WO2006128624A1 - Entschäumerformulierungen - Google Patents
Entschäumerformulierungen Download PDFInfo
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- WO2006128624A1 WO2006128624A1 PCT/EP2006/004948 EP2006004948W WO2006128624A1 WO 2006128624 A1 WO2006128624 A1 WO 2006128624A1 EP 2006004948 W EP2006004948 W EP 2006004948W WO 2006128624 A1 WO2006128624 A1 WO 2006128624A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
Definitions
- the invention relates to antifoam formulations containing (A) antifoams based on siloxanes and (B) polysiloxane copolymers, and to their use for defoaming aqueous media, in particular those resulting from pulp production.
- foaming may cause problems when these systems are brought into more or less intensive contact with gaseous substances, for example when fumigating waste water, during intensive stirring Liquids, in distillation, washing or dyeing processes or in filling operations.
- the control of this foam can be done by mechanical means or by the addition of defoamers.
- Defoamers based on siloxanes have proven particularly useful.
- Defoamers based on siloxanes are prepared, for example, according to DD-A 056 762 by heating hydrophilic silica in polydimethylsiloxanes. This process is quite complicated, but the effectiveness of the antifoams produced in this way is unsatisfactory.
- the distribution of hydrophobized silica in a polydimethylsiloxane, e.g. B. according to DE-A 29 25 722, is a more rational method, the effectiveness of the defoamer obtained but also in need of improvement.
- crosslinked or branched polyorganosiloxanes which carry at least one polyether group are claimed as one of the two components of a defoamer formulation.
- the crosslinking takes place via alkylene groups, via polydimethylsiloxanes or via polyether groups.
- Si-C bonds By linking via Si-C bonds, the products are resistant to hydrolysis.
- the antifoam formulations prepared according to the prior art either do not always have sufficient activity or are not resistant to hydrolysis.
- the object of the invention was therefore to avoid the abovementioned disadvantages and to provide antifoam formulations based on siloxanes, which especially in highly foaming, hot, alkaline media, which are obtained for example in pulp production, have improved efficacy.
- the invention provides antifoam formulations containing
- R 1 is a monovalent optionally substituted hydrocarbon radical to which Si-H groups can be attached in a hydrosilylation reaction, preferably a hydrocarbon radical having an aliphatic C-C multiple bond
- A is a bivalent, polar organic radical selected from the group of -O-, -C (O) -O-, -O-C (O) -, -O-C (O) -O-, -C (O) -NH-, -NH-C (O) -, urethane radical and urea radical , preferably an oxygen atom -O-
- a 1 represents a bivalent, polar organic radical selected from the group of -O-, -NH- and -NR 1 - (wherein R represents a monovalent hydrocarbon radical having 1 to 18 carbon atoms), preferably an oxygen atom -O-, n is an integer of 1 to 20, preferably 1 to 4, preferably 2 or 3, and m is an integer positive number, preferably 5 to 50, are
- the water content refers to room temperature (20 0 C) and the pressure of the surrounding atmosphere (1020 hPa).
- the polysiloxane copolymers according to the invention have a viscosity of preferably 1,000 to 100,000,000 mPa.s at 25 ° C., preferably 1,000 to 10,000,000 mPa.s at 25 ° C.
- Polysiloxane copolymer (B) of crucial importance is crucial importance.
- the antifoam formulations preferably comprise from 0.1 to 75% by weight, preferably from 0.1 to 50% by weight, particularly preferably from 1.5 to 50% by weight, of the polysiloxane copolymers (B) according to the invention.
- polysiloxane copolymers (B) according to the invention are obtained as follows:
- organopolysiloxanes (1) are preferably linear, cyclic or branched organopolysiloxanes of units of the general formula
- R may be the same or different and is a monovalent, optionally substituted hydrocarbon radical having from 1 to 18 carbon atoms per radical, e is 0, 1, 2 or 3, f is 0, 1 or 2 and the sum of e + f is 0.1 , 2 or 3, with the proviso that at least one Si-bonded hydrogen atom, preferably at least 2 Si-bonded hydrogen atoms are present per molecule.
