Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
  • B01D19/0418—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing P-atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D19/00—Degasification of liquids
  • B01D19/02—Foam dispersion or prevention
  • B01D19/04—Foam dispersion or prevention by addition of chemical substances
  • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
  • B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms

Definitions

• the present invention relates to the use of a mixture comprising a solvent and a substance having antifoam properties in aqueous formulations.
• the appearance of a more or less stable foam, in too large a quantity may cause difficulties during the manufacture and / or packaging of the formulations, causing a reduction in productivity at this stage (s) of production.
• Foam can also be a problem when it appears when using formulations. In this case, it can be the cause of tank overflows, difficulties during the application of the formulation with in particular a malfunction of the pumps used. The foam can also cause uncontrolled and significant variations in the viscosity of the formulation. Furthermore, in the case of cement formulations used in the field of construction materials or the exploitation of oil or gas deposits, the appearance of foam can be the cause of a drop in the performance of the formulation, drop in performance due to the presence of air bubbles trapped in the formulation during setting.
• the foaming phenomenon can be dangerous in applications related to platform cleaning. Indeed, not only can the platforms be made slippery, but also the appearance of foam in the well itself, during the cleaning operation of the latter before it goes into production, has the consequence of reducing the density in the well (by inclusion of air) and can, for example, lead to an uncontrolled eruption of oil if it is a blowout well.
• the use of substances having anti-foam properties has been developed. However, in many cases, said anti-foaming substances are not compounds soluble in an aqueous medium. So we can observe phenomena of incompatibility with the formulation, which may for example lead to demixing or precipitation, thereby limiting the effectiveness of such substances.
• Document WO 00/17266 describes an antifoaming mixture comprising 70% by weight of a solvent and 30% by weight of an antifoaming agent. This mixture has beneficial effects in the context of use in weakly basic compositions for washing gases, in particular for the elimination of toxic gases such as H 2 S or CO 2 . These mixtures prove to be interesting between anti-foam performance in these compositions. However, they are not advantageous in aqueous formulations which are desired to be homogeneous and / or sufficiently stable on storage, in the presence of certain compounds.
• the present invention relates to the use in an aqueous formulation, of a mixture comprising at least one solvent and at least one substance having antifoam properties in an aqueous medium; the solvent / substance weight ratio being between 99.95 / 0.05 and 90/10; said solvent being chosen from those for which in all or part of the above-mentioned weight ratio range, the mixture is homogeneous and from those for which the aqueous formulation comprising from 0.01 to 5% by weight of mixture, is homogeneous.
• Another subject of the invention consists of an aqueous formulation comprising from 0.01 to 5% by weight of a mixture comprising at least one solvent and at least one substance having anti-foaming properties in an aqueous medium; the solvent / substance weight ratio being between 99.95 / 0.05 and 90/10; said solvent being chosen from those for which in all or part of the above-mentioned weight ratio range, the mixture is homogeneous and from those for which the aqueous formulation comprising from 0.01 to 5% by weight of mixture, is homogeneous.
• This mixture provides a solution to the foaming problem appearing during the manufacture, dilution and use of the formulation. It has in fact been found completely unexpectedly that the use of this type of mixture makes it possible to destabilize the foam which has appeared while the content of anti-foam agent in the formulation is low.
• the first level is that of performance achieved.
• the anti-foaming substance is not compatible with the aqueous formulation, it has been observed, for identical concentrations (1% by weight of the formulation), that the defoaming or anti-foaming phenomenon was more important for formulations.
• aqueous comprising the above mixture only for aqueous formulations comprising only the solvent or only the antifoam substance. It is specified that an aqueous formulation comprising 1% of anti-foaming substance which is not compatible with an aqueous medium, is of course not stable over time. Consequently, if the concentrated formulation is diluted immediately after its preparation, the antifoaming effect is clearly observed.
• the second level is that of the content of anti-foam substance present in the aqueous formulation.
• the results obtained with the mixture used in the context of the invention were achieved with levels of anti-foam substance of the order of 0.01% in the formulation, or even less.
• the formulation comprising the mixture according to the invention, whether in diluted form or not, is stable on storage, unlike formulations comprising contents of the order of 1% of anti-foam substance.
• mixture will be used for the association of the solvent and the antifoam substance used in the context of the invention.
• the mixture used according to the invention comprises at least one solvent, and at least one substance having antifoaming properties in an aqueous medium, the solvent / substance weight ratio being between 99.95 / 0, 05 and 90/10. This ratio is preferably between 99.95 / 0.05 and 95/5, even more preferably between 99.95 / 05 and 98/2.
• the solvent is chosen from those for which, in all or part of the above-mentioned weight ratio range, the mixture is homogeneous.
