EP0422998A1 - Wässerige Zeolithsuspension, die ein Silikonat enthält - Google Patents

Wässerige Zeolithsuspension, die ein Silikonat enthält Download PDF

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Publication number
EP0422998A1
EP0422998A1 EP90402759A EP90402759A EP0422998A1 EP 0422998 A1 EP0422998 A1 EP 0422998A1 EP 90402759 A EP90402759 A EP 90402759A EP 90402759 A EP90402759 A EP 90402759A EP 0422998 A1 EP0422998 A1 EP 0422998A1
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EP
European Patent Office
Prior art keywords
siliconate
suspension
weight
stabilizer
derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90402759A
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English (en)
French (fr)
Other versions
EP0422998B1 (de
Inventor
Daniel Joubert
Marc Malassis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0422998A1 publication Critical patent/EP0422998A1/de
Application granted granted Critical
Publication of EP0422998B1 publication Critical patent/EP0422998B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/162—Organic compounds containing Si
    • 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 aqueous suspensions of zeolite.
  • aqueous suspensions of zeolites present many industrial handling difficulties due to their very particular rheological behavior.
  • suspensions have a dilating behavior and their viscosity is very high. They are therefore difficult to pump, which makes their use, for example their introduction into possibly sprayable detergent mixtures, difficult or even impossible. In addition, these suspensions tend to sediment or gel, which makes them difficult to transport or store. So there is a real problem there.
  • the main object of the invention is therefore a system for obtaining aqueous suspensions of low viscosity zeolite, in particular pumpable.
  • Another object of the invention is a system which also makes it possible to obtain a stable aqueous suspension.
  • the suspensions according to the invention comprise zeolites and they are characterized in that they also comprise a siliconate and / or a siliconate derivative.
  • the aqueous zeolite suspension also comprises at least one stabilizer.
  • siliconates or derivatives has the effect of considerably lowering the viscosity of the zeolite suspensions. It also makes it possible to obtain manipulable suspensions with a higher dry extract, for example of at least 55%. Finally, it has been noted that the siliconates do not influence the exchange capacity of the zeolites.
  • 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 cited reference 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.
  • 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, ether, ester, epoxy, mercapto, cyano, (poly) glycol group.
  • n 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 hydrolysable 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 that 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.
  • 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 here for a solution at 50% by weight in water of the siliconate or derivative.
  • siliconates has the effect of making the zeolite suspensions pumpable and manipulable due to their low viscosity.
  • suspensions which are stable that is to say which do not settle or little.
  • these suspensions can be transported or stored without difficulty.
  • the suspensions comprise, in addition to the siliconate, a stabilizer.
  • magnesium is preferably used.
  • the cation can, moreover, be provided in the form of a halide, in particular a chloride, more particularly magnesium chloride, for example magnesium chloride hexahydrate, is used.
  • a halide in particular a chloride, more particularly magnesium chloride, for example magnesium chloride hexahydrate, is used.
  • the amount of cation used generally varies between 0.002 and 0.5% relative to the weight of the final suspension.
  • stabilizers which can be used according to the invention, mention may be made of natural polysaccharides of animal origin such as chitosame and chitin; of vegetable origin such as carragenanes, alginates, gum arabic, guar, carob, tara, cassia, konjak mannan, and finally those of bacterial or biogum origin.
  • animal origin such as chitosame and chitin
  • vegetable origin such as carragenanes, alginates, gum arabic, guar, carob, tara, cassia, konjak mannan, and finally those of bacterial or biogum origin.
  • Biogums are polysaccharides of high molecular weight, generally greater than a million, obtained by fermentation of a carbohydrate under the action of a microorganism.
  • biogum which can be used in the suspension which is the subject of the present invention there may be mentioned more particularly, xanthan gum, that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xanthomonas such as Xanthomonas begoniae, Xanthomonas campestris, Xanthomonas carotae, Xanthomonas hederae, Xanthomonas incanae, Xanthomonas malvacearum, Xanthomonas papavericola, Xanthomonas phaseoli, Xanthomonas pisi, Xanthomonas vasculorum, Xanthomonas vesicatoria, Xanthomonas vitians, Xanthomonas pelargonii.
  • Xanthan gum that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xant
  • Xanthan gums are commonly found commercially.
  • gellan gum obtained from Pseudomonas Elodea, Rhamsan and Welan gums obtained from Alcaligenes.
  • cellulose and starch or their derivatives. Mention may be made, for example, of carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, cyanoethylated starch, carboxymethylated starch.
  • polysaccharides are used in solid form, in powder, or in aqueous solution.
  • carboxylic acids and their salts and in particular acetic, formic, oxalic, malic, citric and tartaric acids.
  • alkaline salts such as NaHCO3, NaCl, Na2CO3, Na2SO4 and sodium pyrophosphate or tripolyphosphate.
  • water-soluble polymers of acrylic acid crosslinked with a sucrose polyallylether for example in a proportion of approximately 1% and having an average of approximately 5.8 allyl groups for each sucrose molecule.
  • polymers with a molecular weight greater than 1,000,000 polymers of this type can be found in the CARBOPOL series for example CARBOPOL 934, 940 and 941.
  • CARBOPOL 934, 940 and 941 the quantities used in percentage by weight relative to the final suspension vary between 0.001 and 2%.
  • the zeolite suspensions according to the invention are prepared in a simple manner by introducing the additives described above into the suspension.
  • the pH of the suspensions 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 relates to 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, dyes, enzymes, optical agents.
  • the dry extract of the suspension is given in percentage by weight in% 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 alkalite 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.
  • Sedimentation is determined by introducing the zeolite suspension into graduated cylinders of 50 or 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.
  • Table 1 Example 1 comparison 2 comparison 3 according to the invention 4 according to the invention Suspension% anhydrous zeolite 47.5 47.5 47.2 47.6 Exchange capacity 303 303 303 303 Siliconate% suspension 0 0 0.17 0.08 pH 10.88 11.07 10.87 11.06 Viscosity (in poise) at 5 s ⁇ 1 12.5 27.4 0.17 6.5
  • the siliconate used is the product sold under the name RHODORSIL SILICONATE 51T by the Applicant with the formula CH3Si (OK) 3.
  • Examples 8 to 9 describe the use of xanthan gum as a stabilizer. We always use the same siliconate. The results are given in Table 3. The amount of xanthan gum used is 0.12% and 0.1% by weight relative to the suspension for Examples 8 and 9 respectively.
  • Example 10 relates to the use of oxalic acid as a stabilizer. This is used at 1% by weight relative to the suspension.
  • the siliconate is the same as in Examples 8 and 9.
  • Example 11 relates to the use of Carbopol 941 as a stabilizer at 0.1% by weight relative to the suspension.
  • Table 3 Examples 8 9 10 11 Suspension% anhydrous zeolite 47.5 49.3 49.3 49.7 Exchange capacity 288 288 288 Siliconate (% suspension) 0.17 0.2 0.1 0.1 pH 10.86 11.46 11.03 10.66 Viscosity in poise at 5 s ⁇ 1 10.2 10.2 6.5 3.1 Sunageant (% volume) 5 days 3 1.5 2 2 10 days 4 2 7 Decantate% 5 days ⁇ 0.5 "1 0 1 10 days 0.5 1 "1
  • a suspension of the same zeolite as the preceding examples is used at a concentration of 49.7% and without any additive.
  • the pH is 11.57.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silicon Polymers (AREA)
EP90402759A 1989-10-09 1990-10-05 Wässerige Zeolithsuspension, die ein Silikonat enthält Expired - Lifetime EP0422998B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8913138A FR2652819B1 (fr) 1989-10-09 1989-10-09 Suspension de zeolite comprenant un siliconate.
FR8913138 1989-10-09

