Organopolysiloxane, compositions and powder formulations containing the same, and the use of the same as an antifoaming agent

Abstract

The present disclosure relates to an organopolysiloxane, a composition and powder formulation containing the same, and the use of the same as an antifoaming agent. The organopolysiloxane contains at least 50 mol% of a trifunctional siloxane unit and at least one trifunctional siloxane unit having a polyether group. The composition and powder formulation containing the same have excellent antifoaming and antifoaming properties and can be used as an antifoaming agent in cement-based materials or coatings.

Description

Technology Field

[0001] The present disclosure relates to organopolysiloxanes, compositions and powder formulations containing the same, and the use of the same as defoaming agents. Background Technology

[0002] Cement-based slurries containing solid and liquid components often tend to foam due to the continuous stirring required to keep the solid components of the slurry suspended and additives such as cellulose ether incorporated into the cement-based slurry. If the foam formed is not dissipated within a timely manner, it will have a serious impact on the appearance and strength of the hardened cement-based slurry. Therefore, defoaming agents are an essential component of cement-based slurries.

[0003] Although polydimethylsiloxane-based defoaming agents are known, polydimethylsiloxane is highly undesirable due to its incompatibility with most surfactant systems and its tendency to settle. Polyethersiloxane has been reported to be used as a defoaming agent due to its excellent compatibility. However, since the anti-foaming and / or defoaming effects of polyethersiloxane itself are generally not ideal, a combination of polyethersiloxane with silica and / or MQ silicone resin, or a combination of polyethersiloxane with large amounts of polydimethylsiloxane and / or polyethersiloxane and / or organic oil is used.

[0004] CN101802103A discloses an anti-foaming composition that can be used as a liquid wetting agent, cleaning agent, or detergent comprising a base oil, namely a polyether-modified silicone oil, silica and / or MQ silicone resin, and optionally a polypropylene glycol and / or hydrocarbon oil.

[0005] US3984347A discloses an anti-foaming emulsion comprising polypropylene glycol as a base oil, a foaming agent composed of polydimethylsiloxane as a base oil, silica, and MQ silicone resin, and a polyether-modified silicone oil for dispersing the foaming agent in the base oil.

[0006] US8536109B discloses a silicone anti-foaming agent for a liquid detergent system comprising an aryl-containing silicone oil, MQ silicone resin and silica, a dispersant which is a polyether-containing MQ silicone resin in which polyether groups are bonded to silicon atoms through Si-C bonds, and optionally a cross-linked siloxane having polyether groups and an organic oil.

[0007] US3746653A discloses a foam control agent useful for jet dyeing of fabrics, comprising a linear siloxane glycol copolymer, polydimethylsiloxane, a polyether-containing MQ silicone resin in which polyether groups are bonded to silicon atoms through Si-C or Si-O bonds, silica, and MQ silicone resin.

[0008] Since these anti-foaming agents or foam control agents are mainly liquids, they are inconvenient to store, transport, and use. They are also not suitable for use in cement-based slurries. Recently, some efforts regarding solid defoaming agents have also been reported. However, the anti-foaming and / or defoaming efficiency of these solid defoaming agents still needs to be improved.

[0009] US6129906A discloses a powdered defoaming agent for denture cleaning comprising 50% to 99% of a water-soluble carrier and 3% to 35% of a hydrophobic silicone oil dispersed within the carrier, and optionally a silicone surfactant, wherein the hydrophobic silicone oil is selected from alkyl- and alkoxy-dimethicone copolyols.

[0010] CN103028275B discloses a solid organic silicone defoamer comprising methyl-silicone oil, dimethylsiloxane hydrolysate, fumed silica, polyether-modified silicone oil, emulsion adjuvant, surface modifier, and carrier.

[0011] CN106746889A discloses a solid defoamer for gypsum-based potting materials comprising defoamer particles and a soluble polymeric film wrapped thereon, wherein the defoamer particles comprise a polyether-modified silicone oil, fumed silica, an emulsifier, and a carrier.

