EP0422997A1 - Stable aqueous zeolite suspensions containing a succinoglycane - Google Patents
Stable aqueous zeolite suspensions containing a succinoglycane Download PDFInfo
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- EP0422997A1 EP0422997A1 EP90402758A EP90402758A EP0422997A1 EP 0422997 A1 EP0422997 A1 EP 0422997A1 EP 90402758 A EP90402758 A EP 90402758A EP 90402758 A EP90402758 A EP 90402758A EP 0422997 A1 EP0422997 A1 EP 0422997A1
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- succinoglycan
- suspension
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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
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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
Definitions
- the present invention relates to stable aqueous suspensions of zeolites.
- zeolites in detergency are well known. This use has developed in particular as a result of the at least partial substitution of zeolites for phosphates in detergents. They have been criticized, in fact, for causing eutrophication of the waters and therefore for posing ecological problems.
- Zeolites are generally used in the form of aqueous suspensions or slurries which can for example be introduced into detergent slurries which can then be atomized.
- the main object of the invention is therefore a means of obtaining an aqueous suspension of zeolite which is stable, that is to say which no longer sediments or only very shortly after several days of storage.
- a second object of the invention is a means of obtaining an aqueous suspension of zeolite which is not only stable, but which, moreover, is pumpable, that is to say which has a viscosity suitable for industrial use.
- the suspensions according to the invention comprise zeolites and they are characterized in that they also comprise a succinoglycan.
- the aqueous suspensions of zeolites further comprise a dispersant which is a siliconate and / or one of its derivatives.
- the aqueous suspensions of zeolites further comprise a dispersant which is a silicone resin.
- the zeolites used in the context of the present invention include crystalline, amorphous and mixed crystalline-amorphous, natural or synthetic zeolites.
- finely divided zeolites are used having an average diameter of primary particles of between 0.1 and 10 ⁇ m and, advantageously, between 0.5 and 5 ⁇ m, as well as a theoretical cation exchange power greater than 100 mg of CaCO3 / g of anhydrous product and preferably greater than 200 mg.
- Use is also more particularly made of zeolites of type A, X or Y and in particular 4A and 13X.
- zeolites obtained by the processes described in the French patent applications in the name of the Applicant No. 2,376,074, 2,384,716, 2,392,932, 2,528,722, the teaching of which is also incorporated herein request.
- the last reference cited refers in particular to zeolites having a speed constant, related to the surface of the zeolites per liter of solution greater than 0.15 s ⁇ 1.lm ⁇ 2, preferably greater than 0.25 and advantageously between 0.4 and 4 s ⁇ 1.lm ⁇ 2.
- These zeolites have particularly advantageous qualities in the use in detergency.
- the suspensions may have a variable zeolite concentration depending on the application. In detergency, this concentration is generally between 40 and 51% by weight.
- the pH of the suspensions is also a function of their use. Still in the detergency application, this pH expressed at 1% by weight of dry zeolite is approximately 11.
- succinoglycan is used as a stabilizing agent for zeolite suspensions.
- a succinoglycan is a polysaccharide containing succinic acid and galactose and glucose as sugars.
- the succinoglycans are generally obtained by fermentation of a medium comprising at least one carbon source assimilable by a strain or a recombinant or a mutant of this strain of the type given below: - Pseudomonas, in particular of origin NCIB 11592 - Rhizobium meliloti, in particular of origin U-27, 1021, SU-27, SU-4, SU-231, SU-255, SU-256, K 24 (R 13), A 148 (R 15), J 7017 - Rhizobium trifolii, in particular of origin J-60W - Alcaligenes faecalis of myxogenic varieties, in particular of origin 10C3,22-33 - Agrobacterium radiobacter, in particular of origin IFO 13533 - Agrobacterium rhizogenes, in particular of IFO 13259 origin - Agrobacterium tumefaciens, in particular of origin IFO 3058, A-8, A-10.
- a succinoglycan is chosen from the group of those which, after having passed the transition temperature, have an intrinsic viscosity of at least 14,000 ml / g and more particularly of at least 15,000 ml / q.
- This intrinsic viscosity is determined by the extrapolation at zero concentration of the reduced specific viscosity curve.
- succinoglycans obtained from an Agrobacterium tumefaciens I-736 strain one of its recombinants or one of its mutants.
- Agrobacterium tumefaciens strain was deposited in accordance with the Budapest Treaty with the National Collection of Culture of Microorganisms (CNCM), on March 1, 1988, where it is publicly accessible under number 1736. This strain comes from the National Collection of Phytophathogenic Bacteria and is listed under number CNBP 291 in the 1974 catalog of the curator.
- the pure culture of Agrobacterium tumefaciens I-736 can be carried out in an inclined agar tube (slant) incubated at a temperature between 26 and 32 ° C, and more generally between 28 and 32 ° C.
- the following maintenance media were considered particularly advantageous for the cultivation of Agrobacterium tumefaciens I-736: - MY Agar medium (in g / l) Soy-Peptones 5 Yeast extract 3 Malt extract 3 Glucose 10 Agar 20 - TGY Agar medium (produced by the Pasteur Institute (in g / l) Peptones 5 Yeast extract 2.5 Glucose 1 Agar 20 - Middle Bennett Agar (in g / l) Peptones 1 Meat extract 1 NZ Amine A R 2 (Produced by Sheffield Chemical Co.) Glucose 10 Agar 20 - TS Agar medium (produced by Sté Bio Mérieux) (in g / l) Bio trypcase 17 Bio soyase 3 K2HPO4 2.5 NaCl 5 Glucose 2.5 Agar 20
- the Agrobacterium tumefaciens I-736 strain can also be cultivated in a Petri dish, for example on MY agar or TGY agar medium. Under these conditions, the colonies are visible from 24 to 30 hours, and have the following characteristics, at 48 hours: - cut ; 2 to 3 mm in diameter - smooth and slightly curved appearance - very light brown-yellow color - colonies with a clear edge and less mucoid on a Petri dish than on a slant.
- the Agrobacterium tumefaciens I-736 strain can use the following sugars: - glucose - sucrose - starch hydrolysates and optionally native starch and lactose.
- Glucose and sucrose are preferred sugars.
- succinoglycan obtained from this strain comprises units derived from glucose, galactose and pyruvic, succinic and acetic acids or salts of these acids, generally in proportions molars respectively of 5-8 / 1-2 / 0.5-2 / 0.5-2 / 0.05-2 preferably of 6 -7.5 / 1 - 1.5 / 0.5 - 1/0 , 5 - 1 / 0.05-0.2 and more preferably still from 7/1 / 0.5 - 1 / 0.5 - 1 / 0.05 - 0.1.
- Said pyruvic, succinic and acetic acids are generally in the form of salts such as sodium, potassium, calcium or ammonium salts.
- succinoglycan The methods of analysis of succinoglycan which have made it possible to determine its crude formula as specified above, have as a principle the determination of the constituent elements (sugars and acids) after hydrolysis of said succinoglycan and chromatographic assays by internal or external calibration.
- succinoglycan are hydrolyzed in hermetic tubes with 5 ml of molar trifluoroacetic acid at 105 ° C for three to six hours.
- the sugar dosage is then carried out by gas chromatography with F.I.D detection, on a capillary glass column 25 m long and 0.25 mm in diameter, loaded with methylsilicone phase having a film thickness of 0.14 ⁇ .
- the carrier gas used is hydrogen, with a flow rate of 2 ml / minute.
- the dosage of pyruvic acid is carried out from a stock solution obtained by hydrolysis of 80 mg of succinoglycan using 5 ml of 4N hydrochloric acid for 1 hour at 105 ° C., then addition of 2 mg of acid ketoglutaric (constituting the internal standard) and adjustment to 25 ml by distilled water.
- the assay is then carried out by High Performance Liquid Chromatography (HPLC) using a column loaded with C18 grafted silica of 5 ⁇ in diameter, the length of which is 250 mm and the diameter of 4.6 mm.
- the eluent used is a 50/50 mixture by volume of 0.02 M phosphoric acid and acetonitrile.
- the flow rate is 1.5 ml / minute.
- the detection of pyruvic acid is done by Ultraviolet at 375 nm.
- the determination of succinic acid is carried out after hydrolysis of the succinoglycan under the same conditions as those used for the determination of pyruvic acid.
- the assay is direct, by external calibration.
- the standard succinic acid solution used contains 8 mg of succinic acid in 25 ml of water.
- the HPLC technique is again used on Aminex HPX87H R columns from BIORAD R.
- the eluent is 0.01 N sulfuric acid, and the flow rate is 0.8 ml / minute.
- the detection of succinic acid is refractometric.
- acetic acid is carried out after hydrolysis of 300 to 350 mg of succinoglycan with 5 ml of 4 N trifluoroacetic acid at 120 ° C for three hours. Then 30 mg of propionic acid is added as an internal standard and assayed by gas chromatography with FID detection
- a glass column 2 m long and 3 mm in diameter is used, filled with 5% FFAP phase and 1% phosphoric acid absorbed on chromosorb G R (AW DMCS) from 80 to 100 mesh.
- the carrier gas is helium with a flow rate of 30 ml / minute.
- succinoglycans of the family described above generally also have the following properties:
- Their intrinsic viscosity is between 3000 and 25000 ml / g and more particularly between 14000 and 25000 ml / g and preferably between 15000 and 24000 ml / g.
- the intrinsic viscosity ( ⁇ ) as specified is determined by extrapolation at zero concentration of the reduced viscosity formula in which: - ⁇ is the viscosity of the solution on the Newtonian plateau - ⁇ o is the viscosity of the solvent and - C is the succinoglycan concentration, using the Huggins equation; k ′ being Huggins constant on the 1st Newtonian plateau
- the specific viscosity is measured as follows:
- a stock solution of 0.2 g / l of succinoglycan is prepared in a 0.1 M NaCl aqueous solution.
- succinoglycan at concentrations between 0.03 and 0.1 g / l by dilution of the mother solution with the 0.1 M Nacl aqueous solution.
- the measurements are then carried out at 23 ° C. using a LOW SHEAR viscometer.
- the specific viscosity curve is plotted as a function of the concentration and extrapolated to zero concentration.
- the molecular weights of these succinoglycans measured by light scattering are generally between 6.106 and 10.106, preferably between 6.5.106 and 9.5.106.
- succinoglycans also have very good rheological properties in solution in distilled water, especially at low concentrations.
- solutions at 0.1% by weight of a succinoglycan of this type in distilled water at 25 ° C have viscosities at 24 hours greater than 400 mPa.s and more particularly between 400 and 700 mPa.s; the viscosities being measured at a speed gradient of 1 s ⁇ 1 using a LOW SHEAR viscometer.
- aqueous solutions of one of these succinoglycans at pH 1.7 and at 25 ° C., have a viscosity at 24 hours of between 1000 and 2500 mPa.s, more particularly between 1400 and 2000 mPa.s, the viscosities being measured using a LOW SHEAR viscometer, at a speed gradient of 1 s ⁇ 1.
- succinoglycans from the Agrobacterium tumefaciens I-736 strain can be obtained by a process which will be described in more detail below.
- succinoglycans result from the fermentation by the aforementioned strain of a medium comprising at least one assimilable carbon source.
- the medium is conventionally innoculated by the Agrobacterium tumefaciens I-736 strain.
- the volume of the fermentation medium When the volume of the fermentation medium is large, it can advantageously be inoculated by means of an innoculum medium, seeded with a liquid preculture medium; the latter being previously seeded itself by a pure culture of Agrobacterium tumefaciens I-736.
- any medium conventionally used for this purpose can be used, and advantageously a medium of a mineral nature.
- organic source of carbon constituting the fermentation medium there may be mentioned sugars such as glucose, sucrose, starch hydrolysates, and optionally lactose or native starch, as well as mixtures of these sugars. Glucose and sucrose are preferred sugars.
- the concentration of organic carbon source in the fermentation medium can be between 1 and 100 g / l and preferably between 15 and 60 g / l.
- the fermentation medium can also contain at least one nitrogen source, preferably a source of organic nitrogen and optionally one or more mineral salts.
- the concentration of nitrogenous organic source in the fermentation medium can be between 3 and 80 g / l and preferably between 5 and 50 g / l.
- mineral salts which may optionally be introduced into the fermentation medium, of the sulfates such as magnesium, manganese, zinc, iron sulfates, carbonates such as calcium carbonate, the salts soluble calcium, phosphates such as potassium, sodium phosphates.