• the solvent is chosen from those for which the aqueous formulation comprising from 0.01 to 5% by weight of mixture, is homogeneous.
• homogeneous means that no decantation or macroscopic phase separation is observed, either of the solvent / antifoam mixture, or of the mixture / aqueous formulation as a whole, at 20 ° C., one hour after being put in place. contact.
• the esters of saturated or unsaturated, linear or branched mono- or dicarboxylic acids comprising 2 to 15 carbon atoms, optionally comprising an alkoxy group, preferably methoxy or hydroxyl, and monoalcohol or polyol, saturated or unsaturated, linear or branched, comprising 1 to 13 carbon atoms; - the mono-, di- and / or tri-ester phosphates for which the radical or radicals, identical or different, are alkyl radicals, linear or branched, carrying 2 to 12 carbon atoms; ketones for which the radicals, identical or different, are alkyl radicals, linear or branched, comprising 1 to 5 carbon atoms; - heterocyclic derivatives comprising at least one nitrogen and / or at least one oxygen and / or at least one sulfur; mono- or polyethers of polyalcohols; alone or as a mixture.
• esters of carboxylic acids are more particularly chosen from esters of acetic, caprylic, octanoic, decanoic, dodecanoic, lauric, lauroleic acids, alone or in mixtures.
• the acid is a dicarboxylic acid
• the two carboxylic functions are found in esterified form.
• the alcohol from which the ester is formed is preferably a monoalcohol.
• triglycerides of animal or preferably vegetable origin.
• suitable triglycerides include peanut oil, cottonseed oil, linseed oil, olive oil, palm oil, grape seed oil, soybean oil, castor oil, rapeseed oil, coconut oil, coconut oil.
• n in which R, which may or may not be identical, represent a hydrocarbon radical, linear or not, saturated or unsaturated, with C1-C18, preferably with C2-C12; n is an integer between 1 and 3;
• M which may or may not be identical, represent a hydrogen atom, an alkali, alkaline-earth metal, a radical of type N (R ') 4 + for which the radicals R', identical or different, represent a hydrogen atom or a C1-C6 hydrocarbon radical, linear or not, saturated or unsaturated, optionally substituted by a hydroxyl group.
• ketones mention may be made of acetone, methyl ethyl ketone, methyl isobutyl ketone, alone or as a mixture.
• N-methyl pyrrolidone As regards heterocyclic derivatives comprising at least one nitrogen and / or oxygen and / or sulfur, N-methyl pyrrolidone, tetrahydrofuran, dioxane, etc. are particularly suitable. ; N-methyl pyrrolidone being preferred.
• the mono- or polyethers of polyalcohols are preferably such that the ether part (s) comprise one or more alkyl radicals comprising from 1 to 4 carbon atoms.
• the part deriving from the polyalcohol is preferably of the polyethylene glycol type.
• methyldiglycol can be used.
• the solvent used is chosen from esters of mono- or dicarboxylic acids or heterocyclic derivatives.
• the substance having anti-foaming properties in an aqueous medium can be chosen from all the compounds having this type of properties.
• said substance is chosen from silicones. More particularly, said silicone substances can comprise, in addition to silicon, oxygen, carbon and hydrogen atoms, halogen atoms or nitrogen atoms.
• the silicone substances used are chosen from those comprising or consisting of units of formula R ' 3-a R a SiO ⁇ / 2 and R 2 SiO 2/2 formulas where
• - a is an integer from 0 to 3
• radicals R are identical or different and represent .
• a polar organic group bonded to silicon by an Si-C or Si-O-C bond bonded to silicon by an Si-C or Si-O-C bond
• an aromatic hydrocarbon group containing from 6 to 13 carbon atoms - the radicals R 'are identical or different and represent. an OH group
• an alkoxy or alkenyloxy group containing from 1 to 10 carbon atoms containing from 1 to 10 carbon atoms; . an aryloxy group containing from 6 to 13 carbon atoms; . an acyloxy group containing from 1 to 13 carbon atoms; . a ketiminoxy group containing from 1 to 8 carbon atoms;
• alkyls such as methyl, ethyl, octyl, trifluoropropyl.
• alkoxyalkylene such as -CH 2 -CH 2 -O-CH 3 ; -CH 2 -CH 2 -O-CH 3
• alkenyls such as vinyl, alkyl, hexenyl, decenyl, decadienyl.
• aryls such as phenyl.
• polar organic groups R there may be mentioned the groups:
• hydroxyfunctional such as - (CH 2 ) 3 -OH; - (CH 2 ) 4 N (CH 2 CH 2 OH) 2 ; - (CH 2 ) 3 -N (CH 2 CH 2 OH) -CH 2 -CH 2 -N (CH 2 CH 2 OH) 2 .
