.5 mol / l 0.05 A composition according to any one of claims 1 to 6. 8. Composition according to any one of claims 1 to 7 , characterized in that it is buffered at a pH of 7 to 10. With respect to the total weight of the composition,
4 to 16% by weight of perpropionic acid,
0.1% to 2% by weight dipicolinic acid,
0.5% to 5% by weight sodium hydroxyethyl diethylphosphonate,
5 wt% to 20 wt% surfactant,
The composition according to any one of claims 1 to 8 , characterized in that it comprises 2% to 20% by weight of basifying agent and 5% to 15% by weight of alkaline buffer. The organophosphorus or organosulfur toxic agents and / or contaminants to a process for the decontamination, the toxic and / or contaminants, contacting a composition according to any one of claims 1 9 Including the process. A process for obtaining a decontamination composition according to any one of claims 1 to 9 , comprising the following successive steps:
a) obtaining a composition comprising perpropionic acid, dipicolinic acid and hydroxyethylidene diphosphonic acid;
b) dissolving the composition obtained in step a) in an aqueous composition comprising a surfactant comprising an amine oxide and a basifying agent. A process for obtaining a decontamination composition according to any one of claims 1 to 9 , comprising the following successive steps:
a) obtaining a composition comprising perpropionic acid and dipicolinic acid;
The composition obtained in b) step a), the comprising a surfactant, a basic agent, and a step of dissolving in an aqueous composition comprising hydroxyethylidene diphosphonic acid salts, the process. 13. A process according to claim 12, wherein the hydroxyethylidene diphosphonate is sodium hydroxyethylidene diphosphonate.