- the concentration of each of these mineral salts in the fermentation medium can vary between 0.01 and 5 g / l and preferably between 0.05 and 2 g / l.
- the fermentation medium can also contain trace elements such as traces of cobalt and / or molybdenum salts, as well as vitamins and nucleotides.
- Fermentation can be carried out at pressures between 1 and 4 bar at a temperature between 25 and 35 ° C, preferably between 28 and 32 ° C, under submerged aerobic conditions.
- the pH of the fermentation medium can be between 5 and 9 and preferably between 6 and 8.
- the pH can be adjusted, as the case may be, with a base such as soda or potash or with an acid such as acid sulfuric, phosphoric acid, hydrochloric acid or nitric acid.
- the fermentation medium placed for example in a fermentation tank or container, can advantageously be subjected to stirring.
- This agitation can be exercised for example by means of a reciprocal shaker, a gyratory shaker, a stirring mobile or a bubble column.
- the fermentation time is usually more than 30 hours, but is generally between 40 and 90 hours.
- Fermentation yields are generally greater than 40%, more particularly between 55-75% and very particularly between 60 and 75% by weight of succinoglycan produced relative to the carbon source used.
- the succinoglycan can be separated from the fermentation medium.
- the fermentation must containing the succinoglycan can advantageously be heated to temperatures between 80 and 120 ° C, for 10 to 60 minutes and preferably between 15 and 45 minutes.
- the must subjected to the above heat treatment advantageously has a pH of between 6 and 8.
- this pH can be adjusted if necessary, with a base or an acid as appropriate.
- the latter can be chosen from the bases and the acids mentioned above used for adjusting the pH of the fermentation medium.
- Suitable organic liquids according to the present invention of acetone, alcohols such as ethanol, propanol, isopropanol, butanol and tert-butanol.
- Isopropanol is more particularly preferred in the context of the present invention.
- the volume of organic liquid used is generally 2 to 3 times that of the volume of must to be treated.
- the precipitation of succinoglycan by an organic liquid can also be carried out in the presence of salts such as sulfates, chlorides or phosphates of sodium, potassium, or calcium.
- succinoglycan once precipitated, can then be separated from the organic liquid by filtration, centrifugation or spinning.
- the fibers obtained can be dehydrated, for example using acetone or an alcohol such as ethanol, propanol, isopropanol or tert-butanol.
- the weight of alcohol required to perform this dehydration operation is generally 1 to 10 times that of the fibers to be treated.
- the dehydrated fibers can undergo new centrifugation or spin filtration operations.
- the fibers can then be dried, ground and sieved to obtain a powder.
- enzymes which may be suitable for this purpose, mention may be made of proteases, mutanases, lipoproteases, cellulases and chitinases.
- Enzymatic purification can be combined or replaced by physical purification methods such as the various modes of filtration, of dialysis, or by the various techniques of chromatography.
- Fermentation musts and reconstituted aqueous solutions of succinoglycan, whether or not subjected to a purification treatment, can be concentrated. Concentration can be advantageous in certain cases, in particular insofar as transport costs can be reduced. In addition, concentrated solutions can be implemented more quickly than powders. Concentration can be achieved by techniques such as evaporation, ultrafiltration, or by diafiltration.
- succinoglycans are used, in the context of the invention, in solid form in powder or in aqueous solution.
- succinoglycan generally used from 0.001 to 2% by weight, preferably between 0.01 and 0.5% by weight of succinoglycan relative to the final suspension.
- suspensions of the invention comprising a succinoglycan of the type described above are particularly stable.
- this dispersant is chosen from the group of siliconates and their derivatives.
- Siliconates are well known products, they are salts of siliconic acid or its derivatives.
- R is a hydrocarbon residue generally of 1 to 18 carbon atoms, optionally substituted by a halogen atom, an amino group, ether, ester, epoxy, mercapto, cyano, (poly) glycol
- m is an integer or fractional number varying between 0.1 and 3
- M is an alkali metal or an ammonium or phosphonium group.
- R is a hydrocarbon residue of 1 to 10 carbon atoms and more particularly of 1 to 6 atoms.
- R can be an alkyl radical, for example methyl, ethyl, propyl, butyl, isobutyl; an alkenyl radical such as for example vinyl, an aryl radical, for example phenyl or naphthyl, an arylalkyl radical such as for example benzyl or phenylethyl, alkylaryl such as for example tolyl, xylyl, or an araryl radical such as biphenylyl.
- alkyl radical for example methyl, ethyl, propyl, butyl, isobutyl
- an alkenyl radical such as for example vinyl
- an aryl radical for example phenyl or naphthyl
- an arylalkyl radical such as for example benzyl or phenylethyl
- alkylaryl such as for example tolyl, xylyl, or an araryl radical such as biphenylyl.
- R ′ are identical or different and are hydrocarbon residues of 1 to 6 carbon atoms.
- alkaline siliconates are used.
- Alkaline earth siliconates can also be used.
- alkylsiliconates and in particular alkaline alkylsiliconates such as, for example, sodium or potassium methylsiliconates.
- alkali or alkaline earth siliconates are products, most of which are commercially available.
- silanes having 3 hydrolyzable groups such as halogen atoms, alkoxy radicals, followed by dissolution of the product obtained in a solution of a strong inorganic base in proportions such as there is at least one equivalent in base per atom of silicon (see for example US-A-2,441,422, US-A-2,441,423).
- the dispersant can also be chosen from siliconate derivatives.
- derivative products is meant here the condensation products of the products corresponding in particular to formula (1) described above, or those resulting from the at least partial polymerization into silicone compounds or polymers.
- alkali metal alkylsiliconates can be transformed into polyalkylsiloxanes, in particular by the action of carbon dioxide or other acidifying agent.
- silicone resins As a second type of dispersant suitable for the present invention, mention may also be made of silicone resins.
- silicone resins are well-known and commercially available branched organopolysiloxane polymers. They present, per molecule, at least two different motifs chosen among those of formula R3SiO 0.5 (unit M), R2SiO (unit D), RSiO 1.5 (unit T) and SiO2 (unit Q).
- radicals R are identical or different and are chosen from linear or branched alkyl radicals, these radicals more particularly having from 1 to 6 carbon atoms included, vinyl, phenyl, trifluoro-3,3,3 propyl radicals.
- alkyl radicals R of methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.
- These resins are generally hydroxylated and in this case have a weight content of hydroxyl group of between 0.1 and 10%.
- resins examples include MQ resins, MDQ resins, TD resins and MDT resins.
- Resins having a molecular mass of less than 25,000 can be used more particularly.
- the siliconates are usually used in the form of aqueous solutions.
- the amount of siliconate used depends on the specific surface of the zeolite. This amount is usually between 0.01 and 2%, more particularly between 0.05 and 0.3% by weight relative to the final suspension. This quantity is understood for a solution at 50% by weight in water of the siliconate or derivative.
- the resins can be used in the solid state or in the form of aqueous emulsions or emulsion or solution in an organic solvent.
- the amounts used are between 0.01 and 2% by weight of solid product, more particularly between 0.05 and 0.3 relative to the final suspension.
- siliconates or derivatives and resins as defined above has the effect of considerably lowering the viscosity of the zeolite suspensions. It also makes it possible to obtain stable suspensions with a higher dry extract, for example at least 55%.
- dispersants can be used.
- these dispersants can be used alone or in combination and even optionally in combination with the siliconates, their derivatives or the resins.
- dispersants can be chosen from the group comprising nonionic or anionic surfactants, macromolecular organic polymer compounds carrying carboxyl and / or hydroxyl groups, phosphates.
- nonionic surfactants use may generally be made of compounds obtained by condensation of alkylene oxide with an organic compound which may be aliphatic or alkylaromatic.
- alkali metal soaps alkali sulfonates, such as methylnaphthalene sulfonate, xylenesulfonate, beta-sulfoethyl esters of fatty acids, sulfates and sulfated products such as alkyl sulfates, fatty alcohols polyoxyethylenated and sulphated.
- the polymers of acrylic, hydroxyacrylic, maleic, itaconic acids, the copolymers of the acids mentioned above may be given together or with unsaturated compounds ethylenic such as ethylene, propylene, vinyl alcohol, vinyl acetate, methacrylic acid.
- unsaturated compounds ethylenic such as ethylene, propylene, vinyl alcohol, vinyl acetate, methacrylic acid.
- phosphates these can be chosen from the group of primary or secondary esters of orthophosphoric acid or one of its salts and mono or diesters of this acid or of its polyoxyethylenated salts. Mention may also be made of inorganic in particular alkaline phosphates such as pyrophosphate, tripolyphosphate, sodium hexametaphosphate.
- the zeolite suspensions according to the invention are prepared in a simple manner by introducing the additives described above into the suspension and mixture. If necessary the pH of the zeolite suspension can be adjusted to the desired value in a known manner by the addition of any suitable neutralizing agent.
- Suspensions comprising zeolites and stabilized by the systems which have just been described can be used in numerous applications.
- They can be used in the form of suspensions based essentially on zeolites and the stabilizing additives mentioned above. In this case, they can enter into the preparation of detergent compositions. They can be used in any field other than detergency for which zeolites are used, for example in stationery.
- the present invention also covers detergent compositions, in particular for liquid detergents, comprising, in addition to the suspensions based on zeolite and stabilizers of the invention, all the other additives known in detergency such as bleaching agents, foam control agents, anti-redeposition agents, perfumes, solvents, enzymes, optical agents.
- the dry extract of the suspension is given in percentage by weight of anhydrous zeolite determined by a measurement of loss on ignition at 850 ° C. for one hour.
- the pH indicated is given for an aqueous dispersion containing 1% of dry zeolite and it is measured using a high alkalinity pH electrode.
- the exchange capacity is given by the amount of calcium (expressed in mg of CaCO3) exchanged with 1 g of anhydrous zeolite at 25 ° C.
- the measurement is carried out in the following manner: 0.4 g of zeolite (expressed as anhydrous) is introduced into a solution of 5.10 ⁇ 3 mole / l CaCl2. The mixture is kept stirring for 15 minutes. After filtration, the excess calcium is dosed at pH 10 in return by EDTA in the presence of a colored indicator, black eriochrome T.
- the RHEOMAT 30 equipped with the centered measurement system B is used as rheometer.
- the measurement consists in performing a cycle in speed gradient (ascent plus descent).
- the range of speed gradient explored is between 0.0215 and 157.9 s ⁇ 1, which corresponds to rotational speeds of the mobile from 0.0476 to 350 revolutions per minute.
- the viscosities reported in the examples correspond to measurements obtained during the descent in speed gradient.
- the sedimentation is determined by introducing the zeolite suspension into graduated cylinders from 50 to 100 cc. The volumes of supernatant and decantate are measured every five days. The test pieces are left at room temperature (20 ° C) or placed in a thermostatically controlled enclosure.
- the zeolite used is a 4A zeolite with an average diameter of primary particles of 3.5 ⁇ m.
- succinoglycan used in the following examples can be prepared as follows:
- a medium Agrobacterium tumefaciens I-736 is fermented containing a medium (in g / l): CSL (corn steap liquor) 11 K2 HPO4 4 MgSO4, 7H2O 0.5 Sucrose 25 Drinking water qs 1 l
- This medium is fermented by said strain at a temperature of 28 ° C., in a 20 liter BIOLAFFITE R tank containing a useful volume of 15 liters.
- the medium is subjected to stirring at 400 revolutions / min obtained by means of RUSHTON R type mobiles.
- the medium is aerated under an air flow of 825 l / h.
- the must is heat treated at 90 ° C for 30 min.
- IPA isopropyl alcohol
- the fibers from the precipitation are then dehydrated twice in the presence of 1200 ml of IPA.
- the fibers are then wrung, shredded and dried in an oven at 85 ° C.
- the collected dry matter is crushed and sieved.
- a cream-colored product powder is then obtained.
- the suspension contains 45% by weight of zeolite.
- Table 1 Example 1 2 3 comparative. Succinoglycan% by weight relative to the suspension 0.1 0.05 0 pH 11.48 11.48 11.52 Sedimentation supernatant% volume 20 ° C 50 ° C 20 ° C 20 ° C 50 ° C 5 days 0 2 ⁇ 1 16 21 10 days ⁇ 1 2 2.5 18 23 15 days 1 2 3 20 23 % Volume decantate 5 days 0 0 0 60 60 10 days 0 0 0 60 77 15 days 0 0 "1 80 77
- RHODORSIL 51 T the quantities indicated are in percentages by weight for a 50% aqueous solution of siliconate.