• aminofunctional such as - (CH 2 ) 3 -NH 2 : - (CH 2 ) 3 -NH- (CH 2 ) 2 NH 2 .
• amidofunctional such as - (CH 2 ) 3 -N- (COCH 3 ) - (CH 2 ) 2 NH (COCH 3 ).
• carboxyfunctional such as -CH 2 -CH 2 -S-CH 2 -COOH.
• oils, gums or resins contain reactive and / or polar R radicals (such as H, vinyl, allyl, hexenyl, aminoalkyls), the latter generally do not represent more than 2% by weight of the oil or gum and not more than 10% of the weight of the resin.
• Polydimethylsiloxane and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxane oils as well as polydimethylsiloxane, polyphenylmethylsiloxane and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxane gums are well known commercial products.
• the viscous resins polymethylsiloxanes DT containing from 1 to 2% by weight of silanol functions are also commercial products.
• the silicone substances can comprise at least one filler, in particular mineral.
• the compositions are called compounds.
• the silicone substance / filler proportions range in particular from 2 to 15, preferably from 2 to 10.
• the mineral filler is preferably silica.
• It can be precipitation silica or combustion silica, treated or not.
• the precipitation silica is preferably prehydrophobic by conventional treatment with one or more organosilicon compounds. It can also be incorporated untreated, then treated (hydrophobic) in situ with one or more organosilicon compounds.
• organosilicon compounds include methylpolysiloxanes such as hexamethyldisiloxane, octamethylcyclotetrasiloxane, methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, chlorosilanesethyl dimethyl dichlorosilane, dimethyl dimethyl dichlorosilane, dimethyl dichlorosilane .
• the silicas can increase their starting weight up to a rate of 20%.
• Combustion silica can be used untreated. If necessary, however, it can be treated as precipitated silica. It is also possible to use, in addition to or instead of siliceous fillers, other mineral fillers such as ground quartz, calcined clays and diatomaceous earth.
• the mineral fillers generally have a specific surface, measured according to BET methods, of at least 50 m 2 / g, in particular between 50 and 400 m / g, preferably greater than 70 m 2 / g, an average particle size. less than 0.1 micrometer ( ⁇ m) and an apparent density less than 200 g / liter.
• the silicone substance can comprise at least one surfactant, preferably nonionic.
• nonionic surfactants there may be mentioned, for example:
• alkoxylated mono-, di- and tri-glycerides alkoxylated fatty acids, more particularly comprising from 6 to 22 carbon atoms; alkoxylated sorbitan esters, in particular fatty acid cyclized sorbitol esters comprising from 10 to 20 carbon atoms; alkoxylated fatty amines, more particularly comprising from 6 to 22 carbon atoms; - Alkoxylated alkylphenols, more particularly comprising one or two alkyl groups, linear or branched, having 4 to 12 carbon atoms;
• the surfactant is present, its content is advantageously from 5 to 10% by weight relative to the weight of the silicone substance and, where appropriate, of filler.
• the substance having anti-foaming properties is chosen from perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl phosphoric acids, or their alkali metal or ammonium salts. More particularly, the alkyl radicals contain 6 to 18 carbon atoms.
• the salts can be alkali metal salts, such as sodium, potassium, but also ammonium salts of formula NR_t + ; formula in which R, identical or different, represent a hydrogen atom, an alkyl radical comprising 1 to 18 carbon atoms, optionally carrying at least one hydroxyl or amino group, optionally ethoxylated.
• the solvent / substance weight ratio is between 99.95 / 0.05 and 90/10, preferably between 99.8 / 0.2 and 98/2.
• the aqueous formulation comprises 0.01 to 5% by weight of mixture (solvent / substance), preferably 0.1 to 2% by weight of the aqueous formulation. It should be noted that, depending on the fields of application, the aqueous formulations can be used either as such or after dilution.
• Aqueous formulations comprising the mixture described above can have many applications.
• these formulations can be used in the field of the exploitation of oil or gas deposits, as cementing fluid, as drilling fluid, or even fracturing fluid.
• Drilling fluids are conventionally fluids whose rheological properties are of shear thinning type.
• the fluids include polysaccharides such as galactomannans, such as guar; natural or chemically modified xanthan gum (deacetylated and / or depyruvially partially or totally) or xanthan gum obtained after genetic modification of the strain which produces it.
• polysaccharides such as galactomannans, such as guar
• natural or chemically modified xanthan gum deacetylated and / or depyruvially partially or totally
• xanthan gum obtained after genetic modification of the strain which produces it.
• the polysaccharide content is usually between 0.01 and 2% by weight relative to the total weight of the drilling fluid.