[0012] The object of the present invention is to provide a polyether-containing organopolysiloxane, an antifoaming composition containing the same, and a powdered antifoaming agent. Such an antifoaming composition has superior anti-foaming and antifoaming performance compared to an antifoaming composition containing polyether-containing silicone oil. Additionally, the antifoaming composition as an active ingredient is adsorbed onto a solid carrier and used as a powdered antifoaming agent to rapidly remove foam generated during the manufacture of cement-based materials or coating agents.

[0013] The term "cement-based materials" should be understood to include cement, dry mixtures containing cement, and fluid mixtures containing cement. Cements known by major hydraulic materials include Portland cement, aluminate cement, sulfoaluminate cement, fluoroaluminate cement, and ferroaluminate cement.

[0014] "Dry mixture" generally contains cement and optional cementitious fillers, and may additionally contain one or more of aggregates, polymers, and admixtures. The cement is generally ordinary Portland cement. As used herein, cementitious fillers refer to materials that harden and continue to harden and gain strength through a hydration process, such as cement, including but not limited to fly ash, silica fume, crushed blast furnace slag (referred to as slag), cinder, and pozzolan, as well as non-hydraulic cementitious materials that harden in air, such as limestone and gypsum. Aggregates broadly refer to both coarse and fine particle materials, including but not limited to sand, gravel, and crushed stone. Fine aggregate generally refers to aggregates with a particle size of less than 4.75 mm. Polymers typically include polymers (or (co)polymers) based on one or more ethylene-based unsaturated monomers, such as acrylic acid copolymers and ethylene-vinyl acetate copolymers. The mixture includes, but is not limited to, cellulose ethers, water reducers, water repellents, anticoagulants, retarders, and superplasticizers. In the context of the disclosure, the dry mixture includes the dry mortar referred to in the literature. The dry mortar is a mixture that generally includes cement, fine aggregate, and admixtures, and optionally includes cementitious fillers and / or polymers.

[0015] "Fluid mixtures" may be exemplified by optional cementitious fillers mixed with water, including but not limited to slurry materials derived from cement, pastes, mortars, grouts, and concrete. Pastes are generally mixtures comprising cement, admixtures, and water. Mortar is generally a mixture comprising cement, sand, admixtures, and water. Grout is generally a mixture comprising cement, sand, polymers, admixtures, and water. Concrete is generally a mixture comprising cement, sand, coarse aggregate, admixtures, and water. The pastes, mortars, grouts, and concrete may optionally contain cementitious fillers, and generally the addition of admixtures is less than 3% by weight based on the total weight of the cement and cementitious fillers, and the addition of polymers is greater than 1% by weight and less than 50% by weight. In the context of the disclosure, fluid mixtures may also be understood as cement-based slurries.

[0016] In this document, "T resin" refers to the trifunctional siloxane unit RSiO 3 / 2 Refers to a silicone resin essentially composed of (T), where R is a monovalent, optionally substituted, SiC-bonded organic radical, and each oxygen atom is bonded to a silicon atom at one end and the other is bonded to a silicon atom or a monovalent optionally substituted organic radical. Siloxane units, e.g. , , , , All are trifunctional siloxane units in the context of the present invention, where Me represents methyl, Et represents ethyl, and PPG represents a polyoxypropylene ether group. The phrase “essentially composed of trifunctional siloxane units” means that the silicone resin contains at least 50 mol%, e.g., at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, or even 100 mol% of trifunctional siloxane units based on the total molar amount of siloxane units.