- Resin A is a resin of the type described above for which R is a methyl radical. This resin is used here in the dry or solid state. It is marketed by the Applicant in the form of an emulsion under the reference RHODORSIL 865 A.
- Example 8 is a low quantity example of succinoglycan.
- Example 9 a resin "Resin B” is used which is a resin of the type described above in which R is methyl.
- This resin is used here in the dry state. It is marketed by the Applicant in the form of an emulsion and under the reference RHODORSIL 878 A.
- Example 10 describes the use as a dispersant of a nonionic surfactant of the sucroglyceride type sold by the Applicant under the name CELYNOL X8063.
- Example 11 describes the use as a dispersant of a nonionic surfactant of the ethoxylated tristirylphenol type sold under the name SOPROPHOR S25, sold by the Applicant.
- Example 12 relates to a dispersant of the anionic surfactant type which is a phosphated ethoxylated tristyrylphenol marketed under the name SOPROPHOR FL, marketed by the Applicants.
- Examples 13 to 14 relate to acrylic polymers.
- Polymer 1 is an acrylic homopolymer with a mass of 2000.
- Polymer 2 is an acrylic-maleic copolymer with a mass of 70,000 and an acrylic / maleic ratio of 60/40.
- Example 8 9 Suspension% anhydrous zeolite 49.6 49.3 Exchange capacity 295 Succinoglycan in% by weight relative to the suspension 0.02 0.12 Dispersant% by weight relative to the suspension Siliconate 0.2 Resin B 0.2 pH of the suspension 10.67 11.49 Rheology Viscosity (poises) at 4.74s ⁇ 1 13.3 14 at 32s ⁇ 1 6.9 12.6 Sedimentation Supernatant in% of volume 5 days 1 5 10 days 5 15 days 2 5 Decantate in% of volume 5 days 2.5 0 10 days 0 15 days 0 Example 10 11 12 13 14 Suspension% anhydrous zeolite 49.3 49.3 49.3 49.3 49.3 Exchange capacity Succinoglycan in% by weight relative to the suspension 0.04 0.04 0.04 0.08 0.08 Dispersant% by weight relative to the suspension CELANOL 0.2 SOPROPHOR S25 0.2 SOPROPHOR FL 0.2 POLYMER 1 0.2 POLYMER 2 0.2
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Abstract
Description
La présente invention concerne des suspensions aqueuses stables de zéolites.The present invention relates to stable aqueous suspensions of zeolites.
L'utilisation des zéolites en détergence est bien connue. Cette utilisation s'est développée notamment par suite de la substitution au moins partielle des zéolites aux phosphates dans les lessives. On a reproché, en effet, à ces derniers de provoquer une eutrophisation des eaux et donc de poser des problèmes écologiques.The use of zeolites in detergency is well known. This use has developed in particular as a result of the at least partial substitution of zeolites for phosphates in detergents. They have been criticized, in fact, for causing eutrophication of the waters and therefore for posing ecological problems.
Les zéolites sont généralement employées sous forme de suspensions ou bouillies aqueuses qui peuvent être par exemple introduites dans des bouillies de lessives qui peuvent être ensuite atomisées.Zeolites are generally used in the form of aqueous suspensions or slurries which can for example be introduced into detergent slurries which can then be atomized.
Or, ces suspensions de zéolite ont tendance à sédimenter ou à gélifier, ce qui les rend difficilement transportables ou stockables. On observe, en effet, très souvent à l'issue du transport ou après une plus ou moins longue période de stockage le dépôt d'une couche dure de pigment surmontée d'une bouillie plus fluide mais pauvre en matière sèche.However, these zeolite suspensions tend to sediment or gel, which makes them difficult to transport or store. We observe, in fact, very often at the end of transport or after a more or less long storage period the deposition of a hard layer of pigment topped with a more fluid slurry but poor in dry matter.
En outre, il est généralement impossible de remettre la zéolite en suspension ou d'obtenir une bouillie présentant une viscosité suffisamment faible pour être pompable et donc utilisable industriellement. Il y a donc là un problème bien réel.In addition, it is generally impossible to resuspend the zeolite or to obtain a slurry having a viscosity low enough to be pumpable and therefore usable industrially. So there is a very real problem there.
L'objet principal de l'invention est donc un moyen permettant d'obtenir une suspension aqueuse de zéolite qui soit stable, c'est-à-dire qui ne sédimente plus ou que très peu après plusieurs jours de stockage.The main object of the invention is therefore a means of obtaining an aqueous suspension of zeolite which is stable, that is to say which no longer sediments or only very shortly after several days of storage.
Un second objet de l'invention est un moyen d'obtenir une suspension aqueuse de zéolite qui soit non seulement stable, mais qui, en outre, soit pompable, c'est-à-dire qui présente une viscosité convenable pour une utilisation industrielle.A second object of the invention is a means of obtaining an aqueous suspension of zeolite which is not only stable, but which, moreover, is pumpable, that is to say which has a viscosity suitable for industrial use.
Dans ce but, les suspensions selon l'invention comprennent des zéolites et elles sont caractérisées en ce qu'elles comportent en outre un succinoglycane.For this purpose, the suspensions according to the invention comprise zeolites and they are characterized in that they also comprise a succinoglycan.
Par ailleurs, selon un mode de réalisation particulier de l'invention, les suspensions aqueuses de zéolites comprennent en outre un dispersant qui est un siliconate et/ou un de ses dérivés.Furthermore, according to a particular embodiment of the invention, the aqueous suspensions of zeolites further comprise a dispersant which is a siliconate and / or one of its derivatives.
Enfin, selon un autre mode de réalisation de l'invention, les suspensions aqueuses de zéolites comprennent en outre un dispersant qui est une résine silicone.Finally, according to another embodiment of the invention, the aqueous suspensions of zeolites further comprise a dispersant which is a silicone resin.
D'autres caractéristiques et détails de l'invention seront mieux compris à la lecture de la description qui va suivre et des exemples concrets mais non limitatifs donnés ci-après.Other characteristics and details of the invention will be better understood on reading the description which follows and concrete but nonlimiting examples given below.
Les zéolites utilisées dans le cadre de la présente invention comprennent les zéolites cristallines, amorphes et mixtes cristallines-amorphes, naturelles ou synthétiques.The zeolites used in the context of the present invention include crystalline, amorphous and mixed crystalline-amorphous, natural or synthetic zeolites.
Bien entendu, on choisira de préférence celles capables de réagir suffisamment rapidement avec les ions calcium et/ou magnésium, de manière à pouvoir adoucir les eaux de lavage.Of course, preferably those capable of reacting quickly enough with the calcium and / or magnesium ions will be chosen so as to be able to soften the washing waters.
Généralement, on utilise les zéolites finement divisées présentant un diamètre moyen de particules primaires compris entre 0,1 et 10µm et, avantageusement, entre 0,5 et 5µm, ainsi qu'un pouvoir d'échange théorique de cations supérieur à 100 mg de CaCO₃/g de produit anhydre et de préférence supérieur à 200 mg.Generally, finely divided zeolites are used having an average diameter of primary particles of between 0.1 and 10 μm and, advantageously, between 0.5 and 5 μm, as well as a theoretical cation exchange power greater than 100 mg of CaCO₃ / g of anhydrous product and preferably greater than 200 mg.
On utilise aussi plus particulièrement les zéolites de type A, X ou Y et notamment 4A et 13X.Use is also more particularly made of zeolites of type A, X or Y and in particular 4A and 13X.
A titre d'exemple de zéolites pouvant être employées dans le cadre de la présente invention, on peut citer les produits faisant l'objet des demandes de brevets français n° 2 225 568, 2 269 575, 2 283 220 dont l'enseignement est incorporé ici.By way of example of zeolites which can be used in the context of the present invention, mention may be made of the products which are the subject of French patent applications n ° 2 225 568, 2 269 575, 2 283 220 whose teaching incorporated here.
On peut citer plus particulièrement les zéolites obtenues par les procédés décrits dans les demandes de brevets français au nom de la Demanderesse n° 2 376 074, 2 384 716, 2 392 932, 2 528 722 dont l'enseignement est aussi incorporé à la présente demande. La dernière référence citée fait notamment état de zéolites présentant une constante de vitesse, rapportée à la surface des zéolites par litre de solution supérieure à 0,15 s⁻¹.l.m⁻², de préférence supérieure à 0,25 et avantageusement comprise entre 0,4 et 4 s⁻¹.l.m⁻². Ces zéolites ont des qualités particulièrement intéressantes dans l'utilisation en détergence.Mention may more particularly be made of the zeolites obtained by the processes described in the French patent applications in the name of the Applicant No. 2,376,074, 2,384,716, 2,392,932, 2,528,722, the teaching of which is also incorporated herein request. The last reference cited refers in particular to zeolites having a speed constant, related to the surface of the zeolites per liter of solution greater than 0.15 s⁻¹.lm⁻², preferably greater than 0.25 and advantageously between 0.4 and 4 s⁻¹.lm⁻². These zeolites have particularly advantageous qualities in the use in detergency.
La demande n° 2 392 932 notamment fait état de zéolites obtenues par un procédé consistant à injecter une solution de silicate de sodium dans l'axe d'un venturi alors qu'on injecte une solution d'aluminate de sodium coaxialement au même venturi avec recyclage du mélange obtenu.Application No. 2,392,932 in particular mentions zeolites obtained by a process consisting in injecting a sodium silicate solution in the axis of a venturi while a sodium aluminate solution is injected coaxially with the same venturi with recycling of the mixture obtained.
On obtient notamment des zéolites de formule :
x Na₂O, y Al₂O₃, zSiO₂, wH₂O
dans laquelle si y = 1, x = 1, z = 1,8 à 2, w = 0 à 5 et présentant une granulométrie répondant à la distribution suivante en nombre 95% < 10µm, 99% < 15µm, 50% compris entre 2 et 6µm pour le diamètre moyen.In particular, zeolites of the formula are obtained:
x Na₂O, y Al₂O₃, zSiO₂, wH₂O
in which if y = 1, x = 1, z = 1.8 to 2, w = 0 to 5 and having a particle size corresponding to the following distribution in number 95% <10µm, 99% <15µm, 50% between 2 and 6µm for the average diameter.
Les suspensions peuvent présenter une concentration en zéolite variable et fonction de l'application. En détergence, cette concentration est généralement comprise entre 40 et 51% en poids.The suspensions may have a variable zeolite concentration depending on the application. In detergency, this concentration is generally between 40 and 51% by weight.
Le pH des suspensions est aussi fonction de leur utilisation. Toujours dans l'application détergence, ce pH exprimé à 1% en poids de zéolite sèche, est d'environ 11.The pH of the suspensions is also a function of their use. Still in the detergency application, this pH expressed at 1% by weight of dry zeolite is approximately 11.
Selon la caractéristique principale de l'invention, on emploie un succinoglycane comme agent stabilisant des suspensions de zéolite.According to the main characteristic of the invention, a succinoglycan is used as a stabilizing agent for zeolite suspensions.
Grâce à cet agent stabilisant, on obtient des suspensions qui après plusieurs jours de stockage ne décantent pas ou qui présentent tout au plus un léger sédiment facile à remettre en suspension.Thanks to this stabilizing agent, suspensions are obtained which after several days of storage do not settle or which at most have a slight sediment which is easy to resuspend.
Un succinoglycane est un polysaccharide contenant de l'acide succinique et du galactose et du glucose comme sucres.A succinoglycan is a polysaccharide containing succinic acid and galactose and glucose as sugars.
Les succinoglycanes sont généralement obtenu par fermentation d'un milieu comportant au moins une source de carbone assimilable par une souche ou un recombinant ou un mutant de cette souche du type donné ci-dessous :
- Pseudomonas, notamment d'origine NCIB 11592
- Rhizobium meliloti, notamment d'origine U-27, 1021, SU-27, SU-4, SU-231, SU-255, SU-256, K 24 (R 13), A 148 (R 15), J 7017
- Rhizobium trifolii, notamment d'origine J-60W
- Alcaligenes faecalis de variétés myxogènes, notamment d'origine 10C3,22-33
- Agrobacterium radiobacter, notamment d'origine IFO 13533
- Agrobacterium rhizogenes, notamment d'origine IFO 13259
- Agrobacterium tumefaciens, notamment d'origine IFO 3058, A-8, A-10.The succinoglycans are generally obtained by fermentation of a medium comprising at least one carbon source assimilable by a strain or a recombinant or a mutant of this strain of the type given below:
- Pseudomonas, in particular of origin NCIB 11592
- Rhizobium meliloti, in particular of origin U-27, 1021, SU-27, SU-4, SU-231, SU-255, SU-256, K 24 (R 13), A 148 (R 15), J 7017
- Rhizobium trifolii, in particular of origin J-60W
- Alcaligenes faecalis of myxogenic varieties, in particular of origin 10C3,22-33
- Agrobacterium radiobacter, in particular of origin IFO 13533
- Agrobacterium rhizogenes, in particular of IFO 13259 origin
- Agrobacterium tumefaciens, in particular of origin IFO 3058, A-8, A-10.