• the drilling fluid further comprises salts which are soluble or at least partially soluble in the fluid, mineral and possibly organic acids.
• salts of mineral acids there may be mentioned the halides of alkali or alkaline-earth metals, such as chloride, sodium, potassium or magnesium bromide. It is also possible to use sulfates, carbonates, bicarbonates, silicates, phosphates of alkali or alkaline earth metals, alone or as a mixture.
• salts of organic acids mention may be made especially of the formates of alkali or alkaline earth metals, the acetates of alkali or alkaline earth metals.
• the salt content is more particularly between 5000 and 110,000 ppm.
• the drilling fluid may also include a filtrate reducer or a filtrate control.
• a filtrate reducer or a filtrate control.
• cellulosic compounds in particular carboxymethylcelluloses, hydroxyethylcelluloses
• polyacrylamides in particular polyacrylamides
• high molecular weight polyacrylates succinoglycans, native starch or its derivatives, carbon.
• the quantity of filtrate reducer strongly depends on the nature of the rocks crossed while remaining non-penalizing because these compounds have for the most part a Newtonian rheological profile. As an indication, the quantity of filtrate reducer is less than or equal to 1% relative to the total weight of the fluid.
• Drilling fluids can also comprise fluidifying or dispersing agents, such as polyphosphates, tannins, lignosulfonates, lignin derivatives, peat and lignites, polynaphthalene sulfonates, alone or as a mixture.
• fluidifying or dispersing agents such as polyphosphates, tannins, lignosulfonates, lignin derivatives, peat and lignites, polynaphthalene sulfonates, alone or as a mixture.
• the amount of fluidizing or dispersing agent is variable but generally remains less than or equal to 1% relative to the total weight of the fluid.
• the drilling fluid according to the invention can also comprise an oxygen sensor in order to avoid any degradation of certain additives.
• oxygen sensor for example, hydroxylamines, hydrazine, sulfites, bisulfites, hydrosulfites, borohydrides, are suitable oxygen scavengers.
• the drilling fluid further comprises a weighting compound and / or at least one mineral colloid.
• the weighting elements help maintain sufficient hydrostatic pressure in the well and keep the entrained rocks in suspension during the drilling operation.
• Such compounds are conventionally chosen from the above-mentioned soluble salts and the sparingly or very sparingly soluble salts, such as sulphates, silicates or carbonates of alkaline earth metals, of the type of barium sulphate, of calcium carbonate. It is likewise possible to use bromides of alkaline earth metals or of zinc such as potassium bromide, zinc bromide.
• Mineral colloids which are compounds that are substantially insoluble under the conditions of use of the fluid, are agents which modify the rheology of the medium and make it possible to keep the cuttings in suspension in the latter. Attapulgite, baryte, bentonite, alone or as a mixture, are the most common examples.
• additives can be used such as mineral salts favoring the precipitation of divalent ions, compounds limiting the swelling of clays, free radical transfer agents, biocides, anti-corrosion agents, etc.
• these include a hydraulic binder
• the compounds capable of reacting and hardening when in the presence of water can be used, are conventionally compounds based on silicon, aluminum, calcium, oxygen and / or sulfur.
• compounds based on calcium silicate (Portland cement), pozzolan, gypsum, hydraulic binders with high aluminum content, hydraulic binders based on phosphate and hydraulic binders based on calcium silicate are preferred.
• the cementing fluid may include the additives conventional in the field, such as, for example, filtrate reducing agents, retarding agents or setting accelerators, dispersing agents, rheology modifiers, thickening agents, entraining agents. air, agents preventing gas migration, etc.
• the total content of these additives when present, does not exceed 30% by weight of the hydraulic binder.
• the cementing fluid may further include fillers.
• mineral fillers which may be used, mention may be made of calcium carbonate, fly ash, silica, silica smoke, clays
• organic filler it is possible in particular to use expanded polystyrene.
• the average size of mineral fillers is less than or equal to 120 ⁇ m. preferably less than or equal to 80 ⁇ m.
• fillers in the cement when present, varies according to the subsequent applications for which the cement is intended. Similarly, depending on whether one wishes to densify or lighten the latter, one can use mineral or organic fillers. Again, without intending to be limited thereto, the filler content represents at most the same weight as the hydraulic binder.
• the cementing fluid may comprise reinforcing fibers, long or short. These fibers can be either metallic or polymeric.
• the polymeric fibers are fibers of polyamide, polyvinyl alcohol, polyethylene, polypropylene, etc.
• the size of the reinforcing fibers can vary within a wide range. By way of example, the size can vary between a few tenths of a millimeter to several tens of millimeters.
