WO2023186288A1 - Formulations antimousses contenant des triacylglycérides et des polydiorganosiloxanes en tant qu'additifs - Google Patents

Formulations antimousses contenant des triacylglycérides et des polydiorganosiloxanes en tant qu'additifs Download PDF

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WO2023186288A1
WO2023186288A1 PCT/EP2022/058382 EP2022058382W WO2023186288A1 WO 2023186288 A1 WO2023186288 A1 WO 2023186288A1 EP 2022058382 W EP2022058382 W EP 2022058382W WO 2023186288 A1 WO2023186288 A1 WO 2023186288A1
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oil
acid
weight
parts
units
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PCT/EP2022/058382
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German (de)
English (en)
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Johannes ZIRZLMEIER
Christof Brehm
Elisabeth HÖLZLWIMMER
Stefan Wolfrum
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Wacker Chemie Ag
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Priority to PCT/EP2022/058382 priority Critical patent/WO2023186288A1/fr
Publication of WO2023186288A1 publication Critical patent/WO2023186288A1/fr

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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

Definitions

  • the invention relates to defoamer formulations containing triacylglycerides and special polydiorganosiloxanes, as well as their use in aqueous surfactant systems.
  • This foam can be combated mechanically or by adding defoamers.
  • defoamers especially for detergents, are based on silicones.
  • EP 1 703 958 B1 describes organopolysiloxane-free granulated defoamer formulations in which, instead of organopolysiloxanes, hydrocarbon oils and vegetable oils are used together with a particulate filler and an organopolysiloxane resin. Additionally, an additive composition containing a polyol ester is included in the formulations.
  • the polyol esters described are polyols quantitatively esterified with carboxylate groups with 7 to 36 carbon atoms, such as tristearyl glycerides.
  • 5,693,256 A describes defoamer formulations in which, instead of organopolysiloxanes, water-insoluble organic liquids are used together with a hydrophobic filler and an organopolysiloxane resin.
  • the water-insoluble organic liquid used can also be a vegetable oil.
  • rapeseed oil and/or peanut oil are described as vegetable oils.
  • Vegetable oils are triacylglycerides in which three fatty acid residues are linked together to a glycerol residue via ester bonds.
  • Rapeseed oil is a triacylglyceride whose fatty acid residues are predominantly oleic acid, linoleic acid, linolenic acid and palmitic acid residues, i.e. Gig or Ci 8 fatty acid residues.
  • peanut oil which consists predominantly of oleic acid, linoleic acid and palmitic acid residues, and therefore also of Cig or Gig fatty acid residues.
  • the defoamer formulations based on rapeseed oil or Peanut oil has a very good effect in the applications described there.
  • the foam regulating agents are based on triacylglycerides with predominantly C12 to cis fatty acid residues, for example with lauric, myristic, Palmitic, oleic, linoleic and linolenic acid residues, such as those found as essential Component in the rapeseed oil or peanut oil described, but also in other common vegetable oils, such as soybean oil, palm oil and coconut oil, sometimes only have a very weak effect without another additive.
  • the task was therefore to provide defoamer formulations which do not have the above-mentioned disadvantage and which at the same time contain a significantly reduced amount of polydiorganosiloxanes compared to defoamer formulations based on silicones.
  • the problem is solved by the invention.
  • the invention therefore relates to defoamer formulations (Ef).
  • oils and fats essentially consisting of triacylglycerides of the formula (I),
  • R 4 -CO- (II) are in the
  • R 4 is an aliphatic, linear or branched hydrocarbon radical with 3 to 33 carbon atoms, preferably with 5 to 21 carbon atoms, and 0 or 1-6 double bonds, preferably 0 or 1-3 double bonds, which contains one or more heteroatoms from the group sulfur, Oxygen, such as in the form of a hydroxy group, and halogen, means and
  • R 5 means a methyl radical
  • R 6 represents a monovalent hydrocarbon radical with 2 to 30 carbon atoms
  • R 7 means a methyl radical or a radical OR 8 ,
  • R 8 can be the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical with 1 to 4 carbon atoms, the sum of m and n is an integer, where n is not equal to 0,
  • R 9 can be the same or different and represents a hydrogen atom or a monovalent, optionally substituted, SiC-bonded hydrocarbon residue with 1 to 30 carbon atoms,
  • the defoamer formulations (Ef) preferably contain 100 parts by weight of oils and fats (A), consisting essentially of triacylglycerides of the formula (I) and at least 1 part by weight, preferably at least 1.5 parts by weight, particularly preferred at least 2 parts by weight, and at most 25 parts by weight, preferably at most 20 parts by weight, particularly preferably at most 15 parts by weight, of polydiorganosiloxanes (B) of the general formula (III), each based on 100 parts by weight.
  • oils and fats (A) consisting essentially of triacylglycerides of the formula (I) and at least 1 part by weight, preferably at least 1.5 parts by weight, particularly preferred at least 2 parts by weight, and at most 25 parts by weight, preferably at most 20 parts by weight, particularly preferably at most 15 parts by weight, of polydiorganosiloxanes (B) of the general formula (III), each based on 100 parts by weight.
  • Parts (A) at least 0 parts by weight and at most 25 parts by weight, preferably at most 15 parts by weight, particularly preferably at most 10 parts by weight of water-insoluble organic compound (E), each based on 100 parts by weight.