De préférence, on choisit un succinoglycane dans le groupe de ceux qui, après avoir passé la température de transition, présentent une viscosité intrinsèque d'au moins 14000 ml/g et plus particulièrement d'au moins 15000 ml/q.Preferably, a succinoglycan is chosen from the group of those which, after having passed the transition temperature, have an intrinsic viscosity of at least 14,000 ml / g and more particularly of at least 15,000 ml / q.
Cette viscosité intrinsèque est déterminée par l'extrapolation à concentration nulle de la courbe de viscosité spécifique réduite.This intrinsic viscosity is determined by the extrapolation at zero concentration of the reduced specific viscosity curve.
Dans le cadre de la présente invention, une famille très intéressante de produits s'est révélée être celle comprenant les succinoglycanes obtenus à partir d'une souche Agrobacterium tumefaciens I-736, un de ses recombinants ou un de ses mutants.In the context of the present invention, a very interesting family of products has turned out to be that comprising the succinoglycans obtained from an Agrobacterium tumefaciens I-736 strain, one of its recombinants or one of its mutants.
La dite souche Agrobacterium tumefaciens a été déposée conformément au Traité de Budapest, auprès de la Collection Nationale de Culture des Microorganismes (CNCM), le 1er mars 1988, où elle est publiquement accessible sous le n° 1736. Cette souche provient de la Collection Nationale de Bactéries Phytophathogène et est répertoriée sous le numéro CNBP 291 dans le catalogue 1974 de l'organisme curateur.The so-called Agrobacterium tumefaciens strain was deposited in accordance with the Budapest Treaty with the National Collection of Culture of Microorganisms (CNCM), on March 1, 1988, where it is publicly accessible under number 1736. This strain comes from the National Collection of Phytophathogenic Bacteria and is listed under number CNBP 291 in the 1974 catalog of the curator.
La culture pure d'Agrobacterium tumefaciens I-736 peut être effectuée en tube gélose incliné (slant) incubé à une température comprise entre 26 et 32°C, et plus généralement entre 28 et 32°C.The pure culture of Agrobacterium tumefaciens I-736 can be carried out in an inclined agar tube (slant) incubated at a temperature between 26 and 32 ° C, and more generally between 28 and 32 ° C.
A ces températures et notamment sur des milieux à base de MY agar et de Bennett agar, dont les compositions sont indiquées ci-dessous, on a pu observer la formation d'un tapis mucoïde bactérien recouvrant la totalité du slant dès 20 heures.At these temperatures, and in particular on media based on MY agar and Bennett agar, the compositions of which are indicated below, it has been possible to observe the formation of a bacterial mucoid mat covering the entire slant from 20 hours.
Les milieux d'entretien suivants ont été considérés comme particulièrement avantageux pour la culture d'Agrobacterium tumefaciens I-736 :
La souche Agrobacterium tumefaciens I-736 peut également être cultivée en boîte de Petri, par exemple sur milieu MY agar ou TGY agar.
Dans ces conditions les colonies sont visibles dès 24 à 30 heures, et présentent les caractéristiques suivantes, à 48 heures :
- taille ; 2 à 3 mm de diamètre
- aspect lisse et peu bombé
- couleur brun-jaune très clair
- colonies à bord net et moins mucoïde sur boîte de Petri que sur slant.The Agrobacterium tumefaciens I-736 strain can also be cultivated in a Petri dish, for example on MY agar or TGY agar medium.
Under these conditions, the colonies are visible from 24 to 30 hours, and have the following characteristics, at 48 hours:
- cut ; 2 to 3 mm in diameter
- smooth and slightly curved appearance
- very light brown-yellow color
- colonies with a clear edge and less mucoid on a Petri dish than on a slant.
La souche Agrobacterium tumefaciens I-736 peut utiliser les sucres suivants :
- glucose
- saccharose
- hydrolysats d'amidon
et éventuellement l'amidon natif et le lactose.The Agrobacterium tumefaciens I-736 strain can use the following sugars:
- glucose
- sucrose
- starch hydrolysates
and optionally native starch and lactose.
Le glucose et le saccharose sont des sucres préférés.Glucose and sucrose are preferred sugars.
Il a pu être mis en évidence que, d'une manière générale le succinoglycane obtenu à partir de cette souche comporte des motifs dérivés du glucose, du galactose et des acides pyruvique, succinique et acétique ou des sels de ces acides, généralement selon des proportions molaires respectivement de 5-8/1-2/0,5-2/0,5-2/0,05-2 de préférence de 6 -7,5 / 1 - 1,5/ 0,5 - 1/ 0,5 - 1/0,05-0,2 et plus préférentiellement encore de 7 / 1 / 0,5 - 1 / 0,5 - 1 / 0,05 - 0,1.It has been possible to demonstrate that, in general, the succinoglycan obtained from this strain comprises units derived from glucose, galactose and pyruvic, succinic and acetic acids or salts of these acids, generally in proportions molars respectively of 5-8 / 1-2 / 0.5-2 / 0.5-2 / 0.05-2 preferably of 6 -7.5 / 1 - 1.5 / 0.5 - 1/0 , 5 - 1 / 0.05-0.2 and more preferably still from 7/1 / 0.5 - 1 / 0.5 - 1 / 0.05 - 0.1.
Lesdits acides pyruvique, succinique et acétique se présentent généralement sous forme de sels tels que des sels de sodium, de potassium, de calcium ou d'ammonium.Said pyruvic, succinic and acetic acids are generally in the form of salts such as sodium, potassium, calcium or ammonium salts.
Les méthodes d'analyse du succinoglycane qui ont permis de déterminer sa formule brute telle que spécifiée ci-dessus, ont pour principe la détermination des éléments constitutifs (sucres et acides) après hydrolyse dudit succinoglycane et dosages chromatographiques par étalonnage interne ou externe.The methods of analysis of succinoglycan which have made it possible to determine its crude formula as specified above, have as a principle the determination of the constituent elements (sugars and acids) after hydrolysis of said succinoglycan and chromatographic assays by internal or external calibration.
Ainsi, le dosage des sucres a été réalisé de la manière suivante :
100 mg de succinoglycane sont hydrolysés en tubes hermétiques par 5 ml d'acide trifluoroacétique molaire à 105°C pendant trois à six heures.Thus, the dosage of sugars was carried out as follows:
100 mg of succinoglycan are hydrolyzed in hermetic tubes with 5 ml of molar trifluoroacetic acid at 105 ° C for three to six hours.
Cette opération est suivie d'une évaporation à sec et d'une reprise du résidu sec dans 5 ml de pyridine contenant 15 mg de sorbitol en tant qu'étalon interne ; puis d'une silylation sur 1 ml de solution pyridinique par 0,9 ml d'hexamethyldisilazane. La silylation est catalysée par 0,1 ml d'acide trifluoroacétique.This is followed by dry evaporation and taking up the dry residue in 5 ml of pyridine containing 15 mg of sorbitol as an internal standard; then silylation on 1 ml of pyridine solution with 0.9 ml of hexamethyldisilazane. The silylation is catalyzed with 0.1 ml of trifluoroacetic acid.
Le dosage des sucres est ensuite effectué par chromatographie en phase gazeuse à détection F.I.D, sur colonne capillaire en verre de 25 m de longueur et de 0,25 mm de diamètre, chargée de phase méthylsilicone présentant une épaisseur de film de 0,14 µ. Le gaz vecteur utilisé est l'hydrogène, avec un débit de 2 ml/minute.The sugar dosage is then carried out by gas chromatography with F.I.D detection, on a capillary glass column 25 m long and 0.25 mm in diameter, loaded with methylsilicone phase having a film thickness of 0.14 μ. The carrier gas used is hydrogen, with a flow rate of 2 ml / minute.
Le dosage de l'acide pyruvique est réalisé à partir d'une solution mère obtenue par hydrolyse de 80 mg de succinoglycane au moyen de 5 ml d'acide chlorhydrique 4N pendant 1 heure à 105°C, puis ajout de 2 mg d'acide cétoglutarique (constituant l'talon interne) et ajustement à 25 ml par de l'eau distillée.The dosage of pyruvic acid is carried out from a stock solution obtained by hydrolysis of 80 mg of succinoglycan using 5 ml of 4N hydrochloric acid for 1 hour at 105 ° C., then addition of 2 mg of acid ketoglutaric (constituting the internal standard) and adjustment to 25 ml by distilled water.
Le dosage est alors effectué par Chromatographie Liquide Haute Performance (HPLC) au moyen d'une colonne chargée de silice greffée C₁₈ de 5 µ de diamètre, dont la longueur est de 250 mm et le diamètre de 4,6 mm. L'éluant utilisé est un mélange 50/50 en volume d'acide phosphorique 0,02 M et d'acétonitrile. Le débit est de 1,5 ml/minute.The assay is then carried out by High Performance Liquid Chromatography (HPLC) using a column loaded with C₁₈ grafted silica of 5 μ in diameter, the length of which is 250 mm and the diameter of 4.6 mm. The eluent used is a 50/50 mixture by volume of 0.02 M phosphoric acid and acetonitrile. The flow rate is 1.5 ml / minute.
La détection de l'acide pyruvique se fait par Ultra-violets à 375 nm.The detection of pyruvic acid is done by Ultraviolet at 375 nm.
Le dosage de l'acide succinique se fait après hydrolyse du succinoglycane dans les mêmes conditions que celles utilisées pour le dosage de l'acide pyruvique. Le dosage est direct, par étalonnage externe. La solution étalon d'acide succinique utilisée contient 8 mg d'acide succinique dans 25 ml d'eau.The determination of succinic acid is carried out after hydrolysis of the succinoglycan under the same conditions as those used for the determination of pyruvic acid. The assay is direct, by external calibration. The standard succinic acid solution used contains 8 mg of succinic acid in 25 ml of water.
On utilise à nouveau la technique de la CLHP sur des colonnes Aminex HPX87H R de BIORAD R . L'éluant est l'acide sulfurique 0,01 N, et le débit est de 0,8 ml/minute. La détection de l'acide succinique est réfractométrique.The HPLC technique is again used on Aminex HPX87H R columns from BIORAD R. The eluent is 0.01 N sulfuric acid, and the flow rate is 0.8 ml / minute. The detection of succinic acid is refractometric.
Le dosage de l'acide acétique se fait après hydrolyse de 300 à 350 mg du succinoglycane par 5 ml d'acide trifluoroacétique 4 N à 120°C pendant trois heures. Puis on ajoute 30 mg d'acide propionique en tant qu'étalon interne et on dose par Chromatographie en phase gazeuse à détection F.I.D.The dosage of acetic acid is carried out after hydrolysis of 300 to 350 mg of succinoglycan with 5 ml of 4 N trifluoroacetic acid at 120 ° C for three hours. Then 30 mg of propionic acid is added as an internal standard and assayed by gas chromatography with FID detection
Pour le dosage, on utilise une colonne en verre de 2 m de long et de 3 mm de diamètre remplie de phase FFAP à 5 % et d'acide phosphorique à 1 % absorbés sur chromosorb G R (AW DMCS) de 80 à 100 mesh. Le gaz vecteur est l'hélium avec un débit de 30 ml/minute.For the assay, a glass column 2 m long and 3 mm in diameter is used, filled with 5% FFAP phase and 1% phosphoric acid absorbed on chromosorb G R (AW DMCS) from 80 to 100 mesh. . The carrier gas is helium with a flow rate of 30 ml / minute.