• the content of the fluid in these fibers it can be easily evaluated by a person skilled in the art. It is usually less than or equal to 10% compared to the hydraulic binder.
• compositions of cements, mortar, concrete, etc. intended for the building materials industry can likewise comprise the mixture according to the invention.
• compositions are of the same type as those which have just been described above, in the context of the cementing of wells. They can also include granular elements which are usually chosen from sand, silicon dioxide, titanium, alumina, talc, mica,
• (meta) kaolin bentonite, clinker, vermiculite, perlite, cellulose, slag. he can be synthetic products, crystallized or amorphous, obtained for example by grinding, and sieving to the desired size.
• the particle size distribution of the granular elements can vary widely depending on the intended application.
• the size of the granular elements can vary for example between 1 and 500 ⁇ m.
• the aqueous formulations comprising the mixture can be used in the paper industry. They can in particular be used as a paper coating bath
• the formulations include fillers of the pigment type. They can be mineral pigments such as kaolin, white satin, talc, calcium carbonate, titanium oxide, among others, or even plastic pigments.
• the formulation also comprises binders, whether these are of the natural type, such as starches, or synthetic, such as latexes.
• the latexes are obtained from unsaturated monomers such as vinyl, acrylic, vinyl aromatic monomers, vinyl esters, alkyl esters of unsaturated acids, esters of unsaturated carboxylic acids, vinyl chloride, vinylidene chloride and / or dienes.
• unsaturated monomers such as vinyl, acrylic, vinyl aromatic monomers, vinyl esters, alkyl esters of unsaturated acids, esters of unsaturated carboxylic acids, vinyl chloride, vinylidene chloride and / or dienes.
• suitable latexes mention may be made of styrene / butadiene, styrene / acrylate, styrene / butadiene / acrylate latexes, etc.
• the binders are present in an amount of 5 to 25 parts by weight per 100 parts by weight of pigments.
• the formulations may likewise comprise an optical brightener, in a content of 0.1 to 0.7 parts by weight, preferably combined with an optical brightener support such as polyvinyl alcohol with a content usually between 0.2 and 2 parts by weight.
• an optical brightener support such as polyvinyl alcohol with a content usually between 0.2 and 2 parts by weight.
• the formulations preferably include a thickening agent.
• a thickening agent Such compounds make it possible to control the rheology of the formulation. They may be alkali-soluble copolymers comprising a combination of several monomers such as ethylenically unsaturated carboxylated compounds, nonionic vinyl monomers and ethylenically unsaturated amphiphilic monomers and monomers.
• the formulations can also include slip agents such as calcium stearate, as well as insolubilizing agents.
• slip agents such as calcium stearate, as well as insolubilizing agents.
• the dry matter content of the formulation is 60 to
• compositions for coating bath can also comprise resins such as epoxy resins, being in the form of emulsion.
• These resins can in particular be chosen from aromatic epoxy resins of the Novolak type, epoxy resins of the bisphenol-A type.
• the emulsions further comprise a nonionic surfactant, such as polyethylene and / or polypropylene oxides, polyethylene and / or polypropylene glycol alkylaromatic ethers, polyoxyalkylene derivatives of hexitol including sorbitans and mannitans.
• a nonionic surfactant such as polyethylene and / or polypropylene oxides, polyethylene and / or polypropylene glycol alkylaromatic ethers, polyoxyalkylene derivatives of hexitol including sorbitans and mannitans.
• the mixture according to the invention can likewise be used in formulations intended to make laminated compounds, formulations in which melamine-formaldehyde or urea-formaldehyde resins are present; as well as in adhesive composition formulations.
• aqueous formulations comprising the solvent / substance mixture can likewise be used in the field of deformation or transformation of metals, such as in particular the drawing operations, rolling, for the deformation, and the cutting works for the transformation.
• aqueous formulations conventionally used are presented in a concentrated form which the user dilutes before carrying out the work of the metal.
• the solvent / substance mixture can be used in aqueous formulations of this type.
• carboxylic acids saturated or unsaturated, comprising at least 5 carbon atoms. More particularly, these acids are chosen from mono- or polycarboxylic acids, saturated or unsaturated, comprising 5 to 40 carbon atoms.
• these acids may optionally be in a form neutralized by a mineral base (hydroxides, hydroxycarbonates, (bi) carbonates, etc. of alkali metal, ammonia) or organic (primary, secondary or tertiary amines, optionally substituted by one or several OH or alkoxylated radicals)
• the formulations can likewise comprise acid phosphate esters, having at least one aliphatic, cycloaliphatic or aromatic hydrocarbon radical, saturated or unsaturated, containing 1 to 30 carbon atoms, optionally polyalkoxylated (polyoxyethylenated and / or polyoxypropylenated).