- Preferred organopolysiloxanes (1) are those of the general formula
- R has the meaning given above, g is 0, 1 or 2, o is 0 or an integer from 1 to 1500 and p is 0 or an integer from 1 to 200, with the proviso that per molecule at least one Si bonded hydrogen atom, preferably at least two Si-bonded hydrogen atoms, are present.
- formula (III) is to be understood such that o units - (SiR 2 O) - and p units - (SiRHO) - may be distributed in any desired manner in the organopolysiloxane molecule.
- organopolysiloxanes (1) copolymers of Hydrogenalkylsiloxy- and dialkylsiloxy, especially copolymers of Hydrogenmethylsiloxy- and dimethylsiloxy.
- the organopolysiloxanes (1) preferably have an average viscosity of 10 to 1,000 mPa. s at 25 ° C, preferably 50 to 1000 mPa. s at 25 0 C and particularly preferably 60 to 600 mPa.s at 25 ° C.
- radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl,
- Xylyl radicals and ethylphenyl radicals Xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the ⁇ - and the ⁇ -phenylethyl radical.
- substituted radicals R are haloalkyl radicals, such as the 3, 3, 3-trifluoro-n-propyl radical, the 2, 2, 2, 2 ', 2 ", 2'-hexafluoroisopropyl radical, the heptafluoroisopropyl radical and haloaryl radicals, such as the -, m- and p-chlorophenyl.
- the radical R is preferably a monovalent hydrocarbon radical having 1 to 6 carbon atoms, the methyl radical being particularly preferred.
- radicals R apply in their entirety to radicals R '.
- R 1 is preferably a monovalent
- radicals R 1 are alkenyl radicals, such as the vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl radicals, and alkynyl radicals, such as ethynyl, propargyl and 1 -Propinylrest.
- the radical R 1 is preferably an alkenyl radical, in particular ⁇ -alkenyl radical, the allyl radical being particularly preferred.
- oligomeric or polymeric compounds (2) are polyethers of the general formula
- H 2 C CH-R 2 - (OC n H 2n ) m -OH (IV),
- R 2 is a divalent hydrocarbon radical having 1 to 10 carbon atoms, preferably a radical of the formula -CH 2 -, -CH (CH 3 ) - or -C (CH 3 J 2 - and n and m have the meaning given above.
- Preferred examples of polyethers (2) are those of the general formula
- H 2 C CH-R 2 - (OCH 2 CH 2 ) a [OCH 2 CH (CH 3 )] b -OH (IV),
- R 2 has the meaning given above and a and b is 0 or an integer from 1 to 200, preferably 5 to 50.
- the compounds (2) are preferably in the first process step in amounts of 1.0 to 4.0, preferably 1.3 to 2.5 mol of radical R 1 , which is preferably a radical having a C-C multiple aliphatic bond, preferably an ⁇ -alkenyl radical is used per gram atom of Si-bonded hydrogen in the organopolysiloxane (1).
- radical R 1 is preferably a radical having a C-C multiple aliphatic bond, preferably an ⁇ -alkenyl radical is used per gram atom of Si-bonded hydrogen in the organopolysiloxane (1).
- catalysts (3) preference is given to the addition of Si-bonded hydrogen to an aliphatic multiple bond promoting catalysts (3) used.
- catalysts (3) the same catalysts can also be used in the inventive method, which could also be used to promote the addition of Si-bonded hydrogen to aliphatic multiple bond.
- Catalysts are preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals.
- catalysts are metallic and finely divided platinum, which may be supported on supports such as silica, alumina or activated carbon, compounds or complexes of platinum such as platinum halides, eg PtCl 4 , H 2 PtCl 6 .6H 2 O, Na 2 PtCl 4 * 4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including
- platinum-vinyl-siloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes with or without detectable inorganic content bound halogen, bis (gamma-picoline) -platium dichloride, trimethylenedipyridine platinum dichloride,
- Dicyclopentadiene platinum dichloride dimethylsulfoxydethylenepatin (II) di chloride, cyclooctadiene platinum dichloride, norbornadiene platinum dichloride, gamma picoline platinum dichloride, cyclopentadiene platinum dichloride, and reaction products of platinum tetrachloride with olefin and primary amine or secondary amine or primary and secondary amine such as Reaction product of platinum tetrachloride dissolved in 1-octene with sec. Butylamine or ammonium-platinum complexes.