[0017] A first aspect of the present disclosure provides an organopolysiloxane comprising at least 50 mol% of a trifunctional siloxane unit and at least one trifunctional siloxane unit having a polyether group, selected from the following:

[0018] (i) a polysiloxane containing a unit of chemical formula (I),

[0019]

[0020] In the above chemical formula (I), R 1 In each case, it is independently a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, and

[0021] R 2 In each case, is independently a hydrogen or a monovalent, optionally substituted hydrocarbon radical, and

[0022] R 3 In each case, the chemical formula -OR is independently a -(OR b ) j -OR c It is a radical of, and in this chemical formula, R a is a divalent, selectively substituted hydrocarbon radical, and R b is independently a divalent, optionally substituted hydrocarbon radical in each case, and R c is hydrogen, a monovalent organic radical, or It has a structural fragment of, where R* is independently R in each case 1 , OR2 or -O-, and j is an integer from 1 to 200, preferably from 20 to 200, and

[0023] a is 0, 1, 2, or 3, and

[0024] b is 0, 1, 2, or 3, and

[0025] c is 0, 1, or 2, and

[0026] A polysiloxane containing units of formula (I), wherein in at least 50 mol% of all units of formula (I), a is 1 and the sum of b+c is 0, 1 or 2, and at least one unit c is different from 0; or

[0027] (ii) a polysiloxane containing a unit of chemical formula (II),

[0028]

[0029] In the above chemical formula (II), R 1' In each case, it is independently a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, and

[0030] R 3' In each case, the chemical formula -R is independently a ' -(OR b ' ) j' -OR c ' It is a radical of, and in this chemical formula R a ' is a divalent, selectively substituted hydrocarbon radical, and R b ' is independently a divalent, optionally substituted hydrocarbon radical in each case, and R c ' is hydrogen, a monovalent organic radical, or It has a structural fragment of, where R*' is independently R in each case 1' or -O-, r is an integer from 1 to 6, and j 'is an integer of 1 to 200, preferably 20 to 200, and

[0031] d is 0 or 1, and

[0032] e is 0 or 1, and

[0033] However, the sum of d+e in all units of at least 50 mol% of the chemical formula (II) is 1, and at least one unit e is different from 0.

[0034] The phrase “at least one trifunctional siloxane unit having a polyether group” refers to “at least one polyether-T unit” in the context of the disclosure. Additionally, the polyether-T unit is R of an organopolysiloxane (i) in which a is 1 and the sum of b+c is 0, 1, or 2, and at least one unit c is different from 0. 1 a (R 2 O) b R 3 c SiO (4-a-b-c) / 2 R of an organopolysiloxane (ii) where the sum of the units and d+e is 1 and at least one unit e is different from 0. 1' d R 3' e SiO (4-d-e) / 2 Selected from the unit.

[0035] Radical R 1 Examples of are alkyl radicals, e.g., methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, and 2,2,4-trimethylpentyl; cycloalkyl radicals, e.g., cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; alkenyl radicals, e.g., vinyl, 1-propene, and 2-propene; aryl radicals, e.g., phenyl and naphthyl; alkaryl radicals, e.g., o-, m-, p-tolyl, xylyl, and ethylphenyl; and aralkyl radicals, e.g., benzyl, α-, and β-phenylethyl. Substituted radical R1 Examples of hydrocarbon radicals substituted by organosilyl radicals, such as trimethylsilylethylene, and hydrocarbon radicals substituted by organosiloxanyl groups.

[0036] Preferably, radical R 1 It is an alkyl radical having 1 to 18 carbon atoms or an aromatic radical having 6 to 9 carbon atoms, particularly preferably methyl, n-hexyl, n-heptyl, n-octyl, phenyl and ethylphenyl, particularly methyl.

[0037] Radical R 2 Examples of are hydrogen or radical R 1 Examples given for, preferably hydrogen and hydrocarbon radicals having 1 to 4 carbon atoms, particularly methyl and ethyl.

[0038] Radical R a The is preferably a hydrocarbon radical having 1 to 10 carbon atoms, such as -CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)CH2-, -CH2-CH2-C6H4- and -CH2-CH(CH3)-C6H4-, particularly -CH2-CH(CH3)- and -CH2-CH2-CH2-.

[0039] Radical R b Examples of are -CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)CH2- and -CH2-CH(CH2-CH3)-, preferably -CH2-CH2- and -CH2-CH(CH3)-.