  • Parts (A) and at least 0 parts by weight, preferably at least 0.05 parts by weight, particularly preferably at least 0.1 parts by weight, and at most 2 parts by weight, preferably at most 1 part by weight, particularly preferably at most 0.5 Parts by weight of alkaline or acidic catalysts (F) or their reaction products with components (A) to (E), each based on 100 weight.
  • -Parts (A) at least 0 parts by weight and at most 25 parts by weight, preferably at most 15 parts by weight, particularly preferably at most 10 parts by weight of water-insoluble organic compound (E), each based on 100 parts by weight.
  • Parts (A) and at least 0 parts by weight, preferably at least 0.05 parts by weight, particularly preferably at least 0.1 parts by weight, and at
  • the defoamer formulations (Ef) preferably consist of components (A) to (D) and, if necessary. (E) and if necessary. (F) .
  • Typical examples of the fatty acids R 1 -OH, R 2 -OH and R 3 -OH of the general formula R 4 -COOH are caproic acid, caprylic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, Petroselic acid, linoleic acid, alpha-linolenic acid, gamma-linolenic acid, elaeostearic acid, ricinoleic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and mixtures thereof.
  • Preferred for (A) are the usual natural vegetable or animal oils and fats and any mixtures thereof.
  • avocado oil apricot kernel oil, argan oil, babassu oil, cottonseed oil, borage oil, chaulmoogra oil, peanut oil, safflower oil, pomegranate seed oil, rosehip seed oil, hemp oil, hazelnut oil, blackcurrant seed oil, jojoba oil, cocoa butter, coconut fat, coconut oil, coriander oil, pumpkin seed oil, linseed oil, macadamia nut oil, corn oil, Almond oil , mango butter, marula oil, MCT oil, evening primrose oil, olive kernel oil, olive oil, palm kernel oil, palm oil, perilla oil, peach kernel oil, pistachio kernel oil, rapeseed oil, such as old and new rapeseed oil, rice germ oil, castor oil, Sacha Inchi 01, sea buckthorn pulp oil, black cumin oil, mustard oil, sesame oil, Shea butter, soybean oil, sunflower oil, tea oil, grape seed oil, walnut oil, wheat germ oil
  • the radical R 6 is preferably a hydrocarbon radical with 2 to 30 carbon atoms, particularly preferably a hydrocarbon radical with 8 to 20 carbon atoms, in particular radicals of the formula -C12H25 and -Ci6H 33 .
  • radical R 6 examples include alkyl radicals such as ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert.
  • -Pentyl radical hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals , such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, hexadecyl radicals, such as the n-hexadecyl radical, octadecyl radicals, such as the n-octadecyl radical, eicosyl radicals, such as the n-eicosyl radical; alkenyl radicals, such as the vinyl and allyl radicals; Cycloalkyl radicals,
  • the hydrocarbon radicals R 6 can contain ether or polyether groups.
  • the radical R 8 is preferably the hydrogen atom, the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or the tert.
  • -Butyl radical particularly preferably the methyl radical or the ethyl radical, in particular the methyl radical.
  • n is an integer
  • m and n are chosen such that the polydiorganosiloxanes (B) of the formula (III) preferably have a chain length m + n from 10 to 300, preferably from 30 to 250, in particular from 40 to 200, with the proviso that n is not equal to 0.
  • m can be 0. If m is not equal to 0, the ratio of m and n (m / n) is preferably from 50 to 0.02, preferably from 15 to 0.05, in particular from 5 to 0.2.
  • formula (III) should be understood to mean that m units -(SiR 5 2O)- and n units - (SiR 5 R 6 O)- can be distributed in any way, for example as a block or randomly, in the polydiorganosiloxane molecule .
  • the polydiorganosiloxanes (B) are commercially available products or can be prepared using any methods previously known in organosilicon chemistry, such as by cohydrolysis of the corresponding silanes or via hydrosilylation reactions.
  • the polydiorganosiloxanes (B) can be branched, for example, by incorporating RS1O3/2 or SiO4/2 units. These branched or cross-linked polysiloxanes then have viscoelastic properties.
  • the polydiorganosiloxanes (B) can contain residues of hydrogen (Si-H) bonded to silicon.
  • the polysiloxanes (B) are preferably linear.
  • Component (C) is preferably powdery, hydrophilic and/or hydrophobic fillers.
  • the fillers (C) used are preferably silicon dioxide (silicic acids), titanium dioxide or aluminum oxide.
  • the fillers (C) used in the defoamer formulations according to the invention preferably have a BET surface from 20 to 1000 m 2 /g.
  • the fillers preferably have fe
  • (C) a particle size of less than 10 gm and an agglomerate size of less than 100 gm.
  • component (C) are metal soaps, quartz powder, PTFE powder, fatty acid amides, for example.
  • component (C) are silicas, particularly preferably those with a BET surface area of 50 to 800 m 2 /g, in particular those with a BET surface area of 80 to 500 m 2 /g. These silicas can be pyrogenic or precipitated silicas. Both pretreated silicas can be used as component (C), i.e. commercially available hydrophobic silicas, as well as hydrophilic silicas.
  • hydrophobic silicas examples include HDK® H2000, a pyrogenic silica treated with hexamethyldisilazanes with a BET surface area of 140 m 2 /g (available from Wacker-Chemie AG, Kunststoff, Germany) and a precipitated silica treated with polydimethylsiloxane with a BET surface area of 90 m 2 /g (available under the name Sipernat® D10 from Evonik AG, Essen, Germany).