- the catalyst (3) is preferably in the first process step in amounts of 1 to 50 ppm by weight (parts by weight per million parts by weight), preferably in amounts of 2 to 20 ppm by weight, calculated in each case as elemental platinum and based on the total weight of Organopolysiloxanes (1) and compounds (2) used.
- the first process step is preferably carried out at the pressure of the surrounding atmosphere, ie at about 1020 hPa (abs.), but it can also be done at higher or lower pressures.
- the first process step is preferably conducted at a temperature of 60 0 C to 140 0 C, preferably from 80 ° C to 120 0 C is performed.
- organic compounds (5) which have at least two isocyanate groups per molecule are preferably those of the general formula
- R 3 is a divalent hydrocarbon radical having 4 to 40
- Carbon atoms per radical means used.
- organic compounds (5) are hexamethylene-1, 6-diisocyanate, isophorone diisocyanate, tolylene-2,4-diisocyanate, tolylene-2, ⁇ -diisocyanate, phenylene-1,3-diisocyanate, 4,4'-methylene-bis (cyclohexyl isocyanate), 4,4'-methylene bis (phenyl isocyanate) and dimethyl phenyl diisocyanate.
- Organic compounds (5) are used in the second process step, preferably in amounts of 0.1 to 0.9 mol, preferably 0.2 to 0.7 mol, isocyanate group per mole of H-A ⁇ group in the intermediate (4).
- condensation catalysts (6) such as di-n-butyltin dilaurate, stannous octoate, dibutyltin diacetate, potassium octoate or tert.
- a preferred polysiloxane copolymer is obtained by reacting in the first process step with an excess a methyl-terminated hydrogen-functional polysiloxane (1) which has pendant Si-bonded hydrogen atoms
- Polyether (2) of formula (IV) is reacted and in the second process step, the intermediate product (4), a silicone polyether with comb structure, with a diisocyanate (5) of the formula (V) is reacted, wherein urethane groups are introduced into the polysiloxane.
- free polyether from the 1st step is bound by urethane formation.
- the urethane groups in the hydrophilic polysiloxane copolymers of the invention can act as donors and acceptors in the formation of hydrogen bonds.
- R 4 denotes a hydrogen atom or a radical R which may optionally contain one or more nitrogen atoms
- R 5 denotes a divalent hydrocarbon radical having 1 to 10 carbon atoms per radical
- R 6 is a trivalent organic radical having 1 to 100 carbon atoms per radical, preferably a trivalent Hydrocarbon radical having 1 to 100 carbon atoms, which contains one or more oxygen atoms
- R 7 is a tetravalent organic radical having 1 to 100 carbon atoms per radical, preferably a tetravalent hydrocarbon radical having 1 to 100 carbon atoms, which contains one or more oxygen atoms
- a 1 , n and m have the meaning given above.
- Examples of compounds of formula (VII) are methyl polyethylene oxide, butyl polyethylene oxide, methyl polyethylene oxide / polypropylene oxide and methyl polypropylene oxide.
- Examples of compounds of the formula (VIII) are N-methyldiethanolamine, N-methyldipropanolamine,
- Dimethylaminopropyldipropanolamine, N-dodecyldiethanolamine and N-stearyldipropanolamine Dimethylaminopropyldipropanolamine, N-dodecyldiethanolamine and N-stearyldipropanolamine.
- Examples of compounds of the formula (IX) are N, N-dimethylethanolamine, N, N-diethylpropanolamine, N, N-dimethylaminopropyl-methylethanolamine and dimethyl 2- (2-aminoethoxy) ethanol.