[0040] Radical R c Examples of are hydrogen or radical R 1 The given example for, or -C(O)-R d It is a radical of, where R d is an alkyl, preferably hydrogen, methyl, allyl, butyl, and acetyl. Radical R cIf is any of the radicals mentioned above, one end of the polyether chain is attached to the siloxane via a Si-O bond, and the other end is free. Radical R c An example of is also R * In each case, R as defined above is independently 1 or OR 2 or -O-in Having a structural fragment of, preferably Me representing methyl and Et representing ethyl or It may have structural fragments. In this case, both ends of the polyether chain are attached to the siloxane(s) through Si-O bonds to form a cross-linked structure.

[0041] In one embodiment of the present invention, radical R 3 is of chemical formula (III) and:

[0042]

[0043] In the above formula (III), x is an integer from 1 to 10, preferably an integer from 2 to 6, particularly 3, and

[0044] m is an integer from 0 to 200, preferably an integer from 0 to 100, particularly an integer from 0 to 50, and

[0045] n is an integer from 0 to 200, preferably an integer from 5 to 100, particularly an integer from 20 to 80, and

[0046] The sum of m+n is an integer from 1 to 200.

[0047] R c is hydrogen, C1-C 30 Alkyl, C1-C 30 Alkenyl or R d C1-C 20 -C(O)-R alkyl d or a radical It has a structural fragment of, where R* is independently C1-C in each case 18Alkyl, C6-C9 aryl, hydroxyl, C1-C4 alkoxy or -O-, particularly methyl, hydroxyl, methoxy, ethoxy or -O-, and R c is preferably hydrogen, methyl, allyl, butyl, or acetyl. or It has a structural fragment of, where Me represents methyl and Et represents ethyl;

[0048] The units (OC2H4) and (OC3H6) may exist in a random distribution in the radical of chemical formula (III) or even as blocks.

[0049] In an embodiment of the present invention, the organopolysiloxane (i) is of formula (IV) and:

[0050]

[0051] In the above chemical formula (IV), radical R 1 , R 2 , R 3 is as defined above, and the sum of z+t is greater than 0; preferably, x units (R) based on the total moles of siloxane units. 1 SiO 3 / 2 ) is present in an amount of 10 mol% to 95 mol%, e.g., 10 mol% to 60 mol%, and y units (R 1 (R 2 O)SiO 2 / 2 ) and z unit (R 1 R 3 SiO 2 / 2 The sum of ) exists in an amount of 5 mol% to 90 mol%, for example, 20 mol% to 70 mol%, and in t units (R 1 (R 2 O)R 3 SiO 1 / 2 ) and w units (R 1 (R 2 O)2SiO 1 / 2 The total of ) is present in an amount of 5 mol% to 30 mol%. The molar content is determined by methods well known in the art, for example 29 It can be determined by Si NMR.

[0052] Radical R 1' , R a ' , R b ' An example of this is radical R 1 , R a and R b These are given for each. Radical R c ' Examples of are hydrogen, or radical R 1' The given example for, or R d ' -C(O)-R, which is an alkyl, preferably hydrogen, methyl, allyl, butyl, and acetyl d ' This is an example given for the radical. Radical R c ' If is any of the radicals mentioned above, one end of the polyether chain is attached to the siloxane via a Si-C bond, and the remaining end is free. Radical R c ' An example of this is also R*', which in each case is R as defined above independently. 1' or -O- and r is an integer from 1 to 6 Having a structural fragment of, preferably It may have structural fragments. In this case, both ends of the polyether chain are attached to the siloxane(s) through Si-C bonds to form a cross-linked structure.