• the formulations can optionally include a nonionic surfactant, at a rate of 5% maximum relative to the total weight of the formulation after dilution, such as polyalkoxlated alkylphenols, polyalkoxlated C8-C22 aliphatic alcohols, polyalkoxlated triglycerides, etc.) .
• the aqueous formulations can also be used in the field of cleaning and / or degreasing surfaces.
• surface cleaning is meant both the cleaning of textiles (detergents) and the cleaning of hard surfaces, in particular crockery, household surfaces, and industrial surfaces.
• the formulations for cleaning textile surfaces can be detergents for hand or machine washing.
• the formulations for cleaning the dishes can be products for the dishes by hand or machine. In these formulations, it is often desired to control foaming. Furthermore, there is a strong interest in homogeneous, even transparent formulations.
• the aqueous degreasing formulations of the metal sheets are preferably alkaline formulations.
• the mixture content during the use of these formulations is of the order of 0.01 to 5 g / l.
• aqueous formulation On the order of 0 to 2%, generally 0.01 to 1% by weight (in the aqueous formulation) of at least one anionic or non-ionic detergent surfactant such as (C8-C- ) alkyl 5) benzene sulfonates, alkyls (C8-C2 ⁇ ) s u ⁇ ates, ethoxylated alkylphenols, ethoxylated fatty alcohols, block polymers of ethylene oxide and propylene oxide,
• anionic or non-ionic detergent surfactant such as (C8-C- ) alkyl 5) benzene sulfonates, alkyls (C8-C2 ⁇ ) s u ⁇ ates, ethoxylated alkylphenols, ethoxylated fatty alcohols, block polymers of ethylene oxide and propylene oxide,
• benzenesulfonates - of the order of 5 to 20% by weight (in the aqueous formulation) of at least one hydrotropic electrolyte such as benzenesulfonates, mono- or di-alkyl (C-
• hydrotropic electrolyte such as benzenesulfonates, mono- or di-alkyl (C-
• hydrotropic agents such as alccols and glycols
• nitriloacetic acid ethylenediamine tetraacetic acid, ethylenediamine tetramethylphosphonic acid, nitrilotrimethylene phosphonic acid or their salts
• sequestering agent such as nitriloacetic acid, ethylenediamine tetraacetic acid, ethylenediamine tetramethylphosphonic acid, nitrilotrimethylene phosphonic acid or their salts
• buffering agents such as alkalolamines, ethylenediamine ...
• the aqueous formulations comprise of the order of 0.005 to 0.05 g / l, preferably of the order of 0.015 to 0.025 g / l of the formulation (after dilution) in mixture.
• the aqueous compositions used for degreasing petroleum platforms can comprise, in addition to the solvent / substance mixture: - On the order of 0 to 2%, generally 0.01 to 1% by weight (in the aqueous formulation) of at least one anionic or non-ionic detergent surfactant such as (C8-C-) alkyl g) benzene sulfonates, alkyl (C8-C2 ⁇ ) s ulfates, ethoxylated alkylphenols, ethoxylated fatty alcohols, block polymers of ethylene oxide and propylene oxide,
• anionic or non-ionic detergent surfactant such as (C8-C-) alkyl g) benzene sulfonates, alkyl (C8-C2 ⁇ ) s ulfates, ethoxylated alkylphenols, ethoxylated fatty alcohols, block polymers of ethylene oxide and propylene oxide,
• benzenesulfonates - of the order of 5 to 20% by weight (in the aqueous formulation) of at least one hydrotropic electrolyte such as benzenesulfonates, mono- or di-alkyl (C-
• hydrotropic electrolyte such as benzenesulfonates, mono- or di-alkyl (C-
• hydrotropic agents such as alcohols and glycols
• agent controlling the pH such as, for example, carbonates, sesquicarbonates, bicarbonates of alkali metals,
• additives such as enzymes in amounts up to 5% of the total weight of the aqueous fluid, agents that inhibit corrosion of metals.
• aqueous formulations used for cleaning oil wells include, in addition to the mixture:
• anionic surfactants alkyl esters sulfonates, alkyl sulfates, salts of fatty acids C8-C24, saturated or not, alkylbenzenesulfonates Cg-C20. ' Es alkylsulfonates, etc.
• non surfactants ionic polyoxyalkylenated alkylphenols, polyoxyalkylenated C8-C22 aliphatic alcohols, products resulting from the condensation of ethylene oxide the compound resulting from the condensation of propylene oxide with propylene glycol, etc.