- Examples of compounds of formula (X) are 1, 5-bis (dimethylamino) -pentan-3-ol, 1, 5-bis (methylamino) -pentan-3-ol, 1, 7-bis (dimethylamino) -heptane 4-ol and N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine
- Examples of compounds of the formula (XI) are 2,4,6-tris (dimethylaminomethyl) phenol,
- Examples of compounds of formula (XII) are N, N-bis (dimethylaminopropyl) -3-aminopropane-1,2-diol, N, N-bis (dimethylaminopropyl) -2-aminopropane-1,3-diol, N, N Bis (3-dimethylaminopropyl) -carbamic acid monoglyceride,
- Examples of compounds of the formula (XIII) are dibutylamine, octylamine, benzylamine, 3- (cyclohexylamino) propylamine, 2- (diethylamino) ethylamine, dipropylenetriamine, isophoronediamine, dimethylaminopropylmethylamine, aminopropylmorpholine, N, N-bis (dimethylaminopropyl) amine, dimethylaminopropylamine ,
- Compounds of formula (VII) are used in the second process step in amounts of preferably 0 to 2 mol, preferably 0 to 1 mol, HA 1 group per mole of HA ⁇ group in compound (2).
- Compounds of the formula (VIII) are used in the second process step in amounts of preferably 0 to 2 mol, preferably 0 to 1 mol, of HO group per mole of HA x group in compound (2).
- Compounds of formula (IX) are used in the second process step in amounts of preferably 0 to 2 mol, preferably 0 to 1 mol, HO group per mole of H-A ⁇ group in compound (2).
- Compounds of the formula (X) are used in the second process step in amounts of preferably 0 to 2 mol, preferably 0 to 1 mol, of HO group per mole of HA 1 group in compound (2).
- Compounds of the formula (XI) are used in the second process step in amounts of preferably 0 to 2 mol, preferably 0 to 1 mol, of HO group per mole of HA x group in compound (2).
- Compounds of the formula (XII) are in the second process step in amounts of preferably 0 to 2 mol, preferably 0 to 1 mol, HO group per mole of HA 1 group used in compound (2).
- Compounds of the formula (XIII) are used in the second process step in amounts of preferably 0 to 2 mol, preferably 0 to 1 mol, of HN group per mole of HA 1 group in compound (2).
- polyisocyanate (5) is preferably used in deficit, in order to ensure a safe Abreagieren the harmful isocyanate groups.
- Organic compounds (5) are therefore in the second process step preferably in amounts of 0.1 to 0.9 mol, preferably 0.2 to 0.7 mol, isocyanate group per mole of the sum of isocyanate-reactive functions of the
- the second process step is preferably carried out at the pressure of the surrounding atmosphere, ie at about 1020 hPa (abs.), But it can also be carried out at higher or lower pressures. Furthermore, the second process step is preferably carried out at a temperature of 40 ° C to 160 0 C, preferably 80 0 C to 140 0 C, performed.
- Low molecular weight substances such as alcohols or ethers, may optionally be added to lower the sometimes very high product viscosities.
- alcohols or ethers examples include ethanol, isopropanol, n-butanol, 2-butoxyethanol, diethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, hexaethylene glycol monooctyl ether, tetrahydrofuran,
- Diethylene glycol diethyl ether and dimethoxyethane with tetraethylene glycol monohexyl ether being a preferred example.
- preferred addition amounts are up to 50% by weight, particularly preferably up to 30% by weight, based on the hydrophilic polysiloxane copolymers according to the invention.
- the antifoam formulations according to the invention may additionally comprise polyether-polysiloxane copolymers (F), as described by way of example in DE-A 102 55 649, EP-A 663 225 and EP-A 1076073.
- the polyether-polysiloxane copolymers (F) can be mixed with the polysiloxane copolymers (B) according to the invention.
- the polyether-polysiloxane copolymers (F) can be used in the defoamer formulations according to the invention preferably in amounts of from 0 to 30% by weight, based on the total weight of the defoamer formulation.