Les succinoglycanes de la famille décrite ci-dessus présentent généralement en outre les propriétés suivantes :The succinoglycans of the family described above generally also have the following properties:
1. Leur viscosité intrinsèque est comprise entre 3000 et 25000 ml/g et plus particulièrement comprise entre 14000 et 25000 ml/g et préférentiellement comprise entre 15000 et 24000 ml/g.1. Their intrinsic viscosity is between 3000 and 25000 ml / g and more particularly between 14000 and 25000 ml / g and preferably between 15000 and 24000 ml / g.
La viscosité intrinsèque (η) telle que spécifiée est déterminée par extrapolation à concentration nulle de la viscosité réduite
- η est la viscosité de la solution au plateau Newtonien
- ηo est la viscosité du solvant
et - C est la concentration en succinoglycane,
en utilisant l'équation du Huggins ;
- η is the viscosity of the solution on the Newtonian plateau
- ηo is the viscosity of the solvent
and - C is the succinoglycan concentration,
using the Huggins equation;
La viscosité spécifique
On prépare une solution mère à 0,2 g/l de succinoglycane dans une solution aqueuse 0,1 M NaCl.A stock solution of 0.2 g / l of succinoglycan is prepared in a 0.1 M NaCl aqueous solution.
On prépare ensuite une gamme de solutions comportant le succinoglycane à des concentrations comprises entre 0,03 et 0,1 g/l par dilution de la solution mère avec la solution aqueuse 0,1 M Nacl.We then prepare a range of solutions including succinoglycan at concentrations between 0.03 and 0.1 g / l by dilution of the mother solution with the 0.1 M Nacl aqueous solution.
Les mesures sont ensuite effectuées à 23°C au moyen d'un viscosimètre LOW SHEAR.The measurements are then carried out at 23 ° C. using a LOW SHEAR viscometer.
On trace la courbe de viscosité spécifique en fonction de la concentration et l'on extrapole à concentration nulle.The specific viscosity curve is plotted as a function of the concentration and extrapolated to zero concentration.
2. Les masses moléculaires de ces succinoglycanes mesurées par diffusion de la lumière sont généralement comprises entre 6.10⁶ et 10.10⁶, de préférence comprises entre 6,5.10⁶ et 9,5.10⁶.2. The molecular weights of these succinoglycans measured by light scattering are generally between 6.10⁶ and 10.10⁶, preferably between 6.5.10⁶ and 9.5.10⁶.
3. Ces succinoglycanes présentent en outre de très bonnes propriétés rhéologiques en solution dans l'eau distillée et ceci notamment aux faibles concentrations.3. These succinoglycans also have very good rheological properties in solution in distilled water, especially at low concentrations.
Ainsi des solutions à 0,1 % en poids d'un succinoglycane de ce type dans l'eau distillée à 25°C présentent des viscosités à 24 heures supérieures à 400 mPa.s et plus particulièrement comprises entre 400 et 700 mPa.s ; les viscosités étant mesurées à un gradient de vitesse de 1 s⁻¹ au moyen d'un viscosimètre LOW SHEAR.Thus solutions at 0.1% by weight of a succinoglycan of this type in distilled water at 25 ° C have viscosities at 24 hours greater than 400 mPa.s and more particularly between 400 and 700 mPa.s; the viscosities being measured at a speed gradient of 1 s⁻¹ using a LOW SHEAR viscometer.
De même des solutions aqueuses à 0,2 % en poids d'un de ces succinoglycanes, à pH 1,7 et à 25°C, présentent une viscosité à 24 heures comprise entre 1000 et 2500 mPa.s, plus particulièrement comprise entre 1400 et 2000 mPa.s, les viscosités étant mesurées au moyen d'un viscosimètre LOW SHEAR, à un gradient de vitesse de 1 s⁻¹.Similarly, 0.2% by weight aqueous solutions of one of these succinoglycans, at pH 1.7 and at 25 ° C., have a viscosity at 24 hours of between 1000 and 2500 mPa.s, more particularly between 1400 and 2000 mPa.s, the viscosities being measured using a LOW SHEAR viscometer, at a speed gradient of 1 s⁻¹.
Enfin des solutions de ces mêmes succinoglycanes à 0,2 % en poids dans l'eau distillée, soumises à une température de 80°C durant 24 heures, présentent généralement des viscosités comprises entre 500 et 2500 mPa s et plus particulièrement comprises entre 1000 et 2000 mPa s, les viscosités étant mesurées au moyen d'un viscosimètre LOW SHEAR, à un gradient de vitesse de 1 s⁻¹.Finally solutions of these same succinoglycans at 0.2% by weight in distilled water, subjected to a temperature of 80 ° C for 24 hours, generally have viscosities between 500 and 2500 mPa s and more particularly between 1000 and 2000 mPa s, the viscosities being measured using a LOW SHEAR viscometer, at a speed gradient of 1 s⁻¹.
Les succinoglycanes issus de la souche Agrobacterium tumefaciens I-736 peuvent être obtenus par un procédé qui va être décrit plus en détail ci-dessous.The succinoglycans from the Agrobacterium tumefaciens I-736 strain can be obtained by a process which will be described in more detail below.
Comme on l'a mentionné plus haut, ces succinoglycanes sont issus de la fermentation par la souche précitée d'un milieu comportant au moins une source de carbone assimilable.As mentioned above, these succinoglycans result from the fermentation by the aforementioned strain of a medium comprising at least one assimilable carbon source.
Le milieu est innoculé de manière classique par la souche Agrobacterium tumefaciens I-736.The medium is conventionally innoculated by the Agrobacterium tumefaciens I-736 strain.
Lorsque le volume du milieu de fermentation est important, on peut avantageusement l'innoculer au moyen d'un milieu innoculum, ensemencé par un milieu de préculture liquide ; ce dernier étant préalablement ensemencé lui-même par une culture pure d'Agrobacterium tumefaciens I-736.When the volume of the fermentation medium is large, it can advantageously be inoculated by means of an innoculum medium, seeded with a liquid preculture medium; the latter being previously seeded itself by a pure culture of Agrobacterium tumefaciens I-736.
On peut utiliser en tant que milieu innoculum, tout milieu employé classiquement à cet effet, et avantageusement un milieu de nature minérale. En tant que milieu de préculture on peut citer par exemple le milieu YM bioth DIFCO Ref. 07101 et de préférence un milieu préparé à partir des composés suivants :
Le pH naturel de ce milieu de 7 à 7,2 et n'est pas ajusté.The natural pH of this medium from 7 to 7.2 and is not adjusted.
A titre de source organique de carbone constitutive du milieu de fermentation on peut citer des sucres tels que le glucose, le saccharose, les hydrolysats d'amidon, et éventuellement le lactose ou l'amidon natif, ainsi que les mélanges de ces sucres. Le glucose et le saccharose sont des sucres préférés. La concentration en source organique de carbone dans le milieu de fermentation peut être comprise entre 1 et 100 g/l et de préférence entre 15 et 60 g/l.As organic source of carbon constituting the fermentation medium, there may be mentioned sugars such as glucose, sucrose, starch hydrolysates, and optionally lactose or native starch, as well as mixtures of these sugars. Glucose and sucrose are preferred sugars. The concentration of organic carbon source in the fermentation medium can be between 1 and 100 g / l and preferably between 15 and 60 g / l.
Outre ladite source de carbone assimilable, le milieu de fermentation peut aussi renfermer au moins une source d'azote de préférence une source d'azote organique et éventuellement un ou plusieurs sels minéraux.In addition to said assimilable carbon source, the fermentation medium can also contain at least one nitrogen source, preferably a source of organic nitrogen and optionally one or more mineral salts.
A titre de source organique d'azote on peut citer la caséine et les caséinates, les hydrolysats de poisson, les farines de blé, de maïs ou de soja, les extraits de levure (levure de boulanger, levure de bière, levures lactiques...) Les dry distillers solubles, les protéines de pomme de terre, le corn steap liquor (CSL) et les solubles de CSL qui sont obtenus par dilution du CSL, suivie d'une élimination des particules solides par centrifugation, débourbage ou décantation. Le CSL, et tout spécialement les solubles de CSL, ont été jugés comme particulièrement avantageux dans le cadre de la présente invention.Mention may be made, as organic nitrogen source, of casein and caseinates, fish hydrolysates, wheat, corn or soy flour, yeast extracts (baker's yeast, brewer's yeast, lactic yeasts, etc.). .) Soluble dry distillers, potato proteins, corn steap liquor (CSL) and CSL solubles which are obtained by diluting the CSL, followed by elimination of solid particles by centrifugation, settling or decantation. CSL, and especially CSL solubles, have been found to be particularly advantageous in the context of the present invention.
La concentration en source organique azotée dans le milieu de fermentation peut être comprise entre 3 et 80 g/l et de préférence entre 5 et 50 g/l.The concentration of nitrogenous organic source in the fermentation medium can be between 3 and 80 g / l and preferably between 5 and 50 g / l.
On peut citer à titre de sels minéraux que l'on peut éventuellement introduire dans le milieu de fermentation, les sulfates tels que les sulfates de magnésium, de manganèse, de zinc, de fer, les carbonates tels que le carbonate de calcium, les sels de calcium solubles, les phosphates tels que les phosphates de potassium, de sodium.Mention may be made, as mineral salts which may optionally be introduced into the fermentation medium, of the sulfates such as magnesium, manganese, zinc, iron sulfates, carbonates such as calcium carbonate, the salts soluble calcium, phosphates such as potassium, sodium phosphates.
La concentration de chacun de ces sels minéraux dans le milieu de fermentation peut varier entre 0,01 et 5 g/l et de préférence entre 0,05 et 2 g/l.The concentration of each of these mineral salts in the fermentation medium can vary between 0.01 and 5 g / l and preferably between 0.05 and 2 g / l.
Le milieu de fermentation peut également renfermer des oligoéléments tels que des traces de sels de cobalt et/ou de molybdène, ainsi que des vitamines et des nucléotides.The fermentation medium can also contain trace elements such as traces of cobalt and / or molybdenum salts, as well as vitamins and nucleotides.
La fermentation peut être réalisée à des pressions comprises entre 1 et 4 bar à une température comprise entre 25 et 35°C, de préférence entre 28 et 32°C, dans des conditions aérobies submergées.Fermentation can be carried out at pressures between 1 and 4 bar at a temperature between 25 and 35 ° C, preferably between 28 and 32 ° C, under submerged aerobic conditions.
Le pH du milieu de fermentation peut être compris entre 5 et 9 et de préférence entre 6 et 8. Le pH peut être ajusté, selon le cas, avec une base telle que la soude ou la potasse ou avec un acide tel que l'acide sulfurique, l'acide phosphorique, l'acide chlorhydrique ou l'acide nitrique. Le milieu de fermentation, placé par exemple, dans une cuve ou un récipient de fermentation, peut être avantageusement soumis à une agitation.The pH of the fermentation medium can be between 5 and 9 and preferably between 6 and 8. The pH can be adjusted, as the case may be, with a base such as soda or potash or with an acid such as acid sulfuric, phosphoric acid, hydrochloric acid or nitric acid. The fermentation medium, placed for example in a fermentation tank or container, can advantageously be subjected to stirring.
Cette agitation peut être exercée par exemple au moyen d'un secoueur réciproque, d'un secoueur giratoire, d'un mobile d'agitation ou d'une colonne à bulles. Le temps de fermentation est habituellement supérieur à 30 heures, mais est généralement compris entre 40 et 90 heures.This agitation can be exercised for example by means of a reciprocal shaker, a gyratory shaker, a stirring mobile or a bubble column. The fermentation time is usually more than 30 hours, but is generally between 40 and 90 hours.
Les rendements de fermentation sont généralement supérieurs à 40 % plus particulièrement compris entre 55-75 % et tout particulièrement compris entre 60 et 75 % en poids de succinoglycane produit par rapport à la source de carbone mise en oeuvre.Fermentation yields are generally greater than 40%, more particularly between 55-75% and very particularly between 60 and 75% by weight of succinoglycan produced relative to the carbon source used.
Le succinoglycane peut être séparé du milieu de fermentation.The succinoglycan can be separated from the fermentation medium.
Pour ce faire le moût de fermentation renfermant le succinoglycane peut être avantageusement chauffé à des températures comprises entre 80 et 120°C, pendant 10 à 60 minutes et de préférence entre 15 et 45 minutes.To do this, the fermentation must containing the succinoglycan can advantageously be heated to temperatures between 80 and 120 ° C, for 10 to 60 minutes and preferably between 15 and 45 minutes.
Le moût soumis au traitement thermique ci-dessus présente avantageusement un pH compris entre 6 et 8.The must subjected to the above heat treatment advantageously has a pH of between 6 and 8.
