EP0577525B1 - Stable aqueous zeolite suspensions, their fabrication process and use - Google Patents
Stable aqueous zeolite suspensions, their fabrication process and use Download PDFInfo
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- EP0577525B1 EP0577525B1 EP93420238A EP93420238A EP0577525B1 EP 0577525 B1 EP0577525 B1 EP 0577525B1 EP 93420238 A EP93420238 A EP 93420238A EP 93420238 A EP93420238 A EP 93420238A EP 0577525 B1 EP0577525 B1 EP 0577525B1
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- acrylic
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- zeolites
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Definitions
- the present invention relates to fluid and stable aqueous suspensions of silico-aluminates also called zeolites.
- Zeolites are today more and more used in the formulations of detergent compositions to replace the polyphosphates which are responsible, during their rejection in the natural environment, for the eutrophication phenomena of lakes and rivers.
- these zeolites are increasingly used in the form of an aqueous suspension of approximately 50% in anhydrous zeolite. These suspensions must then be usable industrially, that is to say pumpable after their transport from the place of production to the place of use and / or after their storage for several days before use.
- one of the objects of the invention is a fluid suspension which is stable and stable over time, containing, in addition to one or more zeolites, natural or synthetic and water, a non-crosslinked water-soluble stabilizing agent, an acrylic copolymer comprising as monomeric unit at least one acrylic monomer with carboxylic function, at least one acrylic and / or vinyl monomer without carboxylic function and at least one oxyalkylated monomer with ethylenic unsaturation and terminated by a hydrophobic fatty chain.
- Another object of the invention is a process for obtaining said aqueous suspensions of zeolites, fluid and stable over time, by means of an addition of said non-crosslinked water-soluble stabilizing agent as well as the use as stabilizer of said non-crosslinkable water-soluble copolymer reticle.
- Another object of the invention is also the use of these aqueous suspensions of zeolites, comprising said stabilizing agent, in the field of detergency and as sequestering agent.
- the stabilizing agents mentioned are hydroxylated polymers derived from starch which prove effective but must be used in a large amount of between 0.4% and 2.5% by weight relative to the mass total suspension.
- Patent DE 3,021,295 describes a stable composition of zeolites containing 15% nitrilotriacetic acid in salified form, a product the discharges of which are today highly regulated, or even prohibited in certain countries.
- the patents FR 2 455 479 and FR 2 461 516 claim as a stabilizing agent polymers which have the drawback, that is to cause releases of ammonia in the strongly alkaline medium (pH 10 to 13) of the zeolites in the case of the patent FR 2,455,479, or not to ensure good stability during the preparation, storage and transport of the zeolite suspensions at temperatures between 50 ° C and 60 ° C (FR 2 461 516).
- This other solution also has the drawback of using excessively large amounts of stabilizing agent of the order of 0.4% by dry weight relative to the total weight of the suspension.
- R represents the polymerizable unsaturated radical, belonging to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as maleic, itaconic, vinylphthalic or even unsaturated urethanes such as, for example, acrylurethane, methacrylurethane, ⁇ - ⁇ dimethyl -m-isopropenylbenzylurethane, allylurethane or alternatively allyl ethers, acrylamide and methacrylamide substituted or not, vinyls.
- unsaturated urethanes such as, for example, acrylurethane, methacrylurethane, ⁇ - ⁇ dimethyl -m-isopropenylbenzylurethane, allylurethane or alternatively allyl ethers, acrylamide and methacrylamide substituted or not, vinyls.
- R ' represents the hydrophobic radical with a fatty chain such as linear or branched alkyl, alkylaryl, arylalkyl, aryl groups having from 12 to 40 carbon atoms and preferably from 26 to 40 carbon atoms.
- This copolymer used in the aqueous suspension of zeolites according to the invention, is obtained according to methods known to those skilled in the art by radical polymerization, in direct or reverse emulsion, in suspension or by precipitation in an appropriate solvent.
- This copolymer thus prepared makes it possible to obtain, according to the invention, a fluid and stable aqueous suspension of zeolites having an anhydrous zeolite content of approximately 50%.
- This suspension can be obtained by simple mixing of the water-soluble copolymer added to the aqueous suspension of non-stabilized zeolites.
- the aqueous suspension according to the invention is however often obtained during the process for manufacturing the zeolite itself, by reaction between the filter cake and the water-soluble copolymer added after the washing and filtration step.
- the aqueous suspension of zeolites according to the invention thus obtained by using up to 0.3% by dry weight of the water-soluble copolymer relative to the total weight of the suspension, then has an apparent Brookfield viscosity of less than 2,500 mPa.s (or cP) at 10 revolutions / minute (RPM) and 20 ° C and this even after 40 days of storage without shaking.
- Its tendency not to sediment as well as its ability to be pumped and handled can be expressed by measuring the height of the deposit at the bottom of the suspension after 4 days of storage at room temperature as well as that of the Brookfield viscosity after 40 days of storage at room temperature.
- the aqueous suspension of zeolites according to the invention also has the advantage of being purer than those of the prior art because the dose of stabilizing agent used is less and its complexing power is preserved which allows its use as sequestering agent.
- aqueous zeolite suspensions according to the invention allows their possible use in detergency without further transformation, by mixing with other detergent additives.
- the aqueous suspension of zeolites according to the invention is used in detergency in pulverulent form after drying, for example by spraying or atomization, it is then noted that the products obtained are free of dust.
- the Applicant uses in all of the tests the same aqueous suspension of type 4A zeolite containing 52.5% of dry matter.
- This suspension which is very fluid in appearance, when it is kept in agitation, sediments within a few hours, if it contains no stabilizing agent, and separates into two phases. One in a supernatant liquid and the other leading to a very hard sediment impossible to resuspend without powerful mechanical means.
- the zeolite particle sizes are between 1 and 10 ⁇ m and the suspension has an alkaline pH greater than 12.
- the suspension is divided into 240 g samples. Each fraction is kept in a 230 ml glass bottle fitted with an airtight metal lid.
- each bottle will be used for only one stabilization test.
- the contents of the pot are resuspended in a fluid and homogeneous suspension using a Rayneri-type stirring system before incorporating the stabilizing agent to be tested. Stirring is continued for 15 minutes so as to obtain an intimate mixture of the suspension to be stabilized and the agent tested.
- the rheology of the system is determined using a Brookfield type RVT viscometer equipped with a suitable module.
- the apparent viscosity To is measured at 20 ° C. Each reading is performed at 10 revolutions / minute and at 100 revolutions / minute after 2 minutes of rotation.
- the containers containing the suspension thus stabilized, fitted with their hermetic lids, are left to stand at room temperature for a static aging cycle of four days.
- the aqueous zeolite suspension is considered to be stable if the height of the deposit is less than or equal to 1 mm.
- the rheology of the system is determined by measuring the apparent viscosity of the suspension at 20 ° C, using a Brookfield viscometer type RVT equipped with the appropriate module. The readings are taken at 10 rpm and 100 rpm after two minutes of rotation and are noted T4J.
- the aqueous suspension is considered to be pumpable when the apparent viscosity measured at 10 revolutions / minute is less than or equal to 2500 mPa.s (cP).
- Suspension according to the prior art containing, as stabilizing agent, 0.3% by dry weight relative to the total mass of the suspension of an isotridecyl alcohol with 5 moles of ethylene oxide.
- Reading Table I shows that only the suspensions of tests No. 4, 5 and 6, according to the invention, after 4 days and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than or equal to 2500 mPa.s at 10 revolutions / minute and at 20 ° C as well as a deposit height less than or equal to 1 mm.
- T4J, T40J Brookfield viscosity
- aqueous zeolite suspensions are prepared with the same procedure as that of Example 1, from the same zeolite suspension, and with, as stabilizing agent, copolymers whose percentage of monomer (c) of general formula ( I) varies.
- Reading Table II shows that the suspensions of tests 8 to 15, according to the invention, after 4 and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than or equal to 2500 mPa.s at 10 revolutions / minute and 20 ° C, as well as a deposit height less than or equal to 1 mm.
- T4J, T40J Brookfield viscosity
- Reading Table III shows that the suspensions of tests No. 16 and 17, according to the invention, after 4 and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than 2500 mPa.s at 10 turns / minute and 20 ° C, as well as a deposit height less than or equal to 1 mm.
- T4J, T40J Brookfield viscosity
- aqueous zeolite suspensions are prepared with the same procedure as that of Example No. 1, from the same zeolite suspension and with, as stabilizing agent, copolymers including the hydrophobic chain R 'of the monomer (C) of general formula (I) varies in number of carbon atoms.