- the antifoam formulations according to the invention preferably contain
- siloxane defoamer As an antifoam based on siloxanes (hereinafter also referred to siloxane defoamer) is usually a mixture of silica and polyorganosiloxanes used, the mixture is preferred
- R 8 may be the same or different and is a monovalent, substituted and / or unsubstituted, saturated and / or unsaturated hydrocarbon radical having 1 to 30 carbon atoms each Rest means that R 9 may be the same or different and is a hydrogen atom or a monovalent, substituted and / or unsubstituted, saturated and / or unsaturated hydrocarbon radical having 1 to 30 carbon atoms per radical, d is 0, 1, 2 or 3, where d is average is a value less than 0.5, e is 0, 1, 2 or 3, with the proviso that the sum (d + e) is ⁇ 3 and has an average value of 1.8 to 2.4, (ac) 0 to 10 wt .-% of a silicone resin which consists essentially of units of the general formula R 8 e (R 9 O) d SiO (4 -d) / 2 (XIV) wherein R 8 may be the same or different and is a monovalent, substituted and / or unsubstituted, saturated
- Boiling point greater than 100 0 C selected from mineral oils, native oils, isoparaffins, polyisobutylenes, residues from the Oxoalkoholsynthese, esters of low molecular weight synthetic carboxylic acids, ethers of low molecular weight alcohols, phthalates and esters of phosphoric acid, wherein the wt .-% are each based on the total weight of
- Antifoam agent contains.
- the in situ hydrophobization of the silica (aa) can be carried out by heating the polyorganosiloxane dispersed in the polyorganosiloxane (ab) for several hours at temperatures of 100 to 200 0 C.
- the reaction by the addition of catalysts, such as KOH, and hydrophobing agents, such as short-chain OH-terminated polydimethylsiloxanes, silanes, Silazanes or silicone resins.
- catalysts such as KOH
- hydrophobing agents such as short-chain OH-terminated polydimethylsiloxanes, silanes, Silazanes or silicone resins.
- radicals R 8 in the general formula (II) are unsubstituted, branched or unbranched alkyl radicals, such as methyl, ethyl, propyl, isopropyl, hexyl, 2-ethylhexyl, octyl, or dodecyl radicals; substituted alkyl radicals such as trifluoropropyl, cyanoethyl, glycidoxypropyl, polyalkylene glycolpropyl, aminopropyl or
- Aminoethylaminopropylreste unsaturated radicals, such as vinyl, methacryloxypropyl or allyl radicals; aromatic radicals, such as phenyl, tolyl, xylyl, naphthyl, anthracyl or
- radicals R 8 are the methyl or phenyl radical, it being particularly preferred if more than 80 mol% of the radicals R 8 are methyl radicals.
- radicals R 9 in the general formula (II) are unsubstituted, branched or unbranched alkyl radicals, such as methyl, ethyl, propyl, isopropyl, hexyl, 2-ethylhexyl, octyl, or dodecyl radicals; substituted alkyl radicals such as trifluoropropyl, cyanoethyl, glycidoxypropyl, polyalkylene glycolpropyl, aminopropyl or
- Aminoethylaminopropylreste unsaturated radicals, such as vinyl, methacryloxypropyl or allyl radicals; aromatic radicals, such as phenyl, tolyl, xylyl, naphthyl, anthracyl or benzyl radicals.
- Polydimethylsiloxanes with viscosities of 100 to 1,000,000 mPa's at 25 C C These polydimethylsiloxanes can, for. B. be branched by the incorporation of CH 3 SiO 3/2 or SiO 4/2 units. These branched or cross-linked siloxanes then have viscoelastic properties.
- Such branched viscoelastic polyorganosiloxanes can be obtained, for example, by reacting the dimethyldichlorosilane hydrolysis product or hydroxy-terminated polydimethylsiloxanes with a trimethylsilyl-terminated polydimethylsiloxane and a compound selected from a silane having at least three hydrolyzable groups such as tetraethoxysilane, methyltrimethoxysilane or
- Methyltriacetoxysilane or a silicone resin, which is composed essentially of (CH 3 ) 3 Si0i / 2 - and SiÜ 2 units in the ratio of 2 to 1 to 1 to 2, in the presence of a catalyst.
- Another variant for producing branched viscoelastic polyorganosiloxanes is the reaction of an organosiloxane X 1 having statistically distributed, average less than 2 functional groups per molecule with an organosiloxane X 2 with statistically distributed, average more than 2 functional groups per molecule, wherein per siloxane X 1 or X 2 are each present only one type of functional groups, in the presence of a hydrosilylation-promoting catalyst, such as platinum or platinum compounds.
- a hydrosilylation-promoting catalyst such as platinum or platinum compounds.