  • hydrophilic silica that can be used according to the invention is HDK® T30, a fumed silica with a BET surface area of 300 m 2 /g (available from Wacker-Chemie AG, Kunststoff, Germany).
  • hydrophobic silicas with commercially available hydrophilic silicas.
  • 0.2 to 5 parts of hydrophilic silica are used for each 1 part of hydrophobic silica.
  • residue R 9 is one
  • Hydrocarbon residue with 1 to 30 carbon atoms Hydrocarbon residue with 1 to 30 carbon atoms.
  • radical R 9 are analogous to the radicals given for R 6 and the methyl radical.
  • radicals R 9 are the methyl, ethyl and phenyl radicals.
  • radicals R 10 are the radicals given for the radical R 8 .
  • the radical R 10 is preferably a hydrogen atom or a methyl or ethyl radical.
  • the value for a is preferably equal to 3 or 0.
  • component (D) is organopolysiloxane resins which consist essentially of R 9 3SiOi/2 (M) and SiC>4/2 (Q) units, where R 9 has the meaning given above.
  • Organopolysiloxane resins, which essentially consist of R 9 3SiOi/2 (M) and S1O4/2 (Q) units, are also called MQ resins.
  • the MQ resins may optionally also contain small amounts of R 9 SiO 3 /2 or (R 10 O) SiO 3 /2 (T) units or R 9 2 SiO2/2 (D) - Units, in amounts of preferably 0.01 to 20 mol%, preferably 0.01 to 10 mol%, based on the sum of all siloxane units, where R 10 is that specified above has meaning.
  • the molar ratio of M to Q units is preferably in the range from 0.5 to 2.0, preferably in the range from 0.6 to 1.0.
  • the organopolysiloxane resins (D) can also contain up to 10% by weight of free, Si-bonded hydroxy or alkoxy groups, such as methoxy or ethoxy groups.
  • the organopolysiloxane resins (D) preferably have a viscosity greater than 1000 mPa -s at 25 ° C and 101.425 kPa or they are solids.
  • the weight-average molecular weight Mw (based on a polystyrene standard) of these resins, determined using gel permeation chromatography, is preferably 200 to 200,000 g/mol, in particular 1,000 to 20,000 g/mol.
  • Water-insoluble organic compounds (E) can be used in the defoamer formulations (Ef) according to the invention.
  • water-insoluble should be understood to mean a solubility in water at 25 ° C and a pressure of 101.425 kPa of a maximum of 3 percent by weight.
  • the optionally used component (E) is preferably water-insoluble organic compounds with a boiling point greater than 100 ° C at the pressure of the surrounding atmosphere, i.e. at 900 to 1100 hPa, in particular those selected from hydrocarbons, polyisobutylenes and esters such as Fatty acid esters with monoalcohols.
  • hydrocarbons examples include isoparaffins (for example available under the trade name Isopar® E, Isopar® G, Isopar® H, Isopar® J, Isopar® L, Isopar® M, Isopar® N, Isopar® P, Isopar® V from ExxonMobil ), dearomatized hydrocarbons (for example available under the trade name Exxsol® D40, Exxsol® D60, Exxsol® D95, Exxsol® D100, Exxsol® D130 from ExxonMobil) or white oils. Dearomatized hydrocarbons are particularly preferred.
  • polyisobutylenes examples are products commercially available under the trade names Indopol® (Ineos) or Oppanol® (BASF). Polyisobutylenes with a kinematic viscosity of 20 to 500 cSt, measured at a temperature of 100 ° C and a shear rate of 10 s -1 , are particularly preferred.
  • esters in particular fatty acid esters with monoalcohols, are, for example, methyl laurate, isopropyl laurate, octyl laurate, octyl stearate, octyl oleate, dodecyl palmitate or isopropyl myristate.
  • alkaline catalysts (F) examples include alkali and alkaline earth metal hydroxides, such as NaOH, KOH, CsOH, LiOH and Ca(OH)2.
  • acidic catalysts (F) examples include hydrochloric acid, sulfuric acid and phosphonitrile chlorides.
  • reaction products of (F) with components (A) to (E) are, for example, the product of the silica preferred as filler (C) with alkali metal hydroxides, such as potassium silicate or sodium silicate.
  • the catalysts can be dosed in typical organic solvents such as alcohols (such as methanol, ethanol, isopropanol) or esters (such as ethyl acetate).
  • organic solvents such as alcohols (such as methanol, ethanol, isopropanol) or esters (such as ethyl acetate).
  • the components (A) to (F) used in the defoamer formulations (Ef) according to the invention can each be one type of such component as well as a mixture of at least two types of a respective component.
  • the defoamer formulations (Ef) according to the invention have a viscosity of preferably 50 to 100,000 mPa -s, preferably 100 to 10,000 mPa -s, in particular 200 to 7500 mPa -s, each measured at 25 ° C and an ambient pressure of 1020 hPa.
  • the defoamer formulations (Ef) according to the invention can be produced by known methods, for example by mixing all components, for example by simply stirring with static mixers or using high shear forces in colloid mills, dissolvers and rotor-stator homogenizers. The mixing process can take place at reduced pressure in order to prevent the mixing in of air, which is contained, for example, in highly disperse fillers. If necessary, the fillers can then be hydrophobicized in situ.
  • component (D) is added in dissolved form as a solution in component (E) or parts of component (E).