- Reading Table IV shows that the suspensions of tests n ° 18 to n ° 24, according to the invention, after 4 and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than or equal to 2500 mPa. s at 10 revolutions / minute and 20 ° C, as well as a deposit height less than or equal to 1 mm.
- T4J, T40J Brookfield viscosity
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
La présente invention concerne des suspensions aqueuses fluides et stables de silico-aluminates encore appelées zéolithes.The present invention relates to fluid and stable aqueous suspensions of silico-aluminates also called zeolites.
Les zéolithes sont aujourd'hui de plus en plus utilisées dans les formulations de compositions détergentes pour remplacer les polyphosphates qui sont responsables, lors de leur rejet dans le milieu naturel, des phénomènes d'eutrophisation des lacs et des rivières.Zeolites are today more and more used in the formulations of detergent compositions to replace the polyphosphates which are responsible, during their rejection in the natural environment, for the eutrophication phenomena of lakes and rivers.
Or, pour faciliter leur mise en oeuvre au moment de la fabrication des compositions détergentes, ces zéolithes sont de plus en plus employées sous forme de suspension aqueuse à environ 50% en zéolithe anhydre. Ces suspensions doivent alors être utilisables industriellement c'est-à-dire pompables après leur transport du lieu de production au lieu d'utilisation et/ou après leur stockage pendant plusieurs jours avant utilisation.However, to facilitate their use at the time of the manufacture of the detergent compositions, these zeolites are increasingly used in the form of an aqueous suspension of approximately 50% in anhydrous zeolite. These suspensions must then be usable industrially, that is to say pumpable after their transport from the place of production to the place of use and / or after their storage for several days before use.
Ainsi, un des objets de l'invention est une suspension aqueuse fluide et stable dans le temps contenant, outre une ou plusieurs zéolithes, naturelles ou synthétiques et de l'eau, un agent de stabilisation hydrosoluble non réticulé, copolymère acrylique comprenant comme motif monomérique au moins un monomère acrylique à fonction carboxylique, au moins un monomère acrylique et/ou vinylique sans fonction carboxylique et au moins un monomère oxyalkylé à insaturation éthylénique et terminé par une chaîne grasse hydrophobe.Thus, one of the objects of the invention is a fluid suspension which is stable and stable over time, containing, in addition to one or more zeolites, natural or synthetic and water, a non-crosslinked water-soluble stabilizing agent, an acrylic copolymer comprising as monomeric unit at least one acrylic monomer with carboxylic function, at least one acrylic and / or vinyl monomer without carboxylic function and at least one oxyalkylated monomer with ethylenic unsaturation and terminated by a hydrophobic fatty chain.
Un autre objet de l'invention est un procédé d'obtention desdites suspensions aqueuses de zéolithes, fluides et stables dans le temps, au moyen d'un ajout dudit agent de stabilisation hydrosoluble non réticulé ainsi que l'utilisation comme stabilisant dudit copolymère hydrosoluble non réticulé.Another object of the invention is a process for obtaining said aqueous suspensions of zeolites, fluid and stable over time, by means of an addition of said non-crosslinked water-soluble stabilizing agent as well as the use as stabilizer of said non-crosslinkable water-soluble copolymer reticle.
Un autre but de l'invention est également l'utilisation de ces suspensions aqueuses de zéolithes, comprenant ledit agent de stabilisation, dans le domaine de la détergence et comme agent séquestrant.Another object of the invention is also the use of these aqueous suspensions of zeolites, comprising said stabilizing agent, in the field of detergency and as sequestering agent.
Depuis longtemps déjà, l'homme de l'art propose des adjuvants permettant d'obtenir des suspensions stables de zéolithes. C'est ainsi que les brevets FR 2 287 504 et EP 0 294 694 décrivent la préparation de suspensions de zéolithes stabilisées avec des tensio-actifs appartenant notamment à la famille des alcools gras en C₁₀-C₁₈ éthoxylés avec 1 à 8 moles d'oxyde d'éthylène. Cette solution présente l'inconvénient de mettre en oeuvre des quantités très importantes d'agent stabilisant, de l'ordre de 0,5% à 6% en poids par rapport au poids total de la suspension.For a long time now, those skilled in the art have been offering adjuvants making it possible to obtain stable suspensions of zeolites. Thus the patents FR 2 287 504 and EP 0 294 694 describe the preparation of suspensions of zeolites stabilized with surfactants belonging in particular to the family of C₁₀-C₁₈ fatty alcohols ethoxylated with 1 to 8 moles of oxide ethylene. This solution has the drawback of using very large amounts of stabilizing agent, of the order of 0.5% to 6% by weight relative to the total weight of the suspension.
Dans le brevet FR 2 512 690, les agents stabilisants évoqués sont des polymères hydroxylés issus de l'amidon qui se révèlent efficaces mais doivent être utilisés en quantité importante comprise entre 0,4% et 2,5% en poids par rapport à la masse totale de la suspension.In patent FR 2,512,690, the stabilizing agents mentioned are hydroxylated polymers derived from starch which prove effective but must be used in a large amount of between 0.4% and 2.5% by weight relative to the mass total suspension.
Le brevet DE 3 021 295 décrit une composition stable de zéolithes contenant 15% d'acide nitrilotriacétique sous forme salifiée, produit dont les rejets sont aujourd'hui fortement réglementés, voire interdits dans certains pays.Patent DE 3,021,295 describes a stable composition of zeolites containing 15% nitrilotriacetic acid in salified form, a product the discharges of which are today highly regulated, or even prohibited in certain countries.
Les brevets FR 2 455 479 et FR 2 461 516 revendiquent comme agent stabilisant des polymères qui présentent l'inconvénient, soit de provoquer des dégagements d'ammoniac dans le milieu fortement alcalin (pH 10 à 13) des zéolithes dans le cas du brevet FR 2 455 479, soit de ne pas assurer une bonne stabilité au cours de la préparation, du stockage et du transport des suspensions de zéolithes à des températures situées entre 50°C et 60°C (FR 2 461 516).The patents FR 2 455 479 and FR 2 461 516 claim as a stabilizing agent polymers which have the drawback, that is to cause releases of ammonia in the strongly alkaline medium (pH 10 to 13) of the zeolites in the case of the patent FR 2,455,479, or not to ensure good stability during the preparation, storage and transport of the zeolite suspensions at temperatures between 50 ° C and 60 ° C (FR 2 461 516).
Un autre brevet français, FR 2 658 095, révèle l'utilisation comme agent stabilisant des copolymères acryliques réticulés.Another French patent, FR 2 658 095, discloses the use as crosslinking agent of crosslinked acrylic copolymers.
Cette autre solution a également l'inconvénient d'utiliser des quantités trop importantes d'agent stabilisant de l'ordre de 0,4% en poids sec par rapport au poids total de la suspension.This other solution also has the drawback of using excessively large amounts of stabilizing agent of the order of 0.4% by dry weight relative to the total weight of the suspension.
Confrontée aux inconvénients précités, la Demanderesse a alors mis au point des suspensions aqueuses de zéolithes dont la fluidité et la stabilité au stockage sont, de manière surprenante, considérablement améliorées grâce à l'utilisation de copolymères acryliques hydrosolubles non réticulés à des doses beaucoup plus faibles que dans le cas des produits de l'art antérieur.Confronted with the aforementioned drawbacks, the Applicant then developed aqueous suspensions of zeolites whose fluidity and stability in storage are, surprisingly, considerably improved thanks to the use of non-crosslinked water-soluble acrylic copolymers at much lower doses. than in the case of prior art products.
Selon l'invention, les suspensions aqueuses de zéolithes, de concentration en zéolithe anhydre d'environ 50%, contiennent outre une ou plusieurs zéolithes naturelles ou synthétiques, par exemple du type 4A, X, Y, un agent stabilisant et sont caractérisées en ce que ce dit agent est un copolymère constitué :
- a) d'au moins un monomère acrylique à fonction carboxylique choisi parmi les acides acrylique, méthacrylique, itaconique, cinnamique, crotonique, isocrotonique, fumarique, maléique et son anhydride, aconitique, mésaconique, sinapique, undécylénique, angélique, hydroxyacrylique.
- b) d'au moins un monomère acrylique et/ou vinylique sans fonction carboxylique choisi parmi les esters, les amides et/ou les nitriles des acides acrylique, méthacrylique, itaconique, cinammique, crotonique, isocrotonique, fumarique, maléique, aconitique, mésaconique, sinapique, undécylénique, angélique, hydroxyacrylique ou encore choisi parmi l'acétate de vinyle, le styrène, l'alphaméthylstyrène, le diisobutylène, la vinylpyrrolidone, la vinylcaprolactame.