- the antifoam based on siloxanes 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, of at least one polyorganosiloxane (ab ' ) of the general formula (XIV), wherein R 8 is a methyl radical and R 9 is a linear and / or branched hydrocarbon radical having at least 6 carbon atoms, d has a value of 0.005 to 0.5 and the sum (d + e) assumes a value of 1.9 to 2.1.
- Such products are for example by alkaline catalyzed condensation of silanol terminated polydimethylsiloxanes with a viscosity of 50 to 50,000 mPa.s at 25 0 C and aliphatic alcohols having more than 6 carbon atoms, such as isotridecyl alcohol, n-octanol, stearyl alcohol, 4-ethyl-hexadecanol or eicosanol, accessible,
- antifoam formulations of the invention it is possible to include further known additives or auxiliaries, for example further fillers, such as aluminum oxide, metal soaps, hydrophobized quartz flour or finely divided hydrophobic polyurethanes.
- further fillers such as aluminum oxide, metal soaps, hydrophobized quartz flour or finely divided hydrophobic polyurethanes.
- substances which act as antifoam oils such as mineral oils, paraffin oils, fatty acid esters, fatty alcohols and waxes in amounts of from 1 to 99% by weight, based on the total weight of the formulation.
- compounds known as thickeners such as polyacrylic acid, polyacrylates, cellulose ethers, such as carboxymethylcellulose and hydroxyethylcellulose, natural gums, such as xanthan gum and polyurethanes, may be added.
- the defoamer formulation according to the invention is prepared by known processes, for example using high shear forces in colloid mills or rotor-stator homogenizers.
- the mixing process can be carried out at reduced pressure in order to prevent the mixing in of air which is contained in highly dispersed fillers.
- defoamer formulations according to the invention in oil-in-water emulsions (O / W emulsions) is preferred.
- the specific polysiloxane copolymers used in the defoamer formulations according to the invention have surfactant properties, and are therefore also suitable as emulsifiers for the formation of oil-in-water emulsions, starting from antifoams based on Siloxanes, suitable.
- the defoamer formulations, when used as emulsions may also be supplemented with additional organic emulsifiers which may form O / W emulsions based on siloxanes.
- the polysiloxane copolymers (B) may be used together with the
- antifoam agents (A) may also be emulsified, or the polysiloxane copolymers (B) may also be added directly after emulsion preparation of the antifoam agent (A) to the antifoam emulsion, or in the form of an emulsion to improve the effect.
- defoamer formulations according to the invention in the form of O / W emulsions preferably contain
- the emulsifiers required to prepare the emulsions can be anionic, cationic or nonionic and are known to those skilled in the preparation of stable silicone emulsions.
- Emulsifier mixtures are preferably used, it being necessary to contain at least one nonionic emulsifier, such as, for example, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, ethoxylated fatty acids, ethoxylated linear or branched alcohols having 10 to 20 carbon atoms and / or glycerol esters.
- nonionic emulsifier such as, for example, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, ethoxylated fatty acids, ethoxylated linear or branched alcohols having 10 to 20 carbon atoms and / or glycerol esters.
- technologies for the preparation of silicone emulsions are known. Usually
- the antifoam formulations according to the invention can be used wherever there is a disturbing foam formation during processes which is to be reduced or completely eliminated. This is e.g. the application in detergents and cleaners, the fight against foam in sewage plants, at
- Defoamer formulations are outstandingly suitable for defoaming aqueous media produced during pulp production.
- A2 400 parts of a hydroxy-terminated polydimethylsiloxane a viscosity of 65 mm 2 / s, 40 parts of trimethylsiloxy-terminated polydimethylsiloxane viscosity of 40 mm 2 / s, 4 parts of methyltrimethoxysilane and 1 part of a 0.5% Phosphornitridchloridkatalysators were heated to 100 0 C. In the course of 20 minutes, the pressure was lowered to 35 mbar. Thereafter, the neutralization of the catalyst with 0.03 parts of triisooctylamine. The polyorganosiloxane obtained had a viscosity of 19,000 mm 2 / s. In 95 parts of this oil, 5 parts of a pretreated hydrophobic silica were incorporated and homogenized with a colloid mill.