[0053] In an embodiment of the present invention, radical R 3' is of chemical formula (V) and:

[0054]

[0055] In the above formula (V), x' is an integer from 1 to 10, preferably an integer from 2 to 6, particularly 3, and

[0056] m' is an integer from 0 to 200, preferably an integer from 0 to 100, particularly an integer from 0 to 50, and

[0057] n' is an integer from 0 to 200, preferably an integer from 5 to 100, particularly an integer from 20 to 80, and

[0058] The sum of m'+n' is an integer from 1 to 200, and

[0059] R c ' is hydrogen, C1-C 30 Alkyl, C1-C 30 Alkenyl or R d ' C1-C 20 -C(O)-R alkyl d ' It is a radical of, It has a structural fragment of, where R*' is independently C1-C in each case 18 alkyl, C6-C9 aryl or -O-, particularly methyl or -O-, and r is an integer from 1 to 6; R c ' is preferably hydrogen, methyl, allyl, butyl, or acetyl. It has a structural fragment, where r is an integer from 1 to 6;

[0060] The units (OC2H4) and (OC3H6) can exist as a random distribution or even as blocks in the radicals of chemical formula (V).

[0061] The organopolysiloxane of the present disclosure comprises 5% to 95% by weight, for example 10% to 50% by weight, of R based on the total weight of the organopolysiloxane. 3 or R 3' It has a content. The weight content is determined by methods well known in the art, for example. 1 It can be determined by H NMR.

[0062] The organopolysiloxane of the present disclosure also includes, in addition to the trifunctional siloxane unit defined by the aforementioned conditions, other siloxane units, such as a monofunctional siloxane unit R 1 3SiO 1 / 2 (M), difunctional siloxane unit R1 2SiO 2 / 2 (D) and tetrafunctional siloxane units SiO 4 / 2 It may contain (Q), where radical R 1 It should be understood that it is as defined above. The molar ratio of other siloxane units may be less than 50 mol% based on the total number of moles of the siloxane units, e.g., less than 40 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, or even less than 5 mol%.

[0063] The organopolysiloxane (i) of the present disclosure is a mixture comprising a polysiloxane containing a unit of formula (VI):

[0064]

[0065] In the above chemical formula (VI), radical R 1 and R 2 is as defined above, and

[0066] f is 0 or 1, and

[0067] g is 0, 1, 2, or 3, and

[0068] Provided that f is 1 in at least 50 mol% of all units of formula (VI), and at least one unit g is different from 0; and

[0069] It is derived from the reaction of a polyether compound of chemical formula (VII):

[0070]

[0071] In the above chemical formula (VII), R 4 is hydrogen or a monovalent organic radical, and

[0072] R 5 is hydrogen or C1-C3 alkyl, and

[0073] R 6 In each case, it is independently a divalent, optionally substituted hydrocarbon radical, and

[0074] k is an integer from 1 to 200, preferably an integer from 10 to 200.

[0075] The reaction is typically a condensation reaction, which can be catalyzed by catalysts commonly used in the art, for example, acidic catalysts such as sulfuric acid, trifluoromethanesulfonic acid, fluorine-containing carboxylic acid, solid acid (e.g., acid-activated clay, macroporous cation exchange resin), phosphorus dichloronitride (phosphonitrile chloride) and its oligomer, and basic catalysts such as potassium hydroxide, preferably solid acid catalysts.

[0076] The reaction is suitably carried out at a temperature of 80°C to 120°C for a period of 0.5 to 4 hours. The reaction is advantageously carried out under reduced pressure to extract low molecular weight alcohols produced from the reaction and promote condensation.

[0077] Radical -OR in polysiloxane (VI) 2 is a radical -OR in polyether (VII) through condensation 4 and / or -OR 5 It reacts with, and as a result, the polyether chain is connected to the siloxane through Si-O bonds.

[0078] In an embodiment of the present invention, the polysiloxane (VI) is of the chemical formula (VIII):

[0079]

[0080] In the above chemical formula (VIII), radical R 1 and R 2 is as defined above, and

[0081] o is a number greater than or equal to 0, and

[0082] p is a number greater than 0, and

[0083] q is a number greater than or equal to 0.