  • the invention furthermore relates to defoamer emulsions (Ee) containing the defoamer formulation (Ef) according to the invention, emulsifiers (G), water (L) and optionally thickeners (H).
  • typical emulsifiers (G) can be used which are known to those skilled in the art, for example for the production of silicone emulsions, such as nonionic, anionic or cationic emulsifiers.
  • Emulsifier mixtures are preferably used, which should contain at least one non-ionic emulsifier.
  • Non-limiting examples of nonionic emulsifiers (Gl) used are: 1. Alkyl polyglycol ethers, preferably those with 3 to 30 EO units and alkyl radicals of 8 to 20 carbon atoms.
  • Carboxylic acid polyglycol esters in particular fatty acid polyglycol esters, preferably those with more than 6 EO units and carboxylic acid residues of 8 to 20 carbon atoms.
  • Alkylaryl polyglycol ethers preferably those with 5 to 30 EO units and 8 to 20 carbon atoms in the alkyl and aryl radicals.
  • Ethylene oxide/propylene oxide (EO/PO) block copolymers preferably those with 8 to 30 EO or PO units.
  • Polyvinyl alcohol which still has 5 to 50%, preferably 8 to 20%, vinyl acetate units, with a degree of polymerization of 500 to 3000.
  • Natural substances and their derivatives such as lecithin, lanolin, saponins, cellulose; Cellulose alkyl ethers and carboxyalkyl celluloses, whose alkyl groups each have up to 4 carbon atoms.
  • Linear organo(poly)siloxanes containing polar groups in particular containing the elements 0, N, C, S, P, Si, in particular those with alkoxy groups with up to 24 carbon atoms and/or up to 40 EO and/or or PO groups.
  • Preferred nonionic emulsifiers are: 1. Alkyl polyglycol ethers, preferably those with 3 to 30 EO units and alkyl radicals of 8 to 20 carbon atoms such as Ceteareth-20, Oleth-10, Oleth-20, Laureth-3, Laureth-4, Laureth-20, Laureth- 23, Trideceth-5, Trideceth-6, Trideceth-8, Trideceth-10, Trideceth-12, Trideceth-16, Trideceth-20, Steareth-20 or Steareth-21 (according to INCI designation).
  • Carboxylic acid polyglycol esters in particular fatty acid polyglycol esters, preferably those with more than 6 EO units and carboxylic acid residues of 8 to 20 carbon atoms, such as PEG-20 stearate, PEG-20 laurate, PEG-7 olivate, PEG-8 oleate, PEG -8 Laurate, PEG-6 Stearate, PEG-20 Stearate or PEG-100 Stearate (according to INCI designation).
  • Ethoxylated or non-ethoxylated sorbitan fatty acid esters such as sorbitan laurate, polysorbate 20, polysorbate 60, polysorbate 80 or polysorbate 85 (according to INCI designation).
  • Ethoxylated castor oil or hydrogenated variants such as (name according to INCI nomenclature) PEG 200 Castor Oil or PEG-60 hydrogenated Castor Oil.
  • Polyglycerol carboxylic acid esters such as polyglycerol-10 oleate, polyglycerol-10 laurate or polyglycerol-10 stearate.
  • Non-limiting examples of anionic emulsifiers (G-2) are:
  • Alkyl sulfates especially those with a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic residue and 1 to 30 ethylene oxide (EO) or propylene oxide (PO) units.
  • Sulfonates especially alkyl sulfonates with 8 to 18 carbon atoms, alkylaryl sulfonates with 8 to 18 carbon atoms.
  • Preferred anionic emulsifiers are:
  • Alkaline and ammonium salts of carboxylic acids with 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical particularly preferred anionic emulsifiers are alkali and ammonium salts of fatty acids, preferably those with carboxylic acid radicals of 8 to 20 carbon atoms, such as e.g. sodium salts, potassium salts, triethanolammonium salts of lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid.
  • Non-limiting examples of cationic emulsifiers (G-3) are:
  • Alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts especially those whose alkyl chain has up to 18 carbon atoms, especially the halides, sulfates, phosphates and acetates.
  • Quaternary alkyl and alkylbenzene ammonium salts especially those whose alkyl groups have 6 to 24 carbon atoms, especially the halides, sulfates, phosphates and acetates.
  • thickeners such as polyacrylic acid, polyacrylates, cellulose ethers such as carboxymethyl cellulose and hydroxyethyl cellulose, polyurethanes, natural ones Thickeners, such as B. Xanthan gum, as well as preservatives and other common additives known to those skilled in the art are added.
  • the continuous phase of the defoamer emulsions (Ee) according to the invention is preferably water.
  • defoamer emulsions (Ee) according to the invention can also be produced in which the continuous phase is represented by components (A) or, if necessary. (E) is formed.
  • Processes for producing defoamer emulsions are known. Production is usually carried out by simply mixing all the components and, if necessary, subsequent homogenization with jet dispersers, rotor-stator homogenizers, colloid mills or high-pressure homogenizers.
  • the defoamer emulsions (Ee) according to the invention are preferably oil-in-water emulsions containing
  • the defoamer formulations (Ef) according to the invention can also be formulated as free-flowing powders (Ep). These are e.g. B. preferred when used in powder detergents. These powders are produced starting from the defoamer formulation (Ef) according to the invention using methods known to those skilled in the art, such as spray drying or build-up granulation and with additives known to those skilled in the art.
  • the powders (Ep) according to the invention preferably contain 2 to 20% by weight of the defoamer formulations (Ef) according to the invention.