- A3 a mixture of 89.3 parts of a trimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 5,000 mm 2 / s, 5 parts of a pyrogenic hydrophilic silica having a BET surface area of 300 m 2 / g, 0.7 parts of a 20% methanolic KOH, 2.5 parts of a silicone resin of 40 mol% of trimethylsiloxy units and 60 mol% of SiC> 4/2 units and 2.5 parts of a siloxane obtained by condensation of eicosanol with a hydroxy-terminated
- Polydimethylsiloxane a viscosity of 65 mm 2 / s was prepared, were heated to 150 0 C for 2 h. After cooling, the mixture was homogenized with a colloid mill.
- the mixture is further heated to 130 0 C and removes traces of water in a vacuum. Thereafter, 7 g of hexamethylene diisocyanate are metered in and homogenized for 20 minutes.
- the isocyanate reaction is started with a drop of DBTL. After 2 hours, the NCO content has fallen below the detection limit (IR: 20 ppm), so that 120 g Emulan® HE 50 (BASF) are metered.
- the 80% copolymer solution has a viscosity of 2100 mm 2 / s and a urethane content of 0.139 m eq. /G.
- Polyether-polysiloxane Copolmeres having a viscosity of 800 mPa's at 25 ° C and a cloud point of 30 0 C used.
- polymer 3 As polymer 3, a polymer corresponding to example B3 from EP-A 1 076 073 was used.
- polymer 4 As polymer 4, a polymer corresponding to polymer 1 from DE-A 10255649 was used.
- Foam height of 30 cm was immediately added 5 mg of silicone (total 25 mg of silicone). The time t between the beginning of the test and the time after the last addition when the foam had risen again to 30 cm was measured.
- Silicone defoamer and 10 parts of the polysiloxane copolymer indicated in the table with a laboratory dissolver were prepared.
- a mixture of 20 parts of this defoamer formulation and 80 parts of a mixture of aliphatic hydrocarbons having a viscosity of 3 mm 2 / s and a flash point> 100 ° C with a laboratory dissolver at 1,000 min "1 was prepared.
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/915,941 US7645360B2 (en) | 2005-06-02 | 2006-05-24 | Defoamer formulations |
CN2006800191799A CN101189282B (zh) | 2005-06-02 | 2006-05-24 | 消泡剂配制品 |
JP2008513980A JP2008542010A (ja) | 2005-06-02 | 2006-05-24 | 消泡剤組成物 |
EP06743051A EP1885770B1 (de) | 2005-06-02 | 2006-05-24 | Entschäumerformulierungen |
DE502006001774T DE502006001774D1 (de) | 2005-06-02 | 2006-05-24 | Entschäumerformulierungen |
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DE102005025450.0 | 2005-06-02 | ||
DE102005025450A DE102005025450A1 (de) | 2005-06-02 | 2005-06-02 | Entschäumerformulierungen |
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WO2006128624A1 true WO2006128624A1 (de) | 2006-12-07 |
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US (1) | US7645360B2 (de) |
EP (1) | EP1885770B1 (de) |
JP (1) | JP2008542010A (de) |
KR (1) | KR101006939B1 (de) |
CN (1) | CN101189282B (de) |
DE (2) | DE102005025450A1 (de) |
WO (1) | WO2006128624A1 (de) |
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DE102009045365A1 (de) | 2009-10-06 | 2011-04-07 | Wacker Chemie Ag | Verfahren zum Entlüften von Flüssigkeiten |
WO2011104196A2 (de) | 2010-02-23 | 2011-09-01 | Wacker Chemie Ag | Verfahren zum entlüften von flüssigkeiten |
WO2011134746A1 (de) | 2010-04-28 | 2011-11-03 | Wacker Chemie Ag | Entschäumerzusammensetzungen |
JP2012509376A (ja) * | 2008-11-20 | 2012-04-19 | ワッカー ケミー アクチエンゲゼルシャフト | 消泡剤組成物 |