- c) d'au moins un monomère oxyalkylé à insaturation éthylénique et terminé par une chaîne hydrophobe, de formule générale (I) :
- m et p représentent un nombre de motifs d'oxyde d'alkylène,
- n représente un nombre de motifs d'oxyde d'éthylène,
- q un nombre au moins égal à 1, tels que q(n+m+p) ≤ 100,
- R le radical insaturé polymérisable,
- R' le radical hydrophobe à chaîne grasse,
- R₁ l'hydrogène ou le groupe méthyle,
- R₂ l'hydrogène ou le groupe méthyle.
- a) at least one acrylic monomer having a carboxylic function chosen from acrylic, methacrylic, itaconic, cinnamic, crotonic, isocrotonic, fumaric, maleic acids and its anhydride, aconitic, mesaconic, sinapic, undecylenic, angelic, hydroxyacrylic.
- b) at least one acrylic and / or vinyl monomer without carboxylic function chosen from esters, amides and / or nitriles of acrylic, methacrylic, itaconic, cinammic, crotonic, isocrotonic, fumaric, maleic, aconitic, mesaconic acids, sinapic, undecylenic, angelic, hydroxyacrylic or else chosen from vinyl acetate, styrene, alphamethylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam.
- c) at least one oxyalkylated ethylenically unsaturated monomer terminated by a hydrophobic chain, of general formula (I):
- m and p represent a number of alkylene oxide units,
- n represents a number of ethylene oxide units,
- q a number at least equal to 1, such that q (n + m + p) ≤ 100,
- R the polymerizable unsaturated radical,
- R 'the hydrophobic fatty chain radical,
- R₁ hydrogen or methyl group,
- R₂ hydrogen or methyl group.
Ainsi, alors que l'art antérieur décrit pour l'essentiel des suspensions aqueuses de zéolithes stabilisées au moyen d'agents tels que des tensio-actifs, des complexants ou des polymères acryliques réticulés, la suspension aqueuse de zéolithes de concentration d'environ 50% en zéolithe anhydre, selon l'invention, s'en distingue par le fait qu'elle contient, comme agent stabilisant hydrosoluble, un copolymère constitué :
- a) d'au moins un monomère acrylique disposant d'une fonction carboxylique choisi plus spécifiquement parmi les acides acrylique et/ou méthacrylique et préférentiellement de 15% à 75% en poids par rapport au poids total des monomères, et tout particulièrement de 20% à 50% en poids.
- b) d'au moins un monomère acrylique choisi plus spécifiquement parmi les esters, les amides et/ou nitriles des acides acrylique et/ou méthacrylique et préférentiellement de 23% à 83% en poids par rapport au poids total des monomères, et tout particulièrement de 47% à 77% en poids.
- c) d'au moins un monomère oxyalkylé à insaturation éthylénique et terminé par une chaîne hydrophobe, de formule générale (I) :
- m et p représentent un nombre de motifs d'oxyde d'alkylène inférieur ou égal à 100,
- n représente un nombre de motifs d'oxyde d'éthylène inférieur ou égal à 100,
- q un nombre au moins égal à 1 et tels que : q(n+m+p) ≤ 100
- R₁ représente l'hydrogène ou le radical méthyle,
- R₂ représente l'hydrogène ou le radical méthyle.
- a) at least one acrylic monomer having a carboxylic function chosen more specifically from acrylic and / or methacrylic acids and preferably from 15% to 75% by weight relative to the total weight of the monomers, and very particularly from 20% at 50% by weight.
- b) at least one acrylic monomer chosen more specifically from esters, amides and / or nitriles of acrylic and / or methacrylic acids and preferably from 23% to 83% by weight relative to the total weight of the monomers, and very particularly from 47% to 77% by weight.
- c) at least one oxyalkylated ethylenically unsaturated monomer terminated by a hydrophobic chain, of general formula (I):
- m and p represent a number of alkylene oxide units less than or equal to 100,
- n represents a number of ethylene oxide units less than or equal to 100,
- q a number at least equal to 1 and such that: q (n + m + p) ≤ 100
- R₁ represents hydrogen or the methyl radical,
- R₂ represents hydrogen or the methyl radical.
R représente le radical insaturé polymérisable, appartenant au groupe des esters acrylique, méthacrylique, maléique, itaconique, crotonique, vinylphtalique ainsi que les hémiesters maléique, itaconique, vinylphtalique ou encore les insaturés uréthannes tels que par exemple les acryluréthanne, méthacryluréthanne, α-α diméthyl-m-isopropenylbenzyluréthanne, allyluréthanne ou bien encore les éthers allyliques, les acrylamide et méthacrylamide substituées ou non, les vinyliques.R represents the polymerizable unsaturated radical, belonging to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as maleic, itaconic, vinylphthalic or even unsaturated urethanes such as, for example, acrylurethane, methacrylurethane, α-α dimethyl -m-isopropenylbenzylurethane, allylurethane or alternatively allyl ethers, acrylamide and methacrylamide substituted or not, vinyls.
R' représente le radical hydrophobe à chaîne grasse tels que les groupes linéaires ou ramifiés alkyle, alkylaryle, arylalkyle, aryle ayant de 12 à 40 atomes de carbone et préférentiellement de 26 à 40 atomes de carbone.R 'represents the hydrophobic radical with a fatty chain such as linear or branched alkyl, alkylaryl, arylalkyl, aryl groups having from 12 to 40 carbon atoms and preferably from 26 to 40 carbon atoms.
Ce copolymère, utilisé dans la suspension aqueuse de zéolithes selon l'invention, est obtenu selon des procédés connus de l'homme de l'art par polymérisation radicalaire, en émulsion directe ou inverse, en suspension ou par précipitation dans un solvant approprié.This copolymer, used in the aqueous suspension of zeolites according to the invention, is obtained according to methods known to those skilled in the art by radical polymerization, in direct or reverse emulsion, in suspension or by precipitation in an appropriate solvent.
Ce copolymère ainsi préparé permet d'obtenir selon l'invention, une suspension aqueuse fluide et stable de zéolithes ayant une teneur en zéolithe anhydre d'environ 50%.This copolymer thus prepared makes it possible to obtain, according to the invention, a fluid and stable aqueous suspension of zeolites having an anhydrous zeolite content of approximately 50%.
Cette suspension, selon l'invention, peut être obtenue par simple mélange du copolymère hydrosoluble ajouté dans la suspension aqueuse de zéolithes non stabilisée.This suspension, according to the invention, can be obtained by simple mixing of the water-soluble copolymer added to the aqueous suspension of non-stabilized zeolites.
Elle peut également être obtenue à partir d'une poudre de zéolithe préalablement séchée surtout lorsque la synthèse du silico-aluminate est effectuée en un lieu éloigné de son lieu d'utilisation et que son transport à l'état sec est moins coûteux que les dépenses de séchage.It can also be obtained from a previously dried zeolite powder, especially when the synthesis of the silico-aluminate is carried out at a place far from its place of use and when its transport in the dry state is less costly than the expenses. drying.
La suspension aqueuse selon l'invention est cependant souvent obtenue au cours du procédé de fabrication de la zéolithe même, par réaction entre le gâteau de filtration et le copolymère hydrosoluble ajouté après l'étape de lavage et de filtration.The aqueous suspension according to the invention is however often obtained during the process for manufacturing the zeolite itself, by reaction between the filter cake and the water-soluble copolymer added after the washing and filtration step.
La suspension aqueuse de zéolithes, selon l'invention, ainsi obtenue grâce à l'utilisation jusqu'à 0,3% en poids sec du copolymère hydrosoluble par rapport au poids total de la suspension, présente alors une viscosité apparente Brookfield inférieure à 2 500 mPa.s (ou cP) à 10 tours/minute (T/mn) et 20°C et ceci même après 40 jours de stockage sans agitation.The aqueous suspension of zeolites according to the invention, thus obtained by using up to 0.3% by dry weight of the water-soluble copolymer relative to the total weight of the suspension, then has an apparent Brookfield viscosity of less than 2,500 mPa.s (or cP) at 10 revolutions / minute (RPM) and 20 ° C and this even after 40 days of storage without shaking.
Sa tendance à ne pas sédimenter ainsi que son aptitude à la pompabilité et à la manipulabilité s'expriment par la mesure de la hauteur du dépôt au fond de la suspension après 4 jours de stockage à température ambiante ainsi que celle de la viscosité Brookfield après 40 jours de stockage à température ambiante.Its tendency not to sediment as well as its ability to be pumped and handled can be expressed by measuring the height of the deposit at the bottom of the suspension after 4 days of storage at room temperature as well as that of the Brookfield viscosity after 40 days of storage at room temperature.