  • the carrier (K) comes, for example, B. Zeolites, sodium sulfate, sodium bicarbonate, sodium carbonate, cellulose derivatives, urea as well as urea derivatives and sugar are used.
  • the powders (Ep) according to the invention contain 80 to 98 wt. -% carrier materials (K). Further components of the powders (Ep) according to the invention can, for. B. Be waxes or organic polymers, such as those. B. are described in EP-A 887097 and EP-A 1060778.
  • defoamer formulations (Ef) according to the invention as well as their emulsions (Ee) or powder (Ep) can be used wherever defoamer formulations based on organosilicon compounds have previously been used.
  • a further subject of the present invention is therefore a method for defoaming and/or preventing foaming of media by mixing the defoamer formulations (Ef) according to the invention or their emulsions (Ee) or powder (Ep) with the media.
  • defoamer formulations (Ef) according to the invention or their emulsions (Ee) or powder (Ep) are preferably used for defoaming and/or preventing foaming aqueous media containing anionic and/or nonionic surfactants are used.
  • the defoamer formulations (Ef) according to the invention can also be used in detergents and cleaning agents and care products, such as. B. Fabric softeners can be used, whereby the defoamer formulations (Ef) according to the invention can be used in substance or in the form of emulsions (Ee) or powders (Ep).
  • a further subject of the present invention is therefore detergents, cleaning and laundry care products containing the defoamer formulations (Ef) according to the invention or the defoamer formulations (Ef) according to the invention in the form of emulsions (Ee) or in the form of powders (Ep).
  • the defoamer formulation (Ef) according to the invention can be added directly to the foaming media, dissolved in suitable solvents such as toluene, xylene, methyl ethyl ketone or tert. -Butanol, as a powder (Ep) or as an emulsion (Ee).
  • suitable solvents such as toluene, xylene, methyl ethyl ketone or tert. -Butanol, as a powder (Ep) or as an emulsion (Ee).
  • the amount necessary to achieve the desired defoaming effect depends, for example, on: B. depending on the type of medium, the temperature and the turbulence that occurs.
  • Ametek (annually) about a comparison measurement between the device used and a reference device.
  • liquids that are verifiably connected to international standards (NIST) were used.
  • the measuring temperature is 25°C.
  • the viscosity is given in mPa-s. The measurement uncertainty of the dynamic
  • Viscosity is ⁇ 1%.
  • the speed used and the resulting shear rate were chosen depending on the viscosity.
  • the respective shear rate is shown separately for each viscosity specification.
  • the mixtures HD and LP were filled into Plexiglas cylinders with an internal length (axis of rotation) of approx. 31 cm and an internal diameter (short axis) of approx. 9 cm and these were sealed tightly.
  • the cylinders (at least 2 in parallel with identical test solution) were then clamped into the ContiRotationCAM device.
  • the cylinders rotated around their central short axis at 45 rpm for 120 s and then remained in their vertical position for 10 s.
  • the foam height was then determined (0 - 310 mm). This process was repeated for a total of 90 min.
  • the foam height can then be determined throughout the entire process. The lower this is, the more effective the defoamer formulation is over the entire period (90 minutes) or after a certain (shorter) time interval.
  • Bl 98.16 g of a trimethylsilyl-terminated polymethylhydrosiloxane with a viscosity of 21 mm 2 s -1 , an average degree of polymerization of approximately 55 and a content of 1.63% by weight were added to a reaction vessel with a thermometer and reflux condenser under nitrogen purging Silicon-bonded hydrogen (1.60 mol Si-H) was added.
  • Silicon-bonded hydrogen (1.60 mol Si-H) was added.
  • 184.02 g (0.82 mol) of 1-hexadecene (Sigma Aldrich) were added in portions.
  • the reactants were mixed well and the first portion (one third) of a platinum (Pt) catalyst (solution of hexachloroplatinic acid ⁇ [PtClg] in 1,2-propanediol) was added to achieve a final Pt content of approximately 15 ppm in the overall reaction to surrender. An exothermic reaction was started. After cooling, in a second step, 239.13 g (1.42 mol) of 1-dodecene (Sigma Aldrich) and the second portion (one third) of the above-mentioned platinum (Pt) catalyst were added in portions. An exothermic reaction was started again.
  • Pt platinum
  • the reaction mixture was then kept at a temperature of 140 ° C for a few hours with stirring.
  • the excess olefins were then removed from the reaction mixture on a rotary evaporator and the product was then filtered.
  • the resulting polymer B1 had a viscosity of 2900 mPa-s (80 s -1 ) with an Si-H conversion of 97.8% (according to 1 H-NMR). According to 1 H-NMR, 53.5% of the original Si-H groups were converted to Si-Ci6H 33 and 44.3% of the original Si-H groups were converted to Si-Ci2H 2 5.
  • B2 46.58 g of a trimethylsilyl-terminated poly (dimethylsiloxane-co-methylhydrosiloxane) with a viscosity of 177 mPa -s, an average, were added to a reaction vessel with a thermometer and a reflux condenser under nitrogen purging Degree of polymerization of approximately 120 and 0.64 wt .-% content of silicon-bonded hydrogen (0.30 mol Si-H). In a first step, 33.66 g (0.15 mol) of 1-hexadecene (Sigma Aldrich) were added.