• an agent making it possible to adjust the pH such as, for example, carbonates, sesquicarbonates, bicarbonates of alkali metals, hydroxides of alkali or alkaline earth metals,
• additives such as enzymes in quantities of up to 5% of the total weight of the aqueous fluid, agents that inhibit corrosion of metals,
• weighting agents so as to maintain a satisfactory hydrostatic pressure in the well.
• aqueous formulations such as polysaccharides of plant origin, such as polygalactomannans and their derivatives, such as guar, hydroxypropylguar; cellulose and its derivatives, starches and its derivatives; polysaccharides of bacterial origin such as xanthan gum or deacetylated derivatives.
• the aqueous formulations can also be used in the field of water-based paints, or coatings.
• the paints in addition to the mixture according to the invention, generally comprise a binder and at least one additional component chosen from fillers, pigments, surfactants, thickening agents, antioxidants, natural binders, dispersing agents, biocides, etc.
• the binders are latexes prepared from unsaturated ethylenic monomers.
• suitable monomers special mention may be made of styrene, butadiene, acrylic esters and vinyl nitriles.
• the particle size of the latexes is more particularly between 100 and 500 nm.
• the latex with a nanolatex whose size is between 5 and 40 nm.
• nanolatexes can be homopolymers or copolymers containing units derived from vinyl, acrylic, vinylaromatic monomers, vinyl esters, alkyl esters of unsaturated acids, esters of unsaturated carboxylic acids, vinyl chloride, chloride vinylidene and / or dienes.
• the latex binder is preferably neutralized with a base (for example ammonia or amine).
• the composition also comprises pigments such as zinc and titanium dioxides, zinc sulfides, iron oxides, molybdates or chromates, etc.
• It can likewise include calcium carbonate, talc, baryte, silica, mica, diatomaceous earth, etc.
• the content of these compounds is determined in a conventional manner in the field, so as to obtain both good covering properties and good mechanical properties. As an indication, their content varies between 10 and 50% by volume.
• the aqueous formulations can be intended for the treatment of plants.
• the formulations are in the form of concentrated solutions.
• They also comprise at least one phytosanitary active material, soluble and stable (that is to say not substantially hydrolyzing) in an aqueous medium, at the chosen concentration.
• the concentration of active material (s) in the formulation is less than or equal to 540 g / l expressed relative to the active material, more particularly between 100 and 540 g / l, preferably between 100 and 500 g / l. It should be noted that when the active material is in salified form, the ranges which have just been indicated are expressed relative to the active material in non-salified form.
• the phytosanitary active ingredients are chosen from hydrophilic pesticides, and more especially herbicides, but also hydrophilic nutritive elements promoting the growth and development of plants.
• said active materials are in the form of organic or inorganic salts.
• herbicidal active ingredients in the form of organic or inorganic salts: the aminophosphate or aminophosphonate derivatives, Acifluorfen, Asulam, Bentazon, Bialaphos, Bispyribac, Bromacil, Bromoxynil, Chloramben, Clopyralid, 2, 4-D, 2,4-Db, Dalapon, Dicamba, Dichlorprop, Difenzoquat, Diquat, Endothall, Fenac, Fomesafen, Fosamine, loxynil, MCPA, MCPB, Mecoprop, Methylarsonic Acid, Naptalam, Paraquat, Picloram, Sulfamic Acid, alone or in mixture.
• the aminophosphate or aminophosphonate derivatives Acifluorfen, Asulam, Bentazon, Bialaphos, Bispyribac, Bromacil, Bromoxynil, Chloramben, Clopyralid, 2, 4-D, 2,4-Db, Dalapon
• the active material is chosen from aminophosphate or aminophosphonate derivatives, in the form of organic or inorganic salts, such as glyphosate, sulphosate, glufosinate, in the form of organic or inorganic salts.
• aminophosphate or aminophosphonate derivatives in the form of organic or inorganic salts, such as glyphosate, sulphosate, glufosinate, in the form of organic or inorganic salts.
• glyphosate is meant more particularly N-phosphonomethylglycine as well as any derivative thereof leading in aqueous solution to glyphosate anions.
• suitable salts of the alkali metal salts such as sodium or potassium; ammonium salts, of type N (R) 4 + for which the radicals R, identical or different, represent a hydrogen atom or a hydrocarbon radical in Ci-Ce, linear or not, saturated or not, optionally substituted by a hydroxyl group; or alternatively the sulfonium salts; said salts being present alone or in combination.
• ammonium salts that may be mentioned very particularly, secondary or primary amines such as isopropylamine, dimethylamine or diamines such as ethylenediamine; amines carrying a hydroxyl group such as monoethanolamine.
• secondary or primary amines such as isopropylamine, dimethylamine or diamines such as ethylenediamine; amines carrying a hydroxyl group such as monoethanolamine.
• sulfonium salts trimethylsulfonium is perfectly suitable.