Ces tests permettant de classer les différentes suspensions aqueuses de zéolithes montrent que la suspension aqueuse de zéolithes, selon l'invention, est particulièrement stable, fluide, pompable et manipulable. Ces propriétés ne sont pas altérées par des températures allant jusqu'à 60°C et même après plusieurs jours de stockage dans des cuves non agitées ou après transport dans des camions ou wagons citernes usuels.These tests making it possible to classify the various aqueous suspensions of zeolites show that the aqueous suspension of zeolites, according to the invention, is particularly stable, fluid, pumpable and manipulable. These properties are not affected by temperatures up to 60 ° C and even after several days of storage in unstirred tanks or after transport in standard trucks or tank wagons.
La suspension aqueuse de zéolithes, selon l'invention, présente également l'avantage d'être plus pure que celles de l'art antérieur car la dose d'agent stabilisant utilisée est moindre et son pouvoir complexant est préservé ce qui permet son utilisation comme agent séquestrant.The aqueous suspension of zeolites according to the invention also has the advantage of being purer than those of the prior art because the dose of stabilizing agent used is less and its complexing power is preserved which allows its use as sequestering agent.
La grande stabilité des suspensions aqueuses de zéolithes, selon l'invention, permet leur éventuelle utilisation en détergence sans autre transformation, par mélange à d'autres additifs détergents. Lorsque la suspension aqueuse de zéolithes, selon l'invention, est utilisée en détergence sous forme pulvérulente après séchage comme par exemple par pulvérisation ou atomisation, on remarque alors que les produits obtenus sont exempts de poussière.The high stability of the aqueous zeolite suspensions according to the invention allows their possible use in detergency without further transformation, by mixing with other detergent additives. When the aqueous suspension of zeolites according to the invention is used in detergency in pulverulent form after drying, for example by spraying or atomization, it is then noted that the products obtained are free of dust.
La portée et l'intérêt de l'invention seront mieux perçus grâce à la description illustrative des exemples.The scope and the interest of the invention will be better perceived thanks to the illustrative description of the examples.
Dans le but de préparer les suspensions aqueuses de zéolithes stabilisées par différents agents stabilisants, la Demanderesse utilise dans tous les essais la même suspension aqueuse de zéolithe de type 4A contenant 52,5% de matière sèche.In order to prepare the aqueous suspensions of zeolites stabilized with different stabilizing agents, the Applicant uses in all of the tests the same aqueous suspension of type 4A zeolite containing 52.5% of dry matter.
Cette suspension d'aspect très fluide, lorsqu'elle est maintenue en agitation, sédimente en quelques heures, si elle ne contient aucun agent stabilisant, et se sépare en deux phases. L'une en un liquide surnageant et l'autre conduisant à un sédiment très dur impossible à remettre en suspension sans moyen mécanique puissant.This suspension, which is very fluid in appearance, when it is kept in agitation, sediments within a few hours, if it contains no stabilizing agent, and separates into two phases. One in a supernatant liquid and the other leading to a very hard sediment impossible to resuspend without powerful mechanical means.
Les tailles de particules de zéolithe sont comprises entre 1 et 10 µm et la suspension a un pH alcalin supérieur à 12.The zeolite particle sizes are between 1 and 10 μm and the suspension has an alkaline pH greater than 12.
La suspension est fractionnée en échantillons de 240 g. Chaque fraction est conservée dans un flacon en verre de 230 ml muni d'un couvercle métallique hermétique.The suspension is divided into 240 g samples. Each fraction is kept in a 230 ml glass bottle fitted with an airtight metal lid.
Chaque flacon ne servira qu'à un seul essai de stabilisation. Pour chaque essai, le contenu du pot est remis en suspension fluide et homogène à l'aide d'un système d'agitation du type Rayneri avant d'incorporer l'agent stabilisant à tester. L'agitation est maintenue pendant 15 minutes de façon à obtenir un mélange intime de la suspension à stabiliser et de l'agent testé.Each bottle will be used for only one stabilization test. For each test, the contents of the pot are resuspended in a fluid and homogeneous suspension using a Rayneri-type stirring system before incorporating the stabilizing agent to be tested. Stirring is continued for 15 minutes so as to obtain an intimate mixture of the suspension to be stabilized and the agent tested.
Après ce temps, la rhéologie du système est déterminée à l'aide d'un viscosimètre Brookfield type RVT équipé d'un module adapté. La viscosité apparente To est mesurée à 20°C. Chaque lecture est effectuée à 10 tours/minute et à 100 tours/minute après 2 minutes de rotation. Les récipients contenant la suspension ainsi stabilisée, munis de leurs couvercles hermétiques, sont laissés au repos à température ambiante pour un cycle de vieillissement statique de quatre jours.After this time, the rheology of the system is determined using a Brookfield type RVT viscometer equipped with a suitable module. The apparent viscosity To is measured at 20 ° C. Each reading is performed at 10 revolutions / minute and at 100 revolutions / minute after 2 minutes of rotation. The containers containing the suspension thus stabilized, fitted with their hermetic lids, are left to stand at room temperature for a static aging cycle of four days.
Après ce laps de temps, on détermine pour chaque essai la stabilité puis la rhéologie de la suspension.After this lapse of time, the stability and then the rheology of the suspension are determined for each test.
Elle est déterminée par la mesure à l'aide d'une réglette graduée de la hauteur du sédiment au fond du flacon en verre. La suspension aqueuse de zéolithe est considérée comme stable si la hauteur du dépôt est inférieure ou égale à 1 mm.It is determined by the measurement using a graduated slide of the height of the sediment at the bottom of the glass bottle. The aqueous zeolite suspension is considered to be stable if the height of the deposit is less than or equal to 1 mm.
La rhéologie du système se détermine par la mesure de la viscosité apparente de la suspension à 20°C, à l'aide d'un viscosimètre Brookfield type RVT équipé du module adapté. Les lectures sont faites à 10 tours/minute et à 100 tours/minute après deux minutes de rotation et sont notées T4J.The rheology of the system is determined by measuring the apparent viscosity of the suspension at 20 ° C, using a Brookfield viscometer type RVT equipped with the appropriate module. The readings are taken at 10 rpm and 100 rpm after two minutes of rotation and are noted T4J.
La suspension aqueuse est considérée comme pompable lorsque la viscosité apparente mesurée à 10 tours/minute est inférieure ou égale à 2500 mPa.s (cP).The aqueous suspension is considered to be pumpable when the apparent viscosity measured at 10 revolutions / minute is less than or equal to 2500 mPa.s (cP).
Cette mesure de rhéologie (viscosité Brookfield) effectuée après 4 jours de stockage est répétée après un deuxième cycle de vieillissement statique de 40 jours à température ambiante et notée T40J.This rheology measurement (Brookfield viscosity) carried out after 4 days of storage is repeated after a second static aging cycle of 40 days at room temperature and noted T40J.
Les diverses suspensions testées sont :The various suspensions tested are:
Suspension sans agent stabilisant.Suspension without stabilizing agent.
Suspension selon l'art antérieur contenant, comme agent de stabilisation, 0,3% en poids sec par rapport à la masse totale de la suspension d'un copolymère réticulé composé de:
- 40,4% en poids d'acide méthacrylique,
- 59% en poids d'acrylate d'éthyle,
- 0,6% en poids de réticulant.
- 40.4% by weight of methacrylic acid,
- 59% by weight of ethyl acrylate,
- 0.6% by weight of crosslinker.
Suspension selon l'art antérieur contenant, comme agent de stabilisation, 0,3% en poids sec par rapport à la masse totale de la suspension d'un alcool isotridécylique avec 5 moles d'oxyde d'éthylène.Suspension according to the prior art containing, as stabilizing agent, 0.3% by dry weight relative to the total mass of the suspension of an isotridecyl alcohol with 5 moles of ethylene oxide.
Suspension selon l'invention contenant, comme agent stabilisant, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique hydrosoluble constitué de :
- 35,5% en poids d'acide méthacrylique,
- 55% en poids d'acrylate d'éthyle,
- 9,5% en poids d'hémimaléate comprenant 25 motifs d'oxyde d'éthylène et un radical R' alkyle constitué de 28 atomes de carbone.
- 35.5% by weight of methacrylic acid,
- 55% by weight of ethyl acrylate,
- 9.5% by weight of hemimaleate comprising 25 ethylene oxide units and an alkyl radical R 'consisting of 28 carbon atoms.