Publications (2)

Publication Number Publication Date
EP0422998A1 true EP0422998A1 (de) 1991-04-17
EP0422998B1 EP0422998B1 (de) 1996-06-19

Family

ID=9386194

Family Applications (1)

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EP90402759A Expired - Lifetime EP0422998B1 (de) 1989-10-09 1990-10-05 Wässerige Zeolithsuspension, die ein Silikonat enthält

Country Status (17)

Country Link
US (2) US5401432A (de)
EP (1) EP0422998B1 (de)
JP (1) JPH0633408B2 (de)
KR (1) KR910008123A (de)
AT (1) ATE139560T1 (de)
BR (1) BR9005013A (de)
CA (1) CA2027012A1 (de)
DE (1) DE69027504T2 (de)
DK (1) DK0422998T3 (de)
ES (1) ES2087898T3 (de)
FI (1) FI904947A0 (de)
FR (1) FR2652819B1 (de)
GR (1) GR3020637T3 (de)
IE (1) IE903593A1 (de)
NO (1) NO177064C (de)
PT (1) PT95533B (de)
YU (1) YU47377B (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0733699A2 (de) * 1995-03-24 1996-09-25 The Procter & Gamble Company Waschmittelzusammensetzung
AU720214B2 (en) * 1996-03-25 2000-05-25 Eka Chemicals Ab Zeolite dispersion
EP1247834A1 (de) * 1999-10-21 2002-10-09 Daiso Co., Ltd. Vernetzungsmittel aus einer polyallylethylen-verbindung

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5780412A (en) * 1995-08-09 1998-07-14 The Sherwin-Williams Company Alkaline-stable hard surface cleaning compounds combined with alkali-metal organosiliconates
US5800603A (en) * 1996-03-25 1998-09-01 Eka Chemicals Ab Zeolite dispersion
DE102010031624A1 (de) 2010-07-21 2012-01-26 Wacker Chemie Ag Wasserlösliche Organosiliconatpulver
CN103327959B (zh) * 2011-02-03 2015-09-23 阿克佐诺贝尔化学国际公司 用于个人护理应用的改性淀粉
CA2832814C (en) * 2011-04-12 2019-04-02 Basf Se Hydrophobic, functionalised particles