Cependant ce pH peut être ajusté si nécessaire, avec selon le cas, une base ou un acide.However, this pH can be adjusted if necessary, with a base or an acid as appropriate.
Ces derniers peuvent être choisis parmi les bases et les acides mentionnés ci-dessus utilisés pour l'ajustement du pH du milieu de fermentation.The latter can be chosen from the bases and the acids mentioned above used for adjusting the pH of the fermentation medium.
La récupération du succinoglycane du moût de fin de fermentation peut alors être réalisée par précipitation dudit succinoglycane au moyen d'un liquide organique miscible avec l'eau et dans lequel le succinoglycane est insoluble ou pratiquement insoluble.Recovery of the succinoglycan from the end of fermentation must can then be carried out by precipitation of said succinoglycan using an organic liquid miscible with water and in which the succinoglycan is insoluble or practically insoluble.
A titre de liquides organiques convenables selon la présente invention on peut citer l'acétone, les alcools tels que l'éthanol, le propanol, l'isopropanol, le butanol, le tertio-butanol.Mention may be made, as suitable organic liquids according to the present invention, of acetone, alcohols such as ethanol, propanol, isopropanol, butanol and tert-butanol.
L'isopropanol est plus particulièrement préféré dans le cadre de la présente invention.Isopropanol is more particularly preferred in the context of the present invention.
Le volume de liquide organique utilisé est généralement 2 à 3 fois celui du volume de moût à traiter.The volume of organic liquid used is generally 2 to 3 times that of the volume of must to be treated.
La précipitation du succinoglycane par un liquide organique peut également être réalisée en présence de sels tels que les sulfates, chlorures ou phosphates de sodium, de potassium, ou de calcium.The precipitation of succinoglycan by an organic liquid can also be carried out in the presence of salts such as sulfates, chlorides or phosphates of sodium, potassium, or calcium.
Le succinoglycane une fois précipité, peut ensuite être séparé du liquide organique par filtration, centrifugation ou essorage.The succinoglycan once precipitated, can then be separated from the organic liquid by filtration, centrifugation or spinning.
Les fibres obtenues peuvent être déshydratées par exemple au moyen d'acétone ou d'un alcool tel que l'éthanol, le propanol, l'isopropanol ou le tertio-butanol.The fibers obtained can be dehydrated, for example using acetone or an alcohol such as ethanol, propanol, isopropanol or tert-butanol.
Le poids d'alcool nécessaire pour effectuer cette opération de déshydratation est généralement de 1 à 10 fois celui des fibres à traiter.The weight of alcohol required to perform this dehydration operation is generally 1 to 10 times that of the fibers to be treated.
Les fibres déshydratées peuvent subir de nouvelles opérations de filtration de centrifugation ou d'essorage.The dehydrated fibers can undergo new centrifugation or spin filtration operations.
Les fibres peuvent ensuite être séchées, broyées et tamisées de façon à obtenir une poudre.The fibers can then be dried, ground and sieved to obtain a powder.
Afin d'obtenir une poudre encore plus pure, il est possible de traiter soit le moût de fermentation, soit une solution aqueuse reconstituée à partir de la poudre obtenue selon le procédé décrit ci-dessus, au moyen d'une ou plusieurs enzymes.In order to obtain an even purer powder, it is possible to treat either the fermentation must or an aqueous solution reconstituted from the powder obtained according to the process described above, by means of one or more enzymes.
A titre d'enzymes pouvant convenir à cet effet, on peut citer les protéases, les mutanases, les lipoprotéases, les cellulases et les chitinases.As enzymes which may be suitable for this purpose, mention may be made of proteases, mutanases, lipoproteases, cellulases and chitinases.
La purification enzymatique peut être associée ou remplacée par des procédés physiques de purification tels que les divers modes de filtration, de dialyse, ou par les différentes techniques de chromatographie.Enzymatic purification can be combined or replaced by physical purification methods such as the various modes of filtration, of dialysis, or by the various techniques of chromatography.
Les moûts de fermentation et les solutions aqueuses reconstituées de succinoglycane, ayant subi ou non un traitement de purification peuvent être concentrés. La concentration peut être avantageuse dans certains cas notamment dans la mesure où les coûts de transport peuvent être ainsi réduits. De plus, les solutions concentrées peuvent être plus rapidement mises en oeuvre que les poudres. La concentration peut être réalisée par des techniques telles que l'évaporation, l'ultrafiltration, ou par diafiltration.Fermentation musts and reconstituted aqueous solutions of succinoglycan, whether or not subjected to a purification treatment, can be concentrated. Concentration can be advantageous in certain cases, in particular insofar as transport costs can be reduced. In addition, concentrated solutions can be implemented more quickly than powders. Concentration can be achieved by techniques such as evaporation, ultrafiltration, or by diafiltration.
Les succinoglycanes s'utilisent, dans le cadre de l'invention, sous forme solide en poudre ou en solution aqueuse.The succinoglycans are used, in the context of the invention, in solid form in powder or in aqueous solution.
Selon l'invention, on utilise généralement de 0,001 à 2% en poids, de préférence entre 0,01 et 0,5% en poids de succinoglycane par rapport à la suspension finale.According to the invention, generally used from 0.001 to 2% by weight, preferably between 0.01 and 0.5% by weight of succinoglycan relative to the final suspension.
Les suspensions de l'invention comprenant un succinoglycane du type décrit ci-dessus sont particulièrement stables.The suspensions of the invention comprising a succinoglycan of the type described above are particularly stable.
Toutefois, afin de réduire leur viscosité et sur un plan pratique de les rendre plus manipulables et plus pompables, il est aussi possible de leur incorporer un dispersant.However, in order to reduce their viscosity and on a practical level to make them more manipulable and more pumpable, it is also possible to incorporate a dispersant therein.
Selon un mode de réalisation préférentiel de l'invention, ce dispersant est choisi dans le groupe des siliconates et de leurs dérivés.According to a preferred embodiment of the invention, this dispersant is chosen from the group of siliconates and their derivatives.
Les siliconates sont des produits bien connus, ce sont des sels de l'acide siliconique ou de ses dérivés.Siliconates are well known products, they are salts of siliconic acid or its derivatives.
On peut citer notamment les produits répondant à la formule (1) :
R - Si (OM)m (OH)3-m (1)
et/ou les produits de condensation de ceux-ci, formule dans laquelle R est un reste hydrocarboné généralement de 1 à 18 atomes de carbone, le cas échéant substitué par un atome d'halogène, un groupe amino, éther, ester, époxy, mercapto, cyano, (poly)glycol;
m est un nombre entier ou fractionnaire variant entre 0,1 et 3;
M est un métal alcalin ou un groupe ammonium ou phosphonium.Mention may in particular be made of the products corresponding to formula (1):
R - Si (OM) m (OH) 3-m (1)
and / or the condensation products thereof, formula in which R is a hydrocarbon residue generally of 1 to 18 carbon atoms, optionally substituted by a halogen atom, an amino group, ether, ester, epoxy, mercapto, cyano, (poly) glycol;
m is an integer or fractional number varying between 0.1 and 3;
M is an alkali metal or an ammonium or phosphonium group.
De préférence, R est un reste hydrocarboné de 1 à 10 atomes de carbone et plus particulièrement de 1 à 6 atomes.Preferably, R is a hydrocarbon residue of 1 to 10 carbon atoms and more particularly of 1 to 6 atoms.
Plus précisément, R peut être un radical alkyle par exemple méthyle, éthyle, propyle, butyle, isobutyle; un radical alcényle comme par exemple vinyl, un radical aryle, par exemple phényle ou naphtyle, un radical arylalkyle comme par exemple benzyle ou phényléthyle, alkylaryle comme par exemple tolyle, xylyle, ou un radical araryle comme le biphénylyle.More specifically, R can be an alkyl radical, for example methyl, ethyl, propyl, butyl, isobutyl; an alkenyl radical such as for example vinyl, an aryl radical, for example phenyl or naphthyl, an arylalkyl radical such as for example benzyl or phenylethyl, alkylaryl such as for example tolyl, xylyl, or an araryl radical such as biphenylyl.
Pour M, on peut citer plus particulièrement le sodium ou le potassium ainsi que les groupes N+R′₄, P+R′₄ dans lesquels R′ sont identiques ou différents et sont des restes hydrocarbonés de 1 à 6 atomes de carbone.For M, there may be mentioned more particularly sodium or potassium as well as the groups N + R′₄, P + R′₄ in which R ′ are identical or different and are hydrocarbon residues of 1 to 6 carbon atoms.
On utilise plus particulièrement les siliconates alcalins. On peut aussi employer les siliconates alcalinoterreux.More particularly, alkaline siliconates are used. Alkaline earth siliconates can also be used.
De même, on met en oeuvre particulièrement les alkylsiliconates et notamment les alkylsiliconates alcalins comme par exemple les méthylsiliconates de sodium ou de potassium.Likewise, particular use is made of alkylsiliconates and in particular alkaline alkylsiliconates such as, for example, sodium or potassium methylsiliconates.
On peut aussi utiliser les siliconates de formule 1 pour lesquels R est un radical vinyle ou phényle, et plus particulièrement les siliconates alcalins de ce type.It is also possible to use the siliconates of formula 1 for which R is a vinyl or phenyl radical, and more particularly the alkali siliconates of this type.
Il est à noter que les siliconates alcalins ou alcalino-terreux sont des produits dont la plupart sont disponibles dans le commerce.It should be noted that alkali or alkaline earth siliconates are products, most of which are commercially available.
Ils peuvent être préparés par exemple par hydrolyse des silanes correspondants présentant 3 groupes hydrolysables tels que des atomes d'halogène, des radicaux alcoxy, suivie d'une dissolution du produit obtenu dans une solution d'une base inorganique forte dans des proportions telles qu'il y ait au moins un équivalent en base par atome de silicium (voir par exemple US-A-2 441 422, US-A-2 441 423).They can be prepared for example by hydrolysis of the corresponding silanes having 3 hydrolyzable groups such as halogen atoms, alkoxy radicals, followed by dissolution of the product obtained in a solution of a strong inorganic base in proportions such as there is at least one equivalent in base per atom of silicon (see for example US-A-2,441,422, US-A-2,441,423).
Comme exemple de siliconates de ce type disponibles dans le commerce, on peut citer notamment le RHODORSIL R SILICONATE 51T, commercialisé par la Demanderesse, qui est un méthylsiliconate de potassium.As an example of commercially available siliconates of this type, mention may in particular be made of RHODORSIL R SILICONATE 51T, sold by the Applicant, which is a potassium methylsiliconate.
Comme cela a été indiqué plus haut, le dispersant peut être choisi aussi parmi les dérivés des siliconates.As indicated above, the dispersant can also be chosen from siliconate derivatives.
Par produits dérivés, on entend ici les produits de condensation des produits répondant notamment à la formule (1) décrit ci-dessus, ou ceux résultant de la polymérisation au moins partielle en composés ou polymères siliconiques.By derivative products is meant here the condensation products of the products corresponding in particular to formula (1) described above, or those resulting from the at least partial polymerization into silicone compounds or polymers.
On sait par exemple que les alkylsiliconates de métal alcalin peuvent être transformés en polyalkylsiloxanes, notamment par l'action de l'anhydride carbonique ou autre agent acidifiant.It is known, for example, that the alkali metal alkylsiliconates can be transformed into polyalkylsiloxanes, in particular by the action of carbon dioxide or other acidifying agent.
Comme deuxième type de dispersant convenable pour la présente invention, on peut aussi citer les résines silicones.As a second type of dispersant suitable for the present invention, mention may also be made of silicone resins.
Ces résines silicones sont des polymères organopolysiloxanes ramifiées bien connues et disponibles dans le commerce. Elles présentent, par molécule, au moins deux motifs différents choisis parmi ceux de formule R₃SiO0,5 (motif M), R₂SiO (motif D), RSiO1,5 (motif T) et SiO₂ (motif Q).These silicone resins are well-known and commercially available branched organopolysiloxane polymers. They present, per molecule, at least two different motifs chosen among those of formula R₃SiO 0.5 (unit M), R₂SiO (unit D), RSiO 1.5 (unit T) and SiO₂ (unit Q).