  • the reactants were mixed well and the first portion (one third) of a platinum (Pt) catalyst (solution of hexachloroplatinic acid ⁇ [PtClg] in 1,2-propanediol) was added to achieve a final Pt content of approximately 15 ppm in the overall reaction to surrender.
  • An exothermic reaction was started and over a period of 5 minutes the temperature of the vessel contents increased from 98 °C to 154 °C. After cooling to 110 ° C, 45.47 g (0.27 mol) of 1-dodecene (Sigma Aldrich) and the second portion (one third) of the above-mentioned platinum (Pt) catalyst were added in a second step.
  • the resulting polymer B2 had a viscosity of 3220 mPa-s (80 s -1 ) with an Si-H conversion of 98.2% (according to 1 H-NMR). According to 1 H-NMR, 49.8% of the original Si-H groups were converted to Si-Ci6H 33 and 48.4% of the original Si-H groups were converted to Si-Ci2H 2 5.
  • B3 217.39 g of a trimethylsilyl-terminated poly (dimethylsiloxane-co-methylhydrosiloxane) with a viscosity of 99 mPa -s, an average degree of polymerization of approximately 100 and 0.46 wt. were added to a reaction vessel with a thermometer and reflux condenser under nitrogen purging .-% content of silicon-bonded hydrogen (1.00 mol Si-H). For this purpose, 116.70 g (0.52 mol) of 1-hexadecene were used in a first step (Sigma Aldrich company).
  • the reactants were mixed well and the first portion (one third) of a platinum (Pt) catalyst (solution of hexachloroplatinic acid ⁇ [PtClg] in 1,2-propanediol) was added to achieve a final Pt content of approximately 15 ppm in the overall reaction to surrender.
  • An exothermic reaction was started and over a period of 3 minutes the temperature of the vessel contents increased from 107 °C to 172 °C.
  • 148.19 g (0.88 mol) of 1-dodecene (Sigma Aldrich) and the second portion (one third) of the above-mentioned platinum (Pt) catalyst were added in a second step.
  • the resulting polymer B3 had a viscosity of 1095 mPa-s (200 s -1 ) with an Si-H conversion of 99.8% (according to 1 H-NMR). According to 1 H-NMR, 48.0% of the original Si-H groups were converted to Si-Ci6H 33 and 51.8% of the original Si-H groups were converted to Si-Ci2H 2 5.
  • V-la 27 parts of soybean oil (available from Gustav Heess under the name soybean oil refined IP Ph. Eur. with a content of 48-58% by weight linoleic acid, 17-30% by weight oleic acid, 9-13 % by weight of palmitic acid and 5-11% by weight of linolenic acid), 27 parts of coconut oil (available from Gustav Heess under the name organic coconut oil native with a content of 40-52% by weight of lauric acid, 13-22% by weight myristic acid, 3-12% by weight oleic acid and max. 4
  • linoleic acid % by weight of linoleic acid
  • palm oil available from Gustav Heess under the name palm oil refined SG CU-RSPO SCC-818895 with a content of 39.3-47.5% by weight of palmitic acid, 36-44 % by weight of oleic acid and 8-12% by weight of linoleic acid
  • a pyrogenic silica with a BET surface area of 200 m 2 /g, available from Wacker-Chemie AG under the name HDK® H2000 2 parts of a pyrogenic silica with a BET surface area of 300 m 2 / g, available from Wacker-Chemie AG under the name HDK® T30 and 12 parts of a 55% solution in Exxsol D 100 ULA (available from ExxonMobil Corp.) of a silicone resin that is solid at room temperature and consists of (according to 29 Si-NMR and IR - Analysis) 39 mol% (CH 3 ) 3 Siöi/2, 52 mol% S1 ⁇ 4/2, 7 mol% C2H 3 OSiö 3 /2 and 2 mol% HOSiO 3 /2 units with a weight average molecular weight of 7900 g/mol (based on polystyrene standard).
  • V-2a 20.25 parts of soybean oil (available from Gustav Heess under the name soybean oil refined IP Ph. Eur.) and 60.75 parts of coconut oil (available from Gustav Heess under the name organic coconut oil native) are heated at a slightly elevated temperature Melt (40-50°C) and mix with a spatula.
  • a pyrogenic silica with a BET surface area of 200 m 2 /g available from Wacker-Chemie AG under the name HDK® H2000
  • 2 parts of a pyrogenic silica with a BET surface area of 300 m 2 / g available from Wacker-Chemie AG under the name HDK® T30
  • V-3a 20.25 parts of rapeseed oil (available from Gustav Heess under the name rapeseed oil, refined extracted Ph. Eur. with a content of 50-67% by weight oleic acid, 16-30% by weight linoleic acid and max. 2 % by weight of erucic acid) and 60.75 parts of coconut oil (available from Gustav Heess under the name Organic Coconut Oil Native) are melted at a slightly elevated temperature (40-50°C) and mixed with a spatula.
  • rapeseed oil available from Gustav Heess under the name rapeseed oil, refined extracted Ph. Eur. with a content of 50-67% by weight oleic acid, 16-30% by weight linoleic acid and max. 2 % by weight of erucic acid
  • coconut oil available from Gustav Heess under the name Organic Coconut Oil Native
  • a pyrogenic silica with a BET surface area of 200 m 2 /g, available from Wacker-Chemie AG under the name HDK® H2000 2 parts of a pyrogenic silica with a BET surface area of 300 m 2 / g, available from Wacker-Chemie AG under the name HDK® T30 and 12 parts of a 55% solution in Exxsol D 100 ULA (available from ExxonMobil Corp.) of a silicone resin that is solid at room temperature and consists of (according to 29 Si-NMR and IR -Analysis) 39 mol% (CH 3 ) 3 SiOi/2, 52 mol% S1 ⁇ 4/2, 7 mol% C2H 3 OSiO 3 /2 and 2 mol% HOSiO 3 /2 units with a weight average molecular weight of 7900 g/mol (based on polystyrene standard).