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138363A (en) * 1977-09-14 1979-02-06 Pq Corporation Silane-zeolite compositions
EP0088158A1 (de) * 1982-03-10 1983-09-14 Degussa Aktiengesellschaft Verfahren zur Herstellung von mit Organosilanen oberflächenmodifizierten Zeolithen

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US2441423A (en) * 1945-02-10 1948-05-11 Gen Electric Alkylsilicon sols and gels
US2441422A (en) * 1945-02-10 1948-05-11 Gen Electric Organosilicon-silica sols, gels, and aerogels
AT335035B (de) * 1974-10-10 1977-02-25 Henkel & Cie Gmbh Stabile suspensionen wasserunloslicher, zum binden von calciumionen befahigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
DE2824443A1 (de) * 1978-06-03 1979-12-13 Basf Ag Lagerstabile und fliessfaehige silikatsuspensionen
US4421657A (en) * 1982-04-08 1983-12-20 Colgate-Palmolive Company Heavy duty laundry softening detergent composition and method for manufacture thereof
DE3301577A1 (de) * 1983-01-19 1984-07-19 Henkel KGaA, 4000 Düsseldorf Wasch- und reinigungsmittel
AU3215784A (en) * 1983-08-22 1985-03-29 Aktien Henkel Kommanditgesellschaft Auf Stabilisierte wasrige zeolith-suspension
US4534880A (en) * 1984-03-27 1985-08-13 Dow Corning Corporation Detergent composition with siliconate-zeolite and silicate builder
US4549979A (en) * 1984-03-27 1985-10-29 Dow Corning Corporation Detergent composition with siliconate-silicate copolymer
FR2568790B1 (fr) * 1984-08-10 1990-01-12 Rhone Poulenc Chim Base Procede d'obtention d'une suspension aqueuse stable et pompable de zeolite et suspension ainsi obtenue
US4548733A (en) * 1984-10-05 1985-10-22 Dow Corning Corporation Anionic siliconates of silylorganocarboxylates, sulfonates and phosphonates to reduce viscosities of particulate slurries
JPS61256915A (ja) * 1985-05-10 1986-11-14 Showa Koki Kk ゼオライトスラリ−
JPS62167216A (ja) * 1986-01-17 1987-07-23 Lion Corp 水性ゼオライト懸濁液
US4741862A (en) * 1986-08-22 1988-05-03 Dow Corning Corporation Zeolite built detergent compositions
FR2652818B1 (fr) * 1989-10-09 1994-04-01 Rhone Poulenc Chimie Suspension de zeolite comprenant une resine silicone.
FR2652820B1 (fr) * 1989-10-09 1993-12-24 Rhone Poulenc Chimie Suspensions stables de zeolites comprenant un succinoglycane.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138363A (en) * 1977-09-14 1979-02-06 Pq Corporation Silane-zeolite compositions
EP0088158A1 (de) * 1982-03-10 1983-09-14 Degussa Aktiengesellschaft Verfahren zur Herstellung von mit Organosilanen oberflächenmodifizierten Zeolithen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0733699A2 (de) * 1995-03-24 1996-09-25 The Procter & Gamble Company Waschmittelzusammensetzung
EP0733699A3 (de) * 1995-03-24 1997-08-13 Procter & Gamble Waschmittelzusammensetzung
AU720214B2 (en) * 1996-03-25 2000-05-25 Eka Chemicals Ab Zeolite dispersion
EP1247834A1 (de) * 1999-10-21 2002-10-09 Daiso Co., Ltd. Vernetzungsmittel aus einer polyallylethylen-verbindung
EP1247834A4 (de) * 1999-10-21 2005-11-16 Daiso Co Ltd Vernetzungsmittel aus einer polyallylethylen-verbindung

Also Published As

Publication number Publication date
JPH03188196A (ja) 1991-08-16
BR9005013A (pt) 1991-09-10
KR910008123A (ko) 1991-05-30
US5401432A (en) 1995-03-28
YU188590A (sh) 1993-10-20
FR2652819A1 (fr) 1991-04-12
NO177064C (no) 1995-07-12
US5618874A (en) 1997-04-08
DE69027504D1 (de) 1996-07-25
ES2087898T3 (es) 1996-08-01
FI904947A0 (fi) 1990-10-08
JPH0633408B2 (ja) 1994-05-02
GR3020637T3 (en) 1996-10-31
PT95533A (pt) 1991-08-14
DE69027504T2 (de) 1996-12-12
NO177064B (no) 1995-04-03
NO904359L (no) 1991-04-10
FR2652819B1 (fr) 1994-01-07
DK0422998T3 (da) 1996-07-15
EP0422998B1 (de) 1996-06-19
YU47377B (sh) 1995-01-31
NO904359D0 (no) 1990-10-08
ATE139560T1 (de) 1996-07-15
PT95533B (pt) 1997-07-31
CA2027012A1 (fr) 1991-04-10
IE903593A1 (en) 1991-05-08

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