Suspension selon l'invention contenant, comme agent stabilisant, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique hydrosoluble constitué de :
- 35,5% en poids d'acide méthacrylique,
- 55% en poids d'acrylate d'éthyle,
- 9,5% en poids d'un méthacrylate comprenant 11 motifs d'oxyde d'éthylène et un radical R' alkyle linéaire constitué de 16 à 18 atomes de carbone.
- 35.5% by weight of methacrylic acid,
- 55% by weight of ethyl acrylate,
- 9.5% by weight of a methacrylate comprising 11 ethylene oxide units and a linear alkyl radical R 'consisting of 16 to 18 carbon atoms.
Suspension selon l'invention contenant, comme agent stabilisant, 0,25% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique hydrosoluble constitué de :
- 35,5% en poids d'acide méthacrylique,
- 55% en poids d'acrylate d'éthyle,
- 9,5% en poids d'un acryluréthanne comprenant 50 motifs d'oxyde d'éthylène et un radical R' nonylphényle.
- 35.5% by weight of methacrylic acid,
- 55% by weight of ethyl acrylate,
- 9.5% by weight of an acrylurethane comprising 50 ethylene oxide units and a nonylphenyl R ′ radical.
Les résultats des mesures de viscosité apparente Brookfield To, T4J, T40J et de hauteur de dépôt des divers essais sont rassemblés dans le tableau I suivant :
La lecture du tableau I permet de constater que seules les suspensions des essais n°4, 5 et 6, selon l'invention, possèdent après 4 jours et 40 jours à température ambiante une viscosité Brookfield (T4J, T40J) inférieure ou égale à 2500 mPa.s à 10 tours/minute et à 20°C ainsi qu'une hauteur de dépôt inférieure ou égale à 1 mm.Reading Table I shows that only the suspensions of tests No. 4, 5 and 6, according to the invention, after 4 days and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than or equal to 2500 mPa.s at 10 revolutions / minute and at 20 ° C as well as a deposit height less than or equal to 1 mm.
Ainsi, les suspensions aqueuses de zéolithe contenant selon l'invention jusqu'à 0,3% en poids sec par rapport à la masse totale de la suspension, d'un agent de stabilisation formé d'un copolymère constitué de :
- a) au moins un monomère acrylique à fonction carboxylique,
- b) au moins un monomère acrylique sans fonction carboxylique,
- c) au moins un monomère oxyalkylé à insaturation éthylénique et terminé par une chaîne hydrophobe de formule générale (I) sont fluides et stables dans le temps.
- a) at least one acrylic monomer having a carboxylic function,
- b) at least one acrylic monomer without carboxylic function,
- c) at least one oxyalkylated ethylenically unsaturated monomer terminated by a hydrophobic chain of general formula (I) are fluid and stable over time.
Les suspensions aqueuses de zéolithe sont préparées avec le même mode opératoire que celui de l'exemple 1, à partir de la même suspension de zéolithe, et avec, comme agent stabilisant, des copolymères dont le pourcentage en monomère (c) de formule générale (I) varie.The aqueous zeolite suspensions are prepared with the same procedure as that of Example 1, from the same zeolite suspension, and with, as stabilizing agent, copolymers whose percentage of monomer (c) of general formula ( I) varies.
Ainsi, sont testées pour :
- l'essai n° 7 :
une suspension selon l'art antérieur contenant comme agent de stabilisation, 0,30% en poids sec par rapport à la masse totale de la suspension d'un polymère acrylique sans monomère (c), et constitué de :- 41% en poids d'acide méthacrylique,
- 59% en poids d'acrylate d'éthyle.
- l'essai n°8 :
une suspension selon l'invention contenant, comme agent de stabilisation, 0,20% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 60,5% en poids d'acrylate d'éthyle,
- c. 4% en poids d'un méthacrylate comprenant 11 motifs d'oxyde d'éthylène et un radical R' alkyle linéaire constitué de 16 à 18 atomes de carbone.
- l'essai n°9 :
une suspension selon l'invention contenant comme agent de stabilisation, 0,16% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,4% en poids d'acide méthacrylique,
- b. 59% en poids d'acrylate d'éthyle,
- c. 5,6% en poids du même méthacrylate que pour l'essai n°8.
- l'essai n°10 :
une suspension selon l'invention contenant, comme agent de stabilisation, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 57% en poids d'acrylate d'éthyle,
- c. 7,5% en poids du même méthacrylate que pour l'essai n°8.
- l'essai n°11 :
une suspension selon l'invention contenant, comme agent de stabilisation, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 52,5% en poids d'acrylate d'éthyle,
- c. 12% en poids du même méthacrylate que pour l'essai n°8.
- l'essai n°12 :
une suspension selon l'invention contenant, comme agent de stabilisation 0,20% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 60,5% en poids d'acrylate d'éthyle,
- c. 4% en poids d'hémimaléate comprenant 25 motifs d'oxyde d'éthylène et un radical R' alkyle constitué de 22 atomes de carbone.
- l'essai n°13 :
une suspension selon l'invention contenant, comme agent de stabilisation, 0,19% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,4% en poids d'acide méthacrylique,
- b. 59% en poids d'acrylate d'éthyle,
- c. 5,6% en poids du même hémimaléate que pour l'essai n°12.
- l'essai n°14 :
une suspension selon l'invention contenant, comme agent de stabilisation, 0,16% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 57% en poids d'acrylate d'éthyle,
- c. 7,5% en poids du même hémimaléate que pour l'essai n°12.
- l'essai n°15 :
une suspension selon l'invention contenant, comme agent de stabilisation, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 55% en poids d'acrylate d'éthyle,
- c. 9,5% en poids du même hémimaléate que pour l'essai n°12.
- test n ° 7 :
a suspension according to the prior art containing, as stabilizing agent, 0.30% by dry weight relative to the total mass of the suspension of an acrylic polymer without monomer (c), and consisting of:- 41% by weight of methacrylic acid,
- 59% by weight of ethyl acrylate.
- test # 8 :
a suspension according to the invention containing, as stabilizing agent, 0.20% by dry weight relative to the mass total of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 60.5% by weight of ethyl acrylate,
- vs. 4% by weight of a methacrylate comprising 11 ethylene oxide units and a linear alkyl radical R 'consisting of 16 to 18 carbon atoms.
- test n ° 9 :
a suspension according to the invention containing, as stabilizing agent, 0.16% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.4% by weight of methacrylic acid,
- b. 59% by weight of ethyl acrylate,
- vs. 5.6% by weight of the same methacrylate as for test No. 8.
- test # 10 :
a suspension according to the invention containing, as stabilizing agent, 0.13% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 57% by weight of ethyl acrylate,
- vs. 7.5% by weight of the same methacrylate as for test No. 8.
- test n ° 11 :
a suspension according to the invention containing, as stabilizing agent, 0.13% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 52.5% by weight of ethyl acrylate,
- vs. 12% by weight of the same methacrylate as for test No. 8.
- test # 12:
a suspension according to the invention containing, as stabilizing agent 0.20% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 60.5% by weight of ethyl acrylate,
- vs. 4% by weight of hemimaleate comprising 25 ethylene oxide units and an alkyl radical R 'consisting of 22 carbon atoms.
- test # 13:
a suspension according to the invention containing, as stabilizing agent, 0.19% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.4% by weight of methacrylic acid,
- b. 59% by weight of ethyl acrylate,
- vs. 5.6% by weight of the same hemimaleate as for test No. 12.
- test n ° 14 :
a suspension according to the invention containing, as stabilizing agent, 0.16% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 57% by weight of ethyl acrylate,
- vs. 7.5% by weight of the same hemimaleate as for test No. 12.
- test # 15:
a suspension according to the invention containing, as stabilizing agent, 0.13% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 55% by weight of ethyl acrylate,
- vs. 9.5% by weight of the same hemimaleate as for test No. 12.
Le tableau II qui suit rassemble les résultats des mesures de viscosité apparente Brookfield To, T4J, T40J et de stabilité effectuées dans les mêmes conditions que dans l'exemple n°1.
La lecture du tableau II permet de constater que les suspensions des essais n°8 à 15, selon l'invention, possèdent après 4 et 40 jours à température ambiante une viscosité Brookfield (T4J, T40J) inférieure ou égale à 2500 mPa.s à 10 tours/minute et 20°C, ainsi qu'une hauteur de dépôt inférieure ou égale à 1 mm.Reading Table II shows that the suspensions of tests 8 to 15, according to the invention, after 4 and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than or equal to 2500 mPa.s at 10 revolutions / minute and 20 ° C, as well as a deposit height less than or equal to 1 mm.