Les radicaux R sont identiques ou différents et sont choisis parmi les radicaux alkyles linéaires ou ramifiés, ces radicaux ayant plus particulièrement de 1 à 6 atomes de carbone inclus, les radicaux vinyle, phényle, trifluoro-3,3,3 propyle.The radicals R are identical or different and are chosen from linear or branched alkyl radicals, these radicals more particularly having from 1 to 6 carbon atoms included, vinyl, phenyl, trifluoro-3,3,3 propyl radicals.
Plus particulièrement, on peut citer comme radicaux R alkyle, les radicaux méthyle, éthyle, isopropyle, tertiobutyle et n-hexyle.More particularly, mention may be made, as alkyl radicals R, of methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.
Ces résines sont généralement hydroxylées et ont dans ce cas une teneur pondérale en groupe hydroxyle comprise entre 0,1 et 10%.These resins are generally hydroxylated and in this case have a weight content of hydroxyl group of between 0.1 and 10%.
Comme exemple de résines, on peut citer les résines MQ, les résines MDQ, les résines TD et les résines MDT.Examples of resins include MQ resins, MDQ resins, TD resins and MDT resins.
On peut utiliser plus particulièrement les résines présentant une masse moléculaire inférieure à 25000.Resins having a molecular mass of less than 25,000 can be used more particularly.
Comme résine de ce type, on peut utiliser par exemple les produits commercialisés par la Demanderesse sous les noms RHODORSIL 865 A ou 878 A.As resin of this type, it is possible, for example, to use the products sold by the Applicant under the names RHODORSIL 865 A or 878 A.
Il va de soi que dans le cadre de la présente invention, on peut utiliser en combinaison dans la suspension deux ou plusieurs siliconates ou dérivés ou résines.It goes without saying that in the context of the present invention, it is possible to use in combination in the suspension two or more siliconates or derivatives or resins.
Les siliconates s'utilisent habituellement sous forme de solutions aqueuses.The siliconates are usually used in the form of aqueous solutions.
La quantité de siliconate utilisée est fonction de la surface spécifique de la zéolite. Cette quantité est habituellement comprise entre 0,01 et 2% plus particulièrement entre 0,05 et 0,3% en poids par rapport à la suspension finale. Cette quantité s'entend pour une solution à 50 % en poids dans l'eau du siliconate ou dérivé.The amount of siliconate used depends on the specific surface of the zeolite. This amount is usually between 0.01 and 2%, more particularly between 0.05 and 0.3% by weight relative to the final suspension. This quantity is understood for a solution at 50% by weight in water of the siliconate or derivative.
Les résines peuvent être utilisées à l'état solide ou sous forme d'émulsions aqueuses ou émulsion ou solution dans un solvant organique.The resins can be used in the solid state or in the form of aqueous emulsions or emulsion or solution in an organic solvent.
Les quantités utilisées sont comprises entre 0,01 et 2% en poids de produit solide, plus particulièrement entre 0,05 et 0,3 par rapport à la suspension finale.The amounts used are between 0.01 and 2% by weight of solid product, more particularly between 0.05 and 0.3 relative to the final suspension.
L'emploi des siliconates ou dérivés et des résines tels que définis ci-dessus a pour effet de baisser considérablement la viscosité des suspensions de zéolites. Il permet aussi d'obtenir des suspensions stables à extrait sec plus élevé par exemple d'au moins 55%.The use of siliconates or derivatives and resins as defined above has the effect of considerably lowering the viscosity of the zeolite suspensions. It also makes it possible to obtain stable suspensions with a higher dry extract, for example at least 55%.
Toutefois, sans sortir du cadre de la présente invention, on peut utiliser des dispersants connus. Bien entendu, là aussi, ces dispersants peuvent être mis en oeuvre seuls ou en combinaison et même éventuellement en combinaison avec les siliconates, leurs dérivés ou les résines.However, without departing from the scope of the present invention, known dispersants can be used. Of course, here too, these dispersants can be used alone or in combination and even optionally in combination with the siliconates, their derivatives or the resins.
Ces dispersants peuvent être choisis dans le groupe comprenant les tensioactifs non ioniques ou anioniques, les composés polymères organiques macromoléculaires portant des groupes carboxyles et/ou hydroxyles, les phosphates.These dispersants can be chosen from the group comprising nonionic or anionic surfactants, macromolecular organic polymer compounds carrying carboxyl and / or hydroxyl groups, phosphates.
Comme tensioactifs non ioniques, on peut faire appel d'une manière générale à des composés obtenus par condensation d'oxyde d'alcoylène avec un composé organique qui peut être aliphatique ou alcoylaromatique.As nonionic surfactants, use may generally be made of compounds obtained by condensation of alkylene oxide with an organic compound which may be aliphatic or alkylaromatic.
On peut citer notamment les alcoylphénols polyoxyéthylénés, les alcools aliphatiques polyoxyéthylénés, les amides carboxyliques, les alcools polyoxyéthylénés et polyoxypropylènes, notamment du type "PLURONICS".Mention may in particular be made of polyoxyethylenated alkylphenols, polyoxyethylenated aliphatic alcohols, carboxylic amides, polyoxyethylenated and polyoxypropylene alcohols, in particular of the "PLURONICS" type.
On peut aussi citer à titre d'exemple le tristirylphénol éthoxylé, le nonylphénol éthoxylé.Mention may also be made, by way of example, of ethoxylated tristirylphenol and ethoxylated nonylphenol.
On peut enfin mentionner les tensioactifs du type sucroglycéride.Finally, mention may be made of surfactants of the sucroglyceride type.
Comme tensioactifs anioniques, on mentionne les savons de métaux alcalins, les sulfonates alcalins, tels que le méthylnaphtalène sulfonate, le xylènesulfonate, les esters béta-sulfoéthyliques des acides gras, les sulfates et produits sulfatés tels que les sulfates d'alcoyle, les alcools gras polyoxyéthylénés et sulfatés.As anionic surfactants, there are mentioned alkali metal soaps, alkali sulfonates, such as methylnaphthalene sulfonate, xylenesulfonate, beta-sulfoethyl esters of fatty acids, sulfates and sulfated products such as alkyl sulfates, fatty alcohols polyoxyethylenated and sulphated.
Pour les composés polymères organiques macromoléculaires, on peut donner à titre d'exemple les polymères des acides acryliques, hydroxyacrylique, maléique, itaconique, les copolymères des acides mentionnés ci-dessus entre-eux ou avec des composés à insaturation éthylénique comme l'éthylène, le propylène, l'alcool vinylique, l'acétate de vinyle, l'acide méthacrylique. On pourra se référer notamment aux produits donnés dans FR-A-2 287 504.For macromolecular organic polymer compounds, the polymers of acrylic, hydroxyacrylic, maleic, itaconic acids, the copolymers of the acids mentioned above may be given together or with unsaturated compounds ethylenic such as ethylene, propylene, vinyl alcohol, vinyl acetate, methacrylic acid. We can refer in particular to the products given in FR-A-2 287 504.
En ce qui concerne enfin les phosphates, on pourra choisir ceux-ci dans le groupe des esters primaires ou secondaires de l'acide orthophosphorique ou l'un de ses sels et des mono ou diesters de cet acide ou de ses sels polyoxyéthylénés. On peut mentionner aussi les phosphates minéraux notamment alcalins tel que le pyrophosphate, le tripolyphosphate, l'hexamétaphosphate de sodium.Finally, as regards the phosphates, these can be chosen from the group of primary or secondary esters of orthophosphoric acid or one of its salts and mono or diesters of this acid or of its polyoxyethylenated salts. Mention may also be made of inorganic in particular alkaline phosphates such as pyrophosphate, tripolyphosphate, sodium hexametaphosphate.
Enfin, on notera qu'il est possible d'ajouter un agent bactéricide aux suspensions de l'invention.Finally, it will be noted that it is possible to add a bactericidal agent to the suspensions of the invention.
La préparation des suspensions de zéolite selon l'invention se fait d'une manière simple par introduction des additifs décrits ci-dessus dans la suspension et mélange. Si nécessaire le pH de la suspension de zéolite peut être ajusté à la valeur désirée d'une manière connue par addition de tout agent neutralisant convenable.The zeolite suspensions according to the invention are prepared in a simple manner by introducing the additives described above into the suspension and mixture. If necessary the pH of the zeolite suspension can be adjusted to the desired value in a known manner by the addition of any suitable neutralizing agent.
Les suspensions comprenant les zéolites et stabilisées par les systèmes qui viennent d'être décrits peuvent être utilisées dans de nombreuses applications.Suspensions comprising zeolites and stabilized by the systems which have just been described can be used in numerous applications.
Elles peuvent être utilisées sous la forme de suspensions à base essentiellement de zéolites et des additifs stabilisants mentionnés ci-dessus. Dans ce cas, elles peuvent entrer dans la préparation de compositions lessivielles. Elles peuvent être utilisées dans tout autre domaine que la détergence pour lequel les zéolites sont employées par exemple en papeterie.They can be used in the form of suspensions based essentially on zeolites and the stabilizing additives mentioned above. In this case, they can enter into the preparation of detergent compositions. They can be used in any field other than detergency for which zeolites are used, for example in stationery.
La présente invention couvre aussi les compositions lessivielles notamment pour lessives liquides, comprenant outre les suspensions à base de zéolite et des stabilisants de l'invention, tous les autres additifs connus en détergence tels que des agents de blanchiment, des agents de contrôle des mousses, des agents antirédéposition, des parfums, des solvants, des enzymes, des agents optiques.The present invention also covers detergent compositions, in particular for liquid detergents, comprising, in addition to the suspensions based on zeolite and stabilizers of the invention, all the other additives known in detergency such as bleaching agents, foam control agents, anti-redeposition agents, perfumes, solvents, enzymes, optical agents.
Des exemples concrets vont maintenant être donnés.Concrete examples will now be given.
Quelques définitions et précisions sont données au préalable.Some definitions and details are given beforehand.
L'extrait sec de la suspension est donné en pourcentage pondéral de zéolite anhydre déterminé par une mesure de perte au feu à 850°C pendant une heure.The dry extract of the suspension is given in percentage by weight of anhydrous zeolite determined by a measurement of loss on ignition at 850 ° C. for one hour.
Le pH indiqué est donné pour une dispersion aqueuse contenant 1% de zéolite sèche et il est mesuré à l'aide d'une électrode pH haute alcalinité.The pH indicated is given for an aqueous dispersion containing 1% of dry zeolite and it is measured using a high alkalinity pH electrode.
La capacité d'échange est donnée par la quantité de calcium (exprimée en mg de CaCO₃) échangée par 1 g de zéolite anhydre à 25°C. On réalise la mesure de la manière suivante : 0,4 g de zéolite (exprimé en anhydre) est introduit dans une solution de 5.10⁻³ mole/l CaCl₂. Le mélange est maintenu sous agitation pendant 15 minutes. Après filtration, l'excès de calcium est dosé à pH 10 en retour par l'EDTA en présence d'un indicateur coloré, le noir d'ériochrome T.The exchange capacity is given by the amount of calcium (expressed in mg of CaCO₃) exchanged with 1 g of anhydrous zeolite at 25 ° C. The measurement is carried out in the following manner: 0.4 g of zeolite (expressed as anhydrous) is introduced into a solution of 5.10⁻³ mole / l CaCl₂. The mixture is kept stirring for 15 minutes. After filtration, the excess calcium is dosed at pH 10 in return by EDTA in the presence of a colored indicator, black eriochrome T.
On notera que le système de l'invention stabilisant-dispersant ne perturbe pas cette capacité.It will be noted that the system of the invention stabilizer-dispersant does not disturb this capacity.
En ce qui concerne la rhéologie, on utilise comme rhéomètre le RHEOMAT 30 équipé du système de mesure B centré. La mesure consiste à effectuer un cycle en gradient de vitesse (montée plus descente). La gamme de gradient de vitesse explorée est comprise entre 0,0215 et 157,9 s⁻¹, ce qui correspond à des vitesses de rotation du mobile de 0,0476 à 350 tours par minute. Les viscosités rapportées dans les exemples correspondent à des mesures obtenues durant la descente en gradient de vitesse.As regards rheology, the RHEOMAT 30 equipped with the centered measurement system B is used as rheometer. The measurement consists in performing a cycle in speed gradient (ascent plus descent). The range of speed gradient explored is between 0.0215 and 157.9 s⁻¹, which corresponds to rotational speeds of the mobile from 0.0476 to 350 revolutions per minute. The viscosities reported in the examples correspond to measurements obtained during the descent in speed gradient.