[0084] Preferably, o units (R 1 SiO 3 / 2) exists in an amount of 0 mol% to 80 mol%, e.g., 5 mol% to 50 mol%, based on the total moles of siloxane units, and p units (R 1 (R 2 O)SiO 2 / 2 ) is present in an amount of 5 mol% to 90 mol%, and q units (R 1 (R 2 O)2SiO 1 / 2 ) is present in an amount of 0 mol% to 50 mol%. Polysiloxane (VIII) is available from Wacker Chemie AG under the trade name Trasil.

[0085] Polysiloxane (VI) or (VIII) is less than 50 mol% based on the total moles of siloxane units, e.g., less than 40 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, or less than 5 mol% of other siloxane units, e.g., unit R 1 3SiO 1 / 2 (M), siloxane unit R 1 2SiO 2 / 2 (D) and unit SiO 4 / 2 It may additionally contain (Q), where radical R 1 It is as defined above.

[0086] The polyether (VII) is preferably a compound of the following chemical formula:

[0087]

[0088] In the above chemical formula, R 4 is hydrogen, C1-C 30 Alkyl, C1-C 30 Alkenyl or -C(O)-R d It is a radical of, and here R d is C1-C 20 alkyl, preferably hydrogen, methyl, allyl, or butyl, and

[0089] R 5 is hydrogen or C1-C3 alkyl, preferably hydrogen or methyl, and

[0090] s is an integer from 0 to 200, preferably an integer from 0 to 100, particularly an integer from 0 to 50, and

[0091] t is an integer from 0 to 200, preferably an integer from 5 to 100, particularly an integer from 20 to 80, and

[0092] The sum of s+t is an integer between 10 and 200, and

[0093] The units (OC2H4) and (OC3H6) may exist as a random distribution or even as blocks in the polymer of formula (VII).

[0094] The organopolysiloxane (ii) of the present disclosure is a mixture comprising a polysiloxane containing a unit of the formula (IX):

[0095]

[0096] In the above chemical formula (IX), radical R 1 is as defined above, and

[0097] h is 0 or 1, and

[0098] i is 0 or 1, and

[0099] Provided that the sum of h+1 in at least 50 mole% of all units of formula (IX) is 1, and at least one unit i is different from 0; and

[0100] It is derived from the reaction of a polyether compound of chemical formula (VII'):

[0101]

[0102] In the above chemical formula (VII'), R 4' is C1-C 30 Alkenyl, C1-C 30 It is alkyl or hydrogen, preferably allyl, methyl, or butyl, and

[0103] R 5' is C1-C 30 alkenyl, preferably allyl, and

[0104] R6' In each case, it is independently a divalent, optionally substituted hydrocarbon radical, and

[0105] k' is an integer from 1 to 200, preferably an integer from 10 to 200.

[0106] The reaction conditions may refer to the conditions of conventional hydrosilylation reactions in the art. Hydrogen atoms in polysiloxane (IX) react with alkenyl radicals in polyether (VII') through addition, and as a result, polyether chains are connected to siloxane through Si-C bonds.

[0107] A second aspect of the present disclosure provides a composition:

[0108] (a) at least one organopolysiloxane of the first embodiment of the present disclosure (i) and / or (ii), and

[0109] (b) comprising at least one additive selected from the following:

[0110] (b1) Filler particles and / or

[0111] (b2) Organopolysiloxane resin containing units of chemical formula (X):

[0112]

[0113] In the above chemical formula (X), R 7 In each case, are independently hydrogen or monovalent, optionally substituted, SiC-bonded hydrocarbon radicals, and

[0114] R 8 In each case, is independently hydrogen or a monovalent, optionally substituted hydrocarbon radical, and

[0115] u is 0, 1, 2, or 3, and

[0116] v is 0, 1, 2, or 3, and

[0117] However, the sum of u+v is 3 or less, and the sum of u+v in all units of chemical formula (X) in less than 50 mol% of the organopolysiloxane resin is 2.

[0118] Component (b1) is preferably pulverulent, and more preferably pulverulent and hydrophobic. Examples of component (b1) are silicon dioxide (silica), titanium dioxide, aluminum oxide, metal soap, quartz powder, PTFE powder, finely divided hydrophobic polyurethane, but are not limited thereto.