Ainsi, les suspensions aqueuses de zéolithe selon l'invention contenant un agent de stabilisation formé d'un copolymère constitué de :
- a. au moins un monomère acrylique à fonction carboxylique,
- b. au moins un monomère acrylique sans fonction carboxylique,
- c. 3 à 12% en poids d'un monomère oxyalkylé à insaturation éthylénique et terminé par une chaîne hydrophobe, de formule générale (I), sont fluides et stables dans le temps.
- at. at least one acrylic monomer with a carboxylic function,
- b. at least one acrylic monomer without carboxylic function,
- vs. 3 to 12% by weight of an ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain, of general formula (I), are fluid and stable over time.
Les suspensions aqueuses de zéolithe sont préparées avec le même mode opératoire que celui de l'exemple n°1, à partir de la même suspension de zéolithe et avec, comme agent stabilisant, des copolymères dont le pourcentage en poids d'acide méthacrylique varie entre 20% et 50% et le pourcentage en poids d'acrylate d'éthyle varie entre 47% et 77%. Ainsi, sont testées pour :
- l'essai n°16 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,28% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 20% en poids d'acide méthacrylique,
- b. 75% en poids d'acrylate d'éthyle,
- c. 5% en poids d'hémimaléate comprenant 25 motifs d'oxyde d'éthylène et un radical R' alkyle constitué de 22 atomes de carbone.
- l'essai n°17 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,20% en poids sec par rapport à la masse totale de la suspension d'un copolymère constitué de :- a. 50% en poids d'acide méthacrylique,
- b. 47% en poids d'acrylate d'éthyle,
- c. 3% en poids d'hémimaléate comprenant 25 motifs d'oxyde d'éthylène et un radical R' alkyle constitué de 22 atomes de carbone.
- test n ° 16 :
a suspension according to the invention containing, as stabilizing agent, 0.28% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 20% by weight of methacrylic acid,
- b. 75% by weight of ethyl acrylate,
- vs. 5% by weight of hemimaleate comprising 25 ethylene oxide units and an alkyl radical R 'consisting of 22 carbon atoms.
- test n ° 17 :
a suspension according to the invention containing, as stabilizing agent, 0.20% by dry weight relative to the total mass of the suspension of a copolymer consisting of:- at. 50% by weight of methacrylic acid,
- b. 47% by weight of ethyl acrylate,
- vs. 3% by weight of hemimaleate comprising 25 ethylene oxide units and an alkyl radical R 'consisting of 22 carbon atoms.
Le tableau III qui suit rassemble les résultats des mesures de viscosité apparente Brookfield To, T4J, T40J et de hauteur de dépôt (stabilité) effectuées dans les mêmes conditions que dans l'exemple n°1.
La lecture du tableau III permet de constater que les suspensions des essais n°16 et 17, selon l'invention, possèdent après 4 et 40 jours à température ambiante une viscosité Brookfield (T4J, T40J) inférieure à 2500 mPa.s à 10 tours/minute et 20°C, ainsi qu'une hauteur de dépôt inférieure ou égale à 1 mm.Reading Table III shows that the suspensions of tests No. 16 and 17, according to the invention, after 4 and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than 2500 mPa.s at 10 turns / minute and 20 ° C, as well as a deposit height less than or equal to 1 mm.
Ainsi, les suspensions aqueuses de zéolithe selon l'invention contenant comme agent stabilisant un copolymère composé de :
- a. 20% à 50% en poids d'un monomère acrylique à fonction carboxylique,
- b. 47% à 77% en poids d'un monomère acrylique sans fonction carboxylique,
- c. 3% à 12% en poids d'un monomère oxyalkylé à insaturation éthylénique et terminé par une chaîne hydrophobe, de formule générale (I) sont fluides et stables dans le temps.
- at. 20% to 50% by weight of an acrylic monomer with a carboxylic function,
- b. 47% to 77% by weight of an acrylic monomer without a carboxylic function,
- vs. 3% to 12% by weight of an ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain, of general formula (I) are fluid and stable over time.
Les suspensions aqueuses de zéolithe sont préparées avec le même mode opératoire que celui de l'exemple n°1, à partir de la même suspension de zéolithe et avec, comme agent stabilisant, des copolymères dont la chaîne hydrophobe R' du monomère (C) de formule générale (I) varie en nombre d'atomes de carbone.The aqueous zeolite suspensions are prepared with the same procedure as that of Example No. 1, from the same zeolite suspension and with, as stabilizing agent, copolymers including the hydrophobic chain R 'of the monomer (C) of general formula (I) varies in number of carbon atoms.
Ainsi, sont testées pour :
- l'essai n°18 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,28% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 55% en poids d'acrylate d'éthyle,
- c. 9,5% en poids d'un méthacrylate comprenant 23 motifs d'oxyde d'éthylène et un radical R' alkyle linéaire constitué de 12 atomes de carbone.
- l'essai n°19 :
la suspension de l'essai n°5, selon l'invention, contenant comme agent stabilisant, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 55% en poids d'acrylate d'éthyle,
- c. 9,5% en poids d'un méthacrylate comprenant 11 motifs d'oxyde d'éthylène et un radical R' alkyle linéaire constitué de 16 à 18 atomes de carbone.
- l'essai n°20 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère acrylique constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 55% en poids d'acrylate d'éthyle,
- c. 9,5% en poids d'un hémimaléate comprenant 25 motifs d'oxyde d'éthylène et un radical R' alkyle constitué de 28 atomes de carbone.
- l'essai n°21 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 55% en poids d'acrylate d'éthyle,
- c. 9,5% en poids d'un hémimaléate comprenant 20 motifs d'oxyde d'éthylène et un radical R' alkyle constitué de 36 atomes de carbone.
- l'essai n° 22 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,13% en poids sec par rapport à la masse totale de la suspension d'un copolymère constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 55% en poids d'acrylate d'éthyle,
- c. 9,5% en poids d'un méthacrylate comprenant 70 motifs d'oxyde d'éthylène et un radical R' alkyle linéaire constitué de 16 à 18 atomes de carbone.
- l'essai n°23 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,28% en poids sec par rapport à la masse totale de la suspension d'un copolymère constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 55% en poids d'acrylate d'éthyle,
- c. 9,5% en poids d'un méthacrylate comprenant 6 motifs d'oxyde d'éthylène, 7 motifs d'oxyde de propylène et un radical R' alkyle constitué de 14 atomes de carbone.
- l'essai n°24 :
une suspension selon l'invention contenant, comme agent stabilisant, 0,28% en poids sec par rapport à la masse totale de la suspension d'un copolymère constitué de :- a. 35,5% en poids d'acide méthacrylique,
- b. 62,5% en poids d'acrylate d'éthyle,
- c. 2% en poids d'un méthacrylate comprenant 25 motifs d'oxyde d'éthylène et un radical R' alkyle constitué de 22 atomes de carbone.
- test # 18:
a suspension according to the invention containing, as stabilizing agent, 0.28% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 55% by weight of ethyl acrylate,
- vs. 9.5% by weight of a methacrylate comprising 23 ethylene oxide units and a linear alkyl radical R 'consisting of 12 carbon atoms.
- test n ° 19:
the suspension of test No. 5, according to the invention, containing as stabilizing agent, 0.13% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 55% by weight of ethyl acrylate,
- vs. 9.5% by weight of a methacrylate comprising 11 ethylene oxide units and a linear alkyl radical R 'consisting of 16 to 18 carbon atoms.
- test n ° 20 :
a suspension according to the invention containing, as stabilizing agent, 0.13% by dry weight relative to the total mass of the suspension of an acrylic copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 55% by weight of ethyl acrylate,
- vs. 9.5% by weight of a hemimaleate comprising 25 ethylene oxide units and an alkyl radical R 'consisting of 28 carbon atoms.
- test n ° 21 :
a suspension according to the invention containing, as stabilizing agent, 0.13% by dry weight relative to the total mass of the suspension of a copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 55% by weight of ethyl acrylate,
- vs. 9.5% by weight of a hemimaleate comprising 20 ethylene oxide units and an alkyl radical R 'consisting of 36 carbon atoms.
- test # 22:
a suspension according to the invention containing, as stabilizing agent, 0.13% by dry weight relative to the total mass of the suspension of a copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 55% by weight of ethyl acrylate,
- vs. 9.5% by weight of a methacrylate comprising 70 ethylene oxide units and a linear alkyl radical R 'consisting of 16 to 18 carbon atoms.