DE102011089374A1 (de) | 2011-12-21 | 2013-06-27 | Wacker Chemie Ag | Verfahren zur Herstellung von Entschäumerzusammensetzungen |
DE102016203344A1 (de) | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Entschäumerzusammensetzungen für Waschmittel |
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KR102686775B1 (ko) * | 2021-08-04 | 2024-07-19 | 주식회사 에스엘티 | 실리콘 소포제 조성물의 제조 방법 및 이에 의해 제조된 실리콘 소포제 조성물 |
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- 2006-05-24 US US11/915,941 patent/US7645360B2/en not_active Expired - Fee Related
- 2006-05-24 EP EP06743051A patent/EP1885770B1/de not_active Not-in-force
- 2006-05-24 DE DE502006001774T patent/DE502006001774D1/de active Active
- 2006-05-24 CN CN2006800191799A patent/CN101189282B/zh not_active Expired - Fee Related
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Cited By (19)
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JP2012509376A (ja) * | 2008-11-20 | 2012-04-19 | ワッカー ケミー アクチエンゲゼルシャフト | 消泡剤組成物 |
WO2011042342A1 (de) | 2009-10-06 | 2011-04-14 | Wacker Chemie Ag | Verfahren zum entlüften von flüssigkeiten |
KR101526651B1 (ko) * | 2009-10-06 | 2015-06-05 | 와커 헤미 아게 | 액체의 탈기 방법 |
DE102009045365A1 (de) | 2009-10-06 | 2011-04-07 | Wacker Chemie Ag | Verfahren zum Entlüften von Flüssigkeiten |
US8563640B2 (en) | 2010-02-23 | 2013-10-22 | Wacker Chemie Ag | Method for deaerating liquids |
WO2011104196A2 (de) | 2010-02-23 | 2011-09-01 | Wacker Chemie Ag | Verfahren zum entlüften von flüssigkeiten |
DE102010002234A1 (de) | 2010-02-23 | 2011-10-06 | Wacker Chemie Ag | Verfahren zum Entlüften von Flüssigkeiten |
WO2011134746A1 (de) | 2010-04-28 | 2011-11-03 | Wacker Chemie Ag | Entschäumerzusammensetzungen |
DE102010028306A1 (de) | 2010-04-28 | 2011-11-03 | Wacker Chemie Ag | Entschäumerzusammensetzungen |
US8530401B2 (en) | 2010-04-28 | 2013-09-10 | Wacker Chemie Ag | Antifoam compositions comprising a mixture of organopolysiloxanes |
WO2013092462A1 (de) | 2011-12-21 | 2013-06-27 | Wacker Chemie Ag | Verfahren zur herstellung von entschäumerzusammensetzungen |
DE102011089374A1 (de) | 2011-12-21 | 2013-06-27 | Wacker Chemie Ag | Verfahren zur Herstellung von Entschäumerzusammensetzungen |
US9114333B2 (en) | 2011-12-21 | 2015-08-25 | Wacker Chemie Ag | Method for producing antifoam compositions |
DE102016203344A1 (de) | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Entschäumerzusammensetzungen für Waschmittel |
DE102016203346A1 (de) | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Entschäumerzusammensetzungen für Waschmittel |
WO2017148723A1 (de) | 2016-03-01 | 2017-09-08 | Wacker Chemie Ag | Entschäumerzusammensetzungen für waschmittel |
WO2017148750A1 (de) | 2016-03-01 | 2017-09-08 | Wacker Chemie Ag | Entschäumerzusammensetzungen für waschmittel |
US10744425B2 (en) | 2016-03-01 | 2020-08-18 | Wacker Chemie Ag | Defoaming compositions for detergents |
US10870732B2 (en) | 2016-03-01 | 2020-12-22 | Wacker Chemie Ag | Defoamer compositions for detergents |
Also Published As
Publication number | Publication date |
---|---|
KR20080014060A (ko) | 2008-02-13 |
CN101189282A (zh) | 2008-05-28 |
JP2008542010A (ja) | 2008-11-27 |
US20080200608A1 (en) | 2008-08-21 |
US7645360B2 (en) | 2010-01-12 |
KR101006939B1 (ko) | 2011-01-10 |
EP1885770B1 (de) | 2008-10-08 |
CN101189282B (zh) | 2011-08-03 |
DE102005025450A1 (de) | 2006-12-07 |
DE502006001774D1 (de) | 2008-11-20 |
EP1885770A1 (de) | 2008-02-13 |
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