  • V-lb The proportion of soybean oil, coconut oil and palm oil was reduced by 1.66 parts each compared to V-la to a total of 76 parts (soybean oil + coconut oil + palm oil). Instead, 5 parts of a polydiorganosiloxane were added Dimethylsiloxy and trimethylsiloxy units with a viscosity of 100 mm 2 s -1 (25 ° C) are used. A defoamer formulation V-lb with a viscosity of 591 mPa -s (at 25 ° C and at a shear rate of 200 s -1 ) is obtained.
  • V-2b The proportion of soybean oil was reduced by 1.25 compared to V-2a and the proportion of coconut oil was reduced by 3.75 parts compared to V-2a for a total of 76 parts (soybean oil + coconut oil). Instead, an additional 5 parts of a polydiorganosiloxane consisting of dimethylsiloxy and trimethylsiloxy units with a viscosity of 100 mm 2 s -1 (25 ° C) were used. A defoamer formulation V-2b with a viscosity of 310 mPa-s (at 25 ° C and at a shear rate of 200 s -1 ) is obtained.
  • Ef-la The 5 parts of a polydiorganosiloxane consisting of dimethylsiloxy and trimethylsiloxy units with a viscosity of 100 mm 2 s -1 (25 ° C) from V-lb are replaced with 5 parts of Bl.
  • Ef-2a The 5 parts of a polydiorganosiloxane consisting of dimethylsiloxy and trimethylsiloxy units with a viscosity of 100 mm 2 s -1 (25 ° C) from V-2b are replaced with 5 parts of Bl.
  • Ef-lb The 5 parts of a polydiorganosiloxane consisting of dimethylsiloxy and trimethylsiloxy units with a viscosity of 100 mm 2 s -1 (25 ° C) from V-lb are replaced with 5 parts of B2.
  • a defoamer formulation Ef-lb with a viscosity of 720 mPa-s (at 25° C. and at a shear rate of 200 s -1 ) is obtained.
  • Ef-2b The 5 parts of a polydiorganosiloxane consisting of dimethylsiloxy and trimethylsiloxy units with a viscosity of 100 mm 2 s -1 (25 ° C) from V-2b are replaced with 5 parts of B3.
  • a defoamer formulation Ef-2b with a viscosity of 285 mPa-s (at 25° C. and at a shear rate of 200 s -1 ) is obtained.
  • Ef-3b The proportion of rapeseed oil was reduced by 1.25 compared to V-3a and the proportion of coconut oil was reduced by 3.75 parts compared to V-3a to a total of 76 parts (rapeseed oil + coconut oil). Instead, 5 parts of B3 were used.
  • a defoamer formulation Ef-3b with a viscosity of 308 mPa -s (at 25 ° C and at a shear rate of 200 s -1 ) is obtained.
  • Defoamer emulsion Ee-3b was produced using the following process:
  • Ee-3b Defoamer emulsion Ee-3b is prepared by adding 10 parts by weight of an emulsifier mixture containing an ethoxylated isotridecyl alcohol (HLB value of 11.2), an ethoxylated stearyl alcohol (HLB 9.7), pentaerytrith distearate and ammonium lauryl sulphate with 20 parts by weight of the defoamer formulation Ef-3b and 70 parts by weight of water using an ULTRA-TURRAX®. Finally, 0.3 parts by weight of a biocide mixture consisting of benzylisothiazolinone and chloromethylisothiazolinone are added. The result is a milky-white emulsion Ee-3b with a viscosity of 1070 mPa-s (according to Brookfield at 25 ° C at 2.5 rpm with spindle RV2).
  • HLB value ethoxylated isotridecyl alcohol
  • HLB 9.7
  • the defoamer formulations V-la, V-2a, V-3a, V-lb and V-2b as well as Ef-la, Ef-2a, Ef-lb, Ef-2b, Ef-3b and Ee-3b were used in the detergent formulation W checked for their defoaming performance on the ContiRotationCAM (both at High Dosage (HD) and Low Dosage (LP)).
  • the foam height was determined after ⁇ 550 ⁇ 50 s and after ⁇ 5300 ⁇ 50 s of running time of the system.
  • the foam number was determined using a foam tester.
  • Table 2 *Adjustment of the dosage of Ee-3b to ensure identical active defoamer content! formulation Ef-3b in the Detergent formulation W and thus the overall mixtures LP* and HD*.
  • Defoamer formulations Efla, Ef-2a, Ef-lb, Ef-2b, Ef-3b can be increased significantly compared to V-la, V-2a, V-3a, V-lb and V-2b.
  • Efla shows its advantages especially in its defoaming performance on the ContiRotationCAM at HD, while compared to V-lb its advantages in terms of the measured foam number are significant.
  • Ef-2a Compared to V-2a, Ef-2a also shows its advantages especially in its defoaming performance on the ContiRotationCAM at HD, while compared to V-2b its advantages are again significant in terms of the measured foam number.