- test # 23 :
a suspension according to the invention containing, as stabilizing agent, 0.28% by dry weight relative to the total mass of the suspension of a copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 55% by weight of ethyl acrylate,
- vs. 9.5% by weight of a methacrylate comprising 6 ethylene oxide units, 7 propylene oxide units and an alkyl radical R 'consisting of 14 carbon atoms.
- test n ° 24:
a suspension according to the invention containing, as stabilizing agent, 0.28% by dry weight relative to the total mass of the suspension of a copolymer consisting of:- at. 35.5% by weight of methacrylic acid,
- b. 62.5% by weight of ethyl acrylate,
- vs. 2% by weight of a methacrylate comprising 25 ethylene oxide units and an alkyl radical R 'consisting of 22 carbon atoms.
Le tableau IV qui suit rassemble les résultats des mesures de viscosité apparente Brookfield To, T4J, T40J et de stabilité (hauteur du dépôt) effectuées dans les mêmes conditions que dans l'exemple 1.
La lecture du tableau IV permet de constater que les suspensions des essais n°18 à n°24, selon l'invention, possèdent après 4 et 40 jours à température ambiante une viscosité Brookfield (T4J, T40J) inférieure ou égale à 2500 mPa.s à 10 tours/minute et 20°C, ainsi qu'une hauteur de dépôt inférieure ou égale à 1 mm.Reading Table IV shows that the suspensions of tests n ° 18 to n ° 24, according to the invention, after 4 and 40 days at room temperature have a Brookfield viscosity (T4J, T40J) less than or equal to 2500 mPa. s at 10 revolutions / minute and 20 ° C, as well as a deposit height less than or equal to 1 mm.
Ainsi, les suspensions aqueuses de zéolithe selon l'invention contenant un agent de stabilisation formé d'un copolymère constitué de :
- a. au moins un monomère acrylique à fonction carboxylique,
- b. au moins un monomère acrylique sans fonction carboxylique,
- c. 2% à 12% en poids d'un monomère oxyalkylé à insaturation éthylénique et terminé par une chaîne hydrophobe possédant au moins 12 atomes de carbone et jusqu'à 40 atomes de carbone sont fluides et stables dans le temps.
- at. at least one acrylic monomer with a carboxylic function,
- b. at least one acrylic monomer without carboxylic function,
- vs. 2% to 12% by weight of an ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain having at least 12 carbon atoms and up to 40 carbon atoms are fluid and stable over time.
Claims (11)
- Stable aqueous zeolites suspension, containing moreover one or more natural or synthetic zeolites and water and a stabilising agent, characterised by the fact that the said agent is a copolymer consisting:a. of at least one acrylic monomer with a carboxylic function selected from acrylic acid, methacrylic acid, itaconic acid, cinnamic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid and its anhydride, aconitic acid, mesaconic acid, sinapic acid, undecylenic acid, angelic acid and hydroxyacrylic acid.b. of at least one acrylic and/or vinyl monomer without a carboxylic function selected from the esters, the amides and/or the nitriles of acrylic acid, methacrylic acid, itaconic acid, cinnamic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid, aconitic acid, mesaconic acid, sinapic acid, undecylenic acid, angelic acid, hydroxyacrylic acid, or from vinyl acetate, styrene, alphamethylstyrene, diisobutylene, vinylpyrrolidone and vinylcaprolactam.c. of at least one ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain, of the general formula (I) :
- m and p represent a number of alkylene oxide structures less than or equal to 100,- n represents a number of ethylene oxide structures less than or equal to 100,- q a number at least equal to 1 and such that q(n+m+p) ≤ 100,- R₁hydrogen or the methyl radical,- R₂ hydrogen or the methyl radical,- R a polymerisable unsaturated radical selected from acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters in addition to maleic, itaconic and vinylphthalic hemiesters, or else the unsaturated urethanes for example acrylurethane, methacrylurethane, α-α dimethyl-m-isopropenylbenzylurethane, allylurethane, or else again the allyl ethers, acrylamide and methacrylamide whether substituted or not and the vinyl compounds,- R' a hydrophobic radical with a fatty chain selected from the linear or branched alkyl, alkylaryl, arylalkyl and aryl groups having 12 to 40 carbon atoms. - Stable aqueous zeolite suspension as described in claim 1, characterised by the fact that the said agent is a copolymer consisting:a. of at least one acrylic monomer with a carboxylic function selected from acrylic acid, methacrylic acid, itaconic acid, cinnamic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid and its anhydride, aconitic acid, mesaconic acid, sinapic acid, undecylenic acid, angelic acid and hydroxyacrylic acid.b. of at least one acrylic and/or vinyl monomer without a carboxylic function selected from the esters, the amides and/or the nitriles of acrylic, methacrylic, itaconic, cinnamic, crotonic, isocrotonic, fumaric, maleic, aconitic, mesaconic, sinapic, undecylenic, angelic and hydroxyacrylic acids or from vinyl acetate, styrene, alphamethylstyrene, diisobutylene, vinylpyrrolidone and vinylcaprolactam.c. at least one ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain, of the general formula (I):
- m and p represent a number of alkylene oxide structures less than or equal to 100,- n represents a number of ethylene oxide structures less than or equal to 100,- q a number at least equal to and such that q(n+m+p) ≤ 100,- R₁ hydrogen or the methyl radical,- R₂ hydrogen or the methyl radical,- R a polymerisable unsaturated radical selected from the acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters or else the maleic, itaconic and vinylphthalic hemiesters, or else again the unsaturated urethanes such as for example acrylurethane and methacrylurethane, α-α dimethyl-m-isopropenylbenzylurethane and allylurethane or also the allyl ethers, acrylamide and methacrylamide whether substituted or not, and the vinyl compounds,- R' a hydrophobic radical with a fatty chain, selected from the linear or branched alkyl, alkylaryl, arylalkyl and aryl groups having 26 to 40 carbon atoms. - Stable aqueous zeolites suspension, as described in either of claims 1 or 2, characterised by the fact that the monomer with a carboxylic function constituting the stabilising agent is selected from acrylic and/or methacrylic acids.
- Stable aqueous zeolites suspension as described in either of claims 1 or 2, characterised by the fact that the monomer without a carboxylic function constituting the stabilising agent is selected from the esters, amides and/or nitriles of acrylic and/or methacrylic acid.
- Stable aqueous zeolites suspension as described in claims 3 and 4, characterised by the fact that the stabilising agent is a copolymer consisting:a. of 15% to 75% by weight of an acrylic monomer with a carboxylic function selected from acrylic and/or methacrylic acid,b. of 23% to 83% by weight of an acrylic monomer without a carboxylic function selected from the esters, amides and/or nitriles of acrylic and/or methacrylic acid,c. of 2% to 12% by weight of an ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain, of general formula (I) as described in either of claims 1 or 2.
- Stable aqueous zeolites suspension as described in claims 3 and 4, characterised by the fact that the stabilising agent is a copolymer consisting:a. of 20% to 50% by weight of an acrylic monomer with a carboxylic function selected from acrylic and/or methacrylic acid,b. of 47% to 77% by weight of an acrylic monomer without a carboxylic function selected from the esters, amides and/or nitriles of acrylic and/or methacrylic acid,c. of 3% to 12% by weight of an ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain, of a general formula (I) in accordance with either of claims 1 and 2.
- Use as a stabilising agent for an aqueous zeolites suspension of a copolymer consisting:a. of at least one acrylic monomer with a carboxylic function selected from acrylic and/or methacrylic acid, and preferably from 15% to 75% by weight and more particularly from 20% to 50% by weight,b. of at least one acrylic monomer without a carboxylic function selected from the esters, amides and/or nitriles of acrylic and/or methacrylic acid, and preferably from 23% to 83% by weight and more particularly from 47% to 77% by weight,c. of at least one ethylenically unsaturated oxyalkylated monomer terminated by a hydrophobic chain, of the general formula:
- m and p represent a number of alkylene oxide structures less than or equal to 100,- n represents a number of ethylene oxide structures less than or equal to 100,- q a number at least equal to 1 and such that q(n+m+p) ≤ 100,- R₁ hydrogen or the methyl radical,- R₂ hydrogen or the methyl radical,- R a polymerisable unsaturated radical selected from the acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also the maleic, itaconic, and vinylphthalic hemiesters, or again the unsaturated urethanes such as, for example, acrylurethane, methacrylurethane, α-α dimethyl-m-isopropenylbenzylurethane and allylurethane or yet again the allyl ethers, acrylamide and methacrylamide whether substituted or not, and the vinyl compounds,- R' a hydrophobic radical with a fatty chain selected from the linear or branched alkyl. alkylaryl, arylalkyl and aryl groups having 12 to 40 carbon atoms and preferably from 26 to 40 carbon atoms. - Process for the preparation of a stable aqueous zeolites suspension as described in any one of claims 1 to 6, characterised by the fact that into a non-stabilised aqueous zeolites suspension is mixed up to 0.3% by dry weight, relative to the total mass of the suspension, of the stabilising agent.