La sédimentation est déterminée en introduisant la suspension de zéolite dans des éprouvettes graduées de 50 à 100 cc. Les volumes de surnageant et de décantat sont mesurés tous les cinq jours. Les éprouvettes sont laissées à température ambiante (20°C) ou placées en enceinte thermostatée.The sedimentation is determined by introducing the zeolite suspension into graduated cylinders from 50 to 100 cc. The volumes of supernatant and decantate are measured every five days. The test pieces are left at room temperature (20 ° C) or placed in a thermostatically controlled enclosure.
La zéolite utilisée est une zéolite 4A de diamètre moyen de particules primaires de 3,5µm.The zeolite used is a 4A zeolite with an average diameter of primary particles of 3.5 μm.
Le succinoglycane utilisé dans les exemples qui suivent peut être préparé de la manière suivante :The succinoglycan used in the following examples can be prepared as follows:
On fait fermenter par une souche Agrobacterium tumefaciens I-736 un milieu renfermant (en g/l) :
Ce milieu est fermenté par ladite souche à une température de 28°C, dans une cuve de 20 litres BIOLAFFITE R contenant un volume utile de 15 litres.This medium is fermented by said strain at a temperature of 28 ° C., in a 20 liter BIOLAFFITE R tank containing a useful volume of 15 liters.
Le milieu est soumis à une agitation de 400 tours/mn obtenue au moyen de mobiles de type RUSHTON R .The medium is subjected to stirring at 400 revolutions / min obtained by means of RUSHTON R type mobiles.
Le milieu est aéré sous un débit d'air de 825 l/h.The medium is aerated under an air flow of 825 l / h.
A la fin de la fermentation, la récupération du succinoglycane a été effectuée à partir de 2 kg de moût.At the end of the fermentation, the recovery of the succinoglycan was carried out from 2 kg of must.
Le moût est traité thermiquement à 90°C pendant 30 mn.The must is heat treated at 90 ° C for 30 min.
Au moût ainsi traité sont ajoutés 2300 ml d'alcool isopropylique (IPA). La précipitation est effectuée en présence de 150 g de sulfate de sodium.To the must thus treated are added 2300 ml of isopropyl alcohol (IPA). The precipitation is carried out in the presence of 150 g of sodium sulfate.
Les fibres issues de la précipitation sont ensuite deshydratées 2 fois en présence de 1200 ml d'IPA.The fibers from the precipitation are then dehydrated twice in the presence of 1200 ml of IPA.
Les fibres sont alors essorées, dilacérées et séchées dans une étuve à 85°C.The fibers are then wrung, shredded and dried in an oven at 85 ° C.
La matière sèche récoltée est broyée et tamisée.The collected dry matter is crushed and sieved.
On obtient alors une poudre de produit de couleur crème.A cream-colored product powder is then obtained.
Ces exemples montrent la stabilisation des suspensions de zéolite par le succinoglycane.These examples show the stabilization of the zeolite suspensions by succinoglycan.
La suspension contient 45% en poids de zéolite.The suspension contains 45% by weight of zeolite.
Les résultats sont donnés dans le tableau 1 ci-dessous.
Les résultats sont donnés dans le tableau 2 ci-dessous.The results are given in Table 2 below.
En ce qui concerne le RHODORSIL 51 T, les quantités indiquées sont en pourcentages pondéraux pour une solution aqueuse à 50%de siliconate.With regard to RHODORSIL 51 T, the quantities indicated are in percentages by weight for a 50% aqueous solution of siliconate.
La résine A est une résine du type décrit plus haut pour laquelle R est un radical méthyl. Cette résine est utilisée ici à l'état sec ou solide. Elle est commercialisée par la Demanderesse sous la forme d'une émulsion sous la référence RHODORSIL 865 A.
L'exemple 8 est un exemple à faible quantité de succinoglycane.Example 8 is a low quantity example of succinoglycan.
Dans l'exemple 9, on utilise une résine "Résine B" qui est une résine du type décrit plus haut dans laquelle R est un méthyl.In Example 9, a resin "Resin B" is used which is a resin of the type described above in which R is methyl.
Cette résine est utilisée ici à l'état sec. Elle est commercialisée par la Demanderesse sous la forme d'une émulsion et sous la référence RHODORSIL 878 A.This resin is used here in the dry state. It is marketed by the Applicant in the form of an emulsion and under the reference RHODORSIL 878 A.
Les résultats sont donnés dans le tableau 3 ci-dessous.The results are given in Table 3 below.
L'exemple 10 décrit l'utilisation à titre de dispersant d'un tensio-actif non-ionique du type sucroglycéride commercialisé par la Demanderesse sous le nom CELYNOL X8063.Example 10 describes the use as a dispersant of a nonionic surfactant of the sucroglyceride type sold by the Applicant under the name CELYNOL X8063.
L'exemple 11 décrit l'utilisation à titre de dispersant d'un tensio-actif non-ionique du type tristirylphénol éthoxylé commercialisé sous le nom SOPROPHOR S25, commercialisé par la Demanderesse.Example 11 describes the use as a dispersant of a nonionic surfactant of the ethoxylated tristirylphenol type sold under the name SOPROPHOR S25, sold by the Applicant.
L'exemple 12 concerne un dispersant du type tensio-actif anionique qui est un tristyrylphénol éthoxylé phosphaté commercialisé sous le nom SOPROPHOR FL, commercialisé par la Demanderesse.Example 12 relates to a dispersant of the anionic surfactant type which is a phosphated ethoxylated tristyrylphenol marketed under the name SOPROPHOR FL, marketed by the Applicants.
Les exemples 13 à 14 concernent des polymères acryliques. Le polymère 1 est un homopolymère acrylique de masse 2000. Le polymère 2 est un copolymère acrylique-maléique de masse 70 000 et de rapport acrylique/maléique de 60/40.Examples 13 to 14 relate to acrylic polymers. Polymer 1 is an acrylic homopolymer with a mass of 2000. Polymer 2 is an acrylic-maleic copolymer with a mass of 70,000 and an acrylic / maleic ratio of 60/40.
Les résultats sont donnés dans le tableau 4.
Claims (51)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8913139 | 1989-10-09 | ||
FR8913139A FR2652820B1 (en) | 1989-10-09 | 1989-10-09 | STABLE SUSPENSIONS OF ZEOLITES COMPRISING A SUCCINOGLYCANE. |
Publications (1)
Publication Number | Publication Date |
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EP0422997A1 true EP0422997A1 (en) | 1991-04-17 |
Family
ID=9386195
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90402758A Withdrawn EP0422997A1 (en) | 1989-10-09 | 1990-10-05 | Stable aqueous zeolite suspensions containing a succinoglycane |
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Country | Link |
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US (1) | US5104566A (en) |
EP (1) | EP0422997A1 (en) |
JP (1) | JPH0678552B2 (en) |
KR (1) | KR930010380B1 (en) |
BR (1) | BR9005014A (en) |
CA (1) | CA2027011A1 (en) |
FI (1) | FI904948A0 (en) |
FR (1) | FR2652820B1 (en) |
IE (1) | IE903592A1 (en) |
NO (1) | NO904358L (en) |
PT (1) | PT95534A (en) |
YU (1) | YU188790A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2756488A1 (en) * | 1996-12-04 | 1998-06-05 | Rhodia Chimie Sa | AQUEOUS COSMETIC COMPOSITIONS BASED ON NON-VOLATILE INSOLUBLE SILICONES, STABILIZED BY A SUCCINOGLYCAN AND THEIR PROCESS OF PREPARATION |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5190693A (en) * | 1988-07-29 | 1993-03-02 | Ausidet S.P.A. | Stable aqueous suspensions of inorganic silica-based materials insoluble in water |
FR2652819B1 (en) * | 1989-10-09 | 1994-01-07 | Rhone Poulenc Chimie | SUSPENSION OF ZEOLITE COMPRISING A SILICONATE. |
FR2678939B1 (en) * | 1991-07-10 | 1993-10-08 | Rhone Poulenc Chimie | COMPOSITION DERIVED FROM A SUCCINOGLYCANE, PROCESS FOR THE PREPARATION THEREOF AND ITS APPLICATIONS. |
US5571531A (en) * | 1994-05-18 | 1996-11-05 | Mcmaster University | Microparticle delivery system with a functionalized silicone bonded to the matrix |
US7195071B2 (en) * | 2003-08-05 | 2007-03-27 | Halliburton Energy Services, Inc. | Enzyme compositions and methods of using these compositions to degrade succinoglycan |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0040445A1 (en) * | 1980-05-21 | 1981-11-25 | Shell Internationale Researchmaatschappij B.V. | Fluid displacement with heteropolysaccharide solutions, and the microbial production of heteropolysaccharides |
FR2512690A1 (en) * | 1981-09-16 | 1983-03-18 | Ugine Kuhlmann | STABLE SODIUM SILICO ALUMINATE SUSPENSIONS |
EP0092761A2 (en) * | 1982-04-22 | 1983-11-02 | Hoechst Aktiengesellschaft | Microbial polysaccharides, process for their production, microorganisms suitable therefor and use of the polysaccharides |
EP0351303A1 (en) * | 1988-07-13 | 1990-01-17 | Rhone-Poulenc Chimie | Heteropolysaccharide BM07, process for obtaining it and its use in diverse industries |
-
1989
- 1989-10-09 FR FR8913139A patent/FR2652820B1/en not_active Expired - Fee Related
-
1990
- 1990-10-05 YU YU188790A patent/YU188790A/en unknown
- 1990-10-05 EP EP90402758A patent/EP0422997A1/en not_active Withdrawn
- 1990-10-05 BR BR909005014A patent/BR9005014A/en not_active Application Discontinuation
- 1990-10-05 CA CA002027011A patent/CA2027011A1/en not_active Abandoned
- 1990-10-05 JP JP2266556A patent/JPH0678552B2/en not_active Expired - Lifetime
- 1990-10-08 IE IE359290A patent/IE903592A1/en unknown
- 1990-10-08 KR KR1019900015974A patent/KR930010380B1/en not_active IP Right Cessation
- 1990-10-08 NO NO90904358A patent/NO904358L/en unknown
- 1990-10-08 PT PT95534A patent/PT95534A/en not_active Application Discontinuation
- 1990-10-08 FI FI904948A patent/FI904948A0/en not_active IP Right Cessation
- 1990-10-09 US US07/594,561 patent/US5104566A/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0040445A1 (en) * | 1980-05-21 | 1981-11-25 | Shell Internationale Researchmaatschappij B.V. | Fluid displacement with heteropolysaccharide solutions, and the microbial production of heteropolysaccharides |
FR2512690A1 (en) * | 1981-09-16 | 1983-03-18 | Ugine Kuhlmann | STABLE SODIUM SILICO ALUMINATE SUSPENSIONS |
EP0092761A2 (en) * | 1982-04-22 | 1983-11-02 | Hoechst Aktiengesellschaft | Microbial polysaccharides, process for their production, microorganisms suitable therefor and use of the polysaccharides |
EP0351303A1 (en) * | 1988-07-13 | 1990-01-17 | Rhone-Poulenc Chimie | Heteropolysaccharide BM07, process for obtaining it and its use in diverse industries |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2756488A1 (en) * | 1996-12-04 | 1998-06-05 | Rhodia Chimie Sa | AQUEOUS COSMETIC COMPOSITIONS BASED ON NON-VOLATILE INSOLUBLE SILICONES, STABILIZED BY A SUCCINOGLYCAN AND THEIR PROCESS OF PREPARATION |
WO1998024408A1 (en) * | 1996-12-04 | 1998-06-11 | Rhodia Chimie | Aqueous cosmetic compositions with base of non-volatile insoluble silicon, stabilised by a succinoglycan |
Also Published As
Publication number | Publication date |
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NO904358D0 (en) | 1990-10-08 |
FI904948A0 (en) | 1990-10-08 |
JPH0678552B2 (en) | 1994-10-05 |
KR910008124A (en) | 1991-05-30 |
YU188790A (en) | 1993-10-20 |
IE903592A1 (en) | 1991-05-08 |
KR930010380B1 (en) | 1993-10-23 |
FR2652820B1 (en) | 1993-12-24 |
JPH03188197A (en) | 1991-08-16 |
BR9005014A (en) | 1991-09-10 |
PT95534A (en) | 1991-08-14 |
FR2652820A1 (en) | 1991-04-12 |
CA2027011A1 (en) | 1991-04-10 |
US5104566A (en) | 1992-04-14 |
NO904358L (en) | 1991-04-10 |
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