  • Ef-lb shows its advantages in terms of its defoaming performance both on the ContiRotationCAM (LP and HD) and in terms of the measured foam number.
  • Ef-2b shows its advantages in terms of its defoaming performance both on the ContiRotationCAM (LP and HD) and in terms of the measured foam number.
  • Ef-3b shows its advantages in terms of its defoaming performance both on the ContiRotationCAM (LP and HD) and in terms of the measured foam number.
  • Ee-3b shows a comparable defoaming performance on the ContiRotationCAM in both dosage scenarios (LD* and HD*), which confirms the ability to formulate the defoaming formulations according to the invention as an emulsion without loss of performance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne de nouvelles formulations antimousses (Ef) contenant (A) des huiles et des graisses, essentiellement constituées de triacylglycérides de formule (I) : R1O-CH2-CH(OR2)-CH2-OR3, R1, R 2 , et R3 représentant des résidus d'acides gras de formule générale (II) : R4-CO-, R4 représentant un groupe hydrocarboné aliphatique, linéaire, ou ramifié qui possède 3 à 33 atomes de C et 0 ou 1 à 6 doubles liaisons et peut contenir un ou plusieurs hétéroatomes, tels que le soufre, l'oxygène, et l'halogène, (B) des polydiorganosiloxanes de formule générale (III) : R7-SiR5 2O(SiR5 2O)m(SiR5R6O)nSiR5 2-R7, R5 représentant un groupe méthyle, R6 représentant un groupe hydrocarboné monovalent possédant 2 à 30 atomes de C, R7 représentant un groupe méthyle ou un groupe OR8, et R8 représentant un atome d'hydrogène ou un groupe hydrocarboné monovalent possédant 1 à 4 atomes de C, et la somme de m et n est un nombre entier, n n'étant pas égal à 0, (C) des charges, (D) une résine organopolysiloxane constituée d'unités de formule (IV) R9 a(R10O)bSiO(4-a-b)/2, R9 représentant un atome d'hydrogène ou un groupe hydrocarboné monovalent lié par SiC, éventuellement substitué possédant 1 à 30 atomes de C, R10 représentant un atome d'hydrogène ou un groupe hydrocarboné monovalent éventuellement substitué possédant 1 à 4 atomes de C, et a étant 0, 1, 2, ou 3 et b étant 0, 1, 2, ou 3 à condition que la somme de a + b ≤ 3 et que la somme de a + b = 2 dans moins de 50 % de toutes les unités de formule (IV) dans la résine d'organopolysiloxane, éventuellement (E) des composés organiques insolubles dans l'eau qui diffèrent des huiles et des graisses (A), et éventuellement (F) des catalyseurs alcalins ou acides ou des produits de conversion de ceux-ci comprenant les composants (A) à (E).
PCT/EP2022/058382 2022-03-30 2022-03-30 Formulations antimousses contenant des triacylglycérides et des polydiorganosiloxanes en tant qu'additifs WO2023186288A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5693256A (en) 1994-06-17 1997-12-02 Dow Corning S.A. Foam control agent
EP1060778A1 (fr) 1999-05-21 2000-12-20 Wacker-Chemie GmbH Produit antimousse pulvérulent
WO2004018074A1 (fr) * 2002-08-16 2004-03-04 Dow Corning Corporation Compositions anti-mousse de silicone
WO2004018073A1 (fr) * 2002-08-16 2004-03-04 Dow Corning Corporation Compositions de regulation de mousse silicone
EP1703958B1 (fr) 2003-12-17 2011-01-26 Dow Corning Corporation Agents de regulation de la mousse granulaire
WO2012075611A1 (fr) * 2010-12-10 2012-06-14 The Procter & Gamble Company Détergents de lessive
US20130309498A1 (en) * 2010-12-10 2013-11-21 Dow Corning Corporation Granulated Organopolysiloxane Products
WO2013181948A1 (fr) * 2012-06-08 2013-12-12 Dow Corning Corporation Composition granulée de régulation de mousse
US20130326823A1 (en) * 2012-06-08 2013-12-12 The Procter & Gamble Company Laundry detergents
US20140352076A1 (en) * 2013-05-31 2014-12-04 Haiyan Song Laundry detergents

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5693256A (en) 1994-06-17 1997-12-02 Dow Corning S.A. Foam control agent
EP1060778A1 (fr) 1999-05-21 2000-12-20 Wacker-Chemie GmbH Produit antimousse pulvérulent
WO2004018074A1 (fr) * 2002-08-16 2004-03-04 Dow Corning Corporation Compositions anti-mousse de silicone
WO2004018073A1 (fr) * 2002-08-16 2004-03-04 Dow Corning Corporation Compositions de regulation de mousse silicone
EP1703958B1 (fr) 2003-12-17 2011-01-26 Dow Corning Corporation Agents de regulation de la mousse granulaire
WO2012075611A1 (fr) * 2010-12-10 2012-06-14 The Procter & Gamble Company Détergents de lessive
US20130309498A1 (en) * 2010-12-10 2013-11-21 Dow Corning Corporation Granulated Organopolysiloxane Products
WO2013181948A1 (fr) * 2012-06-08 2013-12-12 Dow Corning Corporation Composition granulée de régulation de mousse
US20130326823A1 (en) * 2012-06-08 2013-12-12 The Procter & Gamble Company Laundry detergents
US20140352076A1 (en) * 2013-05-31 2014-12-04 Haiyan Song Laundry detergents

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