- Process for the preparation of a stable aqueous zeolites suspension as described in any one of claims 1 to 6, characterised by the fact that the stabilising agent is added during the process of manufacture of the zeolite itself, and after the washing and filtration stage, so as to cause it to react with the filtration cake.
- Use of aqueous zeolites suspensions as described in any one of claims 1 to 6, in the cleansing field.
- Use of aqueous zeolites suspensions as described in any one of claims 1 to 6 as a sequestering agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9208398A FR2693127B1 (en) | 1992-07-01 | 1992-07-01 | Stable aqueous suspensions of zeolites, processes for obtaining them and their uses. |
| FR9208398 | 1992-07-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0577525A1 EP0577525A1 (en) | 1994-01-05 |
| EP0577525B1 true EP0577525B1 (en) | 1996-02-21 |
Family
ID=9431653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93420238A Expired - Lifetime EP0577525B1 (en) | 1992-07-01 | 1993-06-11 | Stable aqueous zeolite suspensions, their fabrication process and use |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US5423999A (en) |
| EP (1) | EP0577525B1 (en) |
| CA (1) | CA2096084C (en) |
| DE (1) | DE69301585T2 (en) |
| ES (1) | ES2083840T3 (en) |
| FR (1) | FR2693127B1 (en) |
| HK (1) | HK1006033A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1997838A3 (en) * | 1992-07-01 | 2009-04-15 | Coatex S.A.S. | Filler-containing and/or pigmented aqueous compositions comprising an acrylic copolymer, partially or fully water-soluble, crosslinked or not |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2752584A1 (en) * | 1996-08-26 | 1998-02-27 | Coatex Sa | AGENT COMPATIBLE WITH SURFACTANTS USED IN DETERGENCE OR COSMETICS |
| FR2766106B1 (en) * | 1997-07-18 | 2001-09-07 | Coatex Sa | USE OF A COPOLYMER WITH SURFACTORY STRUCTURE AS A DISPERSING AND / OR GRINDING AID |
| AUPO976597A0 (en) * | 1997-10-14 | 1997-11-06 | Orica Australia Pty Ltd | Method and composition (I) |
| AU735584B2 (en) * | 1997-10-14 | 2001-07-12 | Huntsman Surfactants Technology Corportion | Method and composition |
| FR2774694B1 (en) * | 1998-01-19 | 2003-08-08 | Rhodia Chimie Sa | USE OF COPOLYMERS BASED ON UNSATURATED ACIDS OR DERIVATIVES THEREOF AS FOAMENING AGENTS |
| FR2796403B1 (en) * | 1999-07-16 | 2001-09-28 | Coatex Sa | NOVEL HYDROSOLUBLE WATER RETENTION AGENT IN NEUTRAL OR ALKALINE MEDIUM OF VINYL-ACRYLIC COPOLYMER TYPE, APPLICATIONS TO COATING SAUCES FOR PAPER AND CARDBOARD, AND COATING SAUCERS AND PAPER AND CARDBOARD THUS OBTAINED |
| AU1460001A (en) * | 1999-11-10 | 2001-06-06 | Dow Chemical Company, The | Low odor floor covering system |
| FR2810261B1 (en) * | 2000-06-15 | 2002-08-30 | Coatex Sa | USE OF LOW ANIONIC COPOLYMERS AS A DISPERSING AGENT AND / OR AID FOR GRINDING AQUEOUS SUSPENSION OF MINERALS, AQUEOUS SUSPENSIONS OBTAINED AND USES THEREOF |
| FR2872815B1 (en) * | 2004-07-08 | 2008-06-27 | Coatex Soc Par Actions Simplif | USE OF WATER-SOLUBLE ACRYLIC COPOLYMERS IN AQUEOUS FORMATIONS POSSIBLY PIGMENTED AND FORMULATIONS OBTAINED |
| FR2950061B1 (en) * | 2009-09-11 | 2013-12-20 | Coatex Sas | ASSOCIATIVE MONOMERS BASED ON POLYCOSANOLS, CORRESPONDING ASSOCIATIVE THICKENERS AND USES THEREOF |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3320726A1 (en) * | 1983-06-09 | 1984-12-13 | Henkel KGaA, 4000 Düsseldorf | DETERGENT AND CLEANING AGENT CONTAINING ACYLCYANAMIDE SALTS |
| DE3444960A1 (en) * | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | GRAINY ADSORPTION |
| DE3528460A1 (en) * | 1985-08-08 | 1987-02-19 | Basf Ag | USE OF NEUTRALIZED AND AMIDATED CARBOXYL GROUPS OF POLYMERISATES AS ADDITION TO DETERGENTS AND CLEANING AGENTS |
| GB8813978D0 (en) * | 1988-06-13 | 1988-07-20 | Unilever Plc | Liquid detergents |
| DE3900207A1 (en) * | 1989-01-05 | 1990-07-12 | Basf Ag | USE OF COPOLYMERISES FROM 1,2-DI-ALKOXYETHYLENES AND MONOETHYLENICALLY UNSATURATED DICARBONE ACID ANHYDRIDES IN DETERGENTS AND DETERGENTS CONTAINING SUCH COPOLYMERISES |
| DE3915070A1 (en) * | 1989-05-09 | 1990-11-15 | Basf Ag | ISOPROPANOL SOLUBLE COPOLYMERISATES, MONOMERS CONTAINING POLYALKYLENE OXIDE BLOECKE, INCLUDED IN POLYMERIZED, THEIR PREPARATION AND THEIR USE |
| US4946627A (en) * | 1989-07-19 | 1990-08-07 | National Starch And Chemical Investment Holding Corporation | Hydrophobically modified polycarboxylate polymers utilized as detergent builders |
| IT1236966B (en) * | 1989-10-25 | 1993-05-07 | Ausidet Srl | PROCESS FOR THE PRODUCTION OF AQUEOUS SOLUTIONS OF ANTI-INCRUSTATION AGENTS AND SOLUTIONS SO OBTAINED |
| GB8928023D0 (en) * | 1989-12-12 | 1990-02-14 | Unilever Plc | Detergent compositions |
| US5216100A (en) * | 1989-12-18 | 1993-06-01 | Coatex S.A. | Non-toxic stabilizing agent for aqueous suspensions of sodium silico-aluminates |
| FR2658095B1 (en) * | 1989-12-18 | 1993-10-01 | Coatex Sa | NON-TOXIC STABILIZING AGENT FOR AQUEOUS SODIUM SILICO ALUMINATE SUSPENSIONS. |
| US5409629A (en) * | 1991-07-19 | 1995-04-25 | Rohm And Haas Company | Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents |
-
1992
- 1992-07-01 FR FR9208398A patent/FR2693127B1/en not_active Expired - Fee Related
-
1993
- 1993-05-12 CA CA002096084A patent/CA2096084C/en not_active Expired - Fee Related
- 1993-06-11 EP EP93420238A patent/EP0577525B1/en not_active Expired - Lifetime
- 1993-06-11 DE DE69301585T patent/DE69301585T2/en not_active Expired - Fee Related
- 1993-06-11 ES ES93420238T patent/ES2083840T3/en not_active Expired - Lifetime
- 1993-06-29 US US08/083,255 patent/US5423999A/en not_active Expired - Fee Related
-
1994
- 1994-12-08 US US08/354,811 patent/US5474702A/en not_active Expired - Fee Related
-
1998
- 1998-06-11 HK HK98105170A patent/HK1006033A1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1997838A3 (en) * | 1992-07-01 | 2009-04-15 | Coatex S.A.S. | Filler-containing and/or pigmented aqueous compositions comprising an acrylic copolymer, partially or fully water-soluble, crosslinked or not |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1006033A1 (en) | 1999-02-05 |
| DE69301585D1 (en) | 1996-03-28 |
| US5474702A (en) | 1995-12-12 |
| CA2096084A1 (en) | 1994-01-02 |
| DE69301585T2 (en) | 1996-10-02 |
| CA2096084C (en) | 2000-08-15 |
| FR2693127A1 (en) | 1994-01-07 |
| ES2083840T3 (en) | 1996-04-16 |
| EP0577525A1 (en) | 1994-01-05 |
| US5423999A (en) | 1995-06-13 |
| FR2693127B1 (en) | 1994-08-26 |
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