• the isopropylamine salt and the trimethylsulfonium salt are preferably metal salts such as zinc, iron, and preferably manganese. These salts are used in the form of EDTA type chelates for example or of sulfates.
• the phytosanitary formulation comprises at least one biological activator of the phytosanitary active ingredient.
• polyalkoxylated amines more especially comprising at least one hydrocarbon radical having from 4 to 30 carbon atoms
• polyethoxylates polyalkoxylated amidoamines (for example polyethoxylated or polyethoxylated / polypropoxylated).
• polyalkoxylated phosphate mono- and diesters for example polyethoxylated or polyethoxylated / polypropoxylated
• aliphatic hydrocarbon alcohols linear or not, saturated or unsaturated, more particularly comprising 4 to 30 carbon atoms, or aromatic alcohols ( more particularly those for which the aromatic nucleus comprises 6 carbon atoms) optionally comprising one or more substituents on the aromatic nucleus, chosen from alkyl, alkenyl radicals, comprising up to 30 carbon atoms, or chosen from alkylaryl radicals for which the alkyl part, linear or not, comprises 1 to 10 carbon atoms and the aryl part comprises 6 carbon atoms;
• the counterion is generally chosen from alkali metals, such as sodium, potassium, ammonium ions of NR4 + type with R, identical or not, representing a hydrogen atom, an alkyl radical comprising 1 to 10 carbon atoms, preferably 1 to 4, optionally carrying a hydroxyl radical.
• mineral salts soluble in the aqueous phase such as for example the alkali metal salts, such as sodium, potassium, or ammonium of the compounds chosen from carbonates; bicarbonates; halides, such as chlorides, fluorides; nitrates, phosphates; hydrogen phosphates; sulfates; bisulfates; bisulfites, alone or as a mixture.
• alkali metal salts such as sodium, potassium, or ammonium of the compounds chosen from carbonates; bicarbonates; halides, such as chlorides, fluorides; nitrates, phosphates; hydrogen phosphates; sulfates; bisulfates; bisulfites, alone or as a mixture.
• the activators which have just been mentioned can be used alone or in mixtures.
• the amount of biological activator generally represents 10 to 70% by weight relative to the phytosanitary active ingredient (s), preferably between 20 and 60% by weight.
• a last object of the invention consists of an aqueous formulation comprising from 0.01 to 5% by weight of a mixture comprising at least one solvent and at least one substance having antifoam properties in an aqueous medium; the solvent / substance weight ratio being between 99.95 / 0.05 and 90/10; said solvent being chosen from those for which in all or part of the weight ratio range above, the mixture is homogeneous and among those for which the aqueous formulation comprising from 0.01 to 5% by weight of mixture, is homogeneous.
• formulations include the usual additives, depending on the fields in which they are used. Again, reference may be made to the appropriate passages in the description.
• a phytosanitary formulation comprising glyphosate in the form of an isopropylamine salt, and the glyphosate concentration of which is 360 g / l expressed in acid equivalent, by mixing with stirring of the following compounds:
• the foam test is carried out on the formulation described above, without adding anti-foaming / defoaming agent.
• the test according to the invention is a formulation as described above comprising 1% of a 99/1 weight mixture of Phytorob® 810.01 respectively (comprising a mixture of methyl esters of C ⁇ -C-10 and sold by the Novance) and Rhodorsil® 481 (marketed by Rhodia Chimie).
• the formulation obtained is clear and stable on storage.
• Such a mixture is sold in particular by the company Rhodia under the name Geronol CF / AR.
• the foam test (CIPAC MT 47, foam persistence, Cipac Handbook F page 152) is as follows:
• 0.5 ml of the composition to be tested is added to a graduated cylinder with 50 ml of water (Cipac D water); The test piece is capped and 30 complete reversals are carried out, leaving the air bubble to rise at the top at each reversal.
• the sample is uncorked and the volume of foam is measured at 10 seconds, 1 minute, 3 minutes and 12 minutes.
• a formulation comprising 1% of Rhodorsil® 481, without solvent, is cloudy and is not stable on storage.
• a formulation comprising 1% of Phytorob® 810.01, without Rhodorsil® 481, is clear, stable on storage. On the other hand, the level of defoaming is much lower than that reached with the mixture according to the invention.

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• Life Sciences & Earth Sciences (AREA)
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• 2003
  • 2003-02-06 EP EP20030717378 patent/EP1471984A2/de not_active Withdrawn
  • 2003-02-06 US US10/503,805 patent/US20050164884A1/en not_active Abandoned
  • 2003-02-06 WO PCT/FR2003/000376 patent/WO2003065803A2/fr not_active Application Discontinuation
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