[0119] Component (b1) is preferably 20 to 1000 m 2 / g, especially 50 to 400 m 2 It has a BET surface area of ​​ / g.

[0120] The component (b1) preferably has a particle size of less than 10 μm, particularly 10 nm to 5 μm.

[0121] As component (b1), silica, particularly 50 to 800 m 2 Silica having a BET surface area of ​​1 / g is particularly preferred. These silicas may be fumed or precipitated silica. Hydrophobic silica is advantageous for the desired effectiveness of the composition as an antifoaming agent. Methods for hydrophobizing silica are well known.

[0122] Component (b2) is preferably an organopolysiloxane resin in which the sum of u+v is 2 in 0 to 30 mol% of all units, more preferably 0 to 5 mol%.

[0123] Radical R 7 An example of this is radical R 1 Examples given for, preferably alkyl radicals having 1 to 4 carbon atoms or phenyl, particularly methyl.

[0124] Radical R 8 An example of this is radical R 2 The given example is an alkyl radical having 1 to 4 carbon atoms, preferably methyl or ethyl.

[0125] Component (b2) is particularly preferably R 73SiO 1 / 2 (M) and SiO 4 / 2 It is an organopolysiloxane resin essentially composed of (Q) units, where R 7 ...has the meaning described above; these resins are also referred to as MQ resins. The molar ratio of M units to Q units is preferably in the range of 0.5 to 2.0, particularly 0.6 to 1.0. Furthermore, these silicone resins may contain up to 10 weight percent of free hydroxy or alkoxy radicals. R 7 Here, it is preferably methyl.

[0126] The molar ratio of component (a) to component (b) is preferably (5-30) : 1, for example (10-30) : 1.

[0127] The composition of the present disclosure is preferably,

[0128] (c) further comprising a polyether compound of formula (XI):

[0129]

[0130] In the above chemical formula (XI), R 9 In each case, it is independently hydrogen or a monovalent organic radical, and

[0131] R 10 In each case, it is independently a divalent, optionally substituted hydrocarbon radical, and

[0132] k is an integer from 1 to 200.

[0133] The polyether (XI) is preferably a compound of formula (XII):

[0134]

[0135] In the above chemical formula (XII), R 9 In each case, independently hydrogen, C1-C30 alkyl, C1-C 30 Alkenyl or -C(O)-R d It is a radical of, and here R d is C1-C20 alkyl, preferably hydrogen, methyl, allyl, or butyl, particularly hydrogen,

[0136] s is an integer from 0 to 200, preferably an integer from 0 to 100, particularly an integer from 0 to 50, and

[0137] t is an integer from 0 to 200, preferably an integer from 5 to 100, particularly an integer from 20 to 80, and

[0138] The sum of s+t is 10 to 200, and

[0139] The units (OC2H4) and (OC3H6) may exist as a random distribution or even as blocks in the polymer of formula (XII).

[0140] A polyether of formula (XII) in which s is 0 and t is an integer from 20 to 200 is preferred.

[0141] The polyether preferably has a number-average molecular weight (Mn) of 1200 to 12000. More preferably, the polyether is a polypropylene glycol having a number-average molecular weight (Mn) of 1200 to 8000.

[0142] The molar ratio of component (a) to component (c) is preferably 1:(0.1-100), preferably 1:(5-30), for example 1:(8-25).

[0143] The composition of the present disclosure may further comprise (d) at least one hydrocarbon oil, e.g., mineral oil, native oil, isoparaffin, polyisobutylene, fatty acid ester, fatty alcohol. Component (d) may also be a commercially available hydrogenated light distillate (petroleum). Component (d) is used in an amount preferably from 0 to 50 parts by weight, particularly from 0 to 30 parts by weight, based on 100 parts by weight of the defoaming agent composition. Considering that possible oil settling may occur when a composition containing component (D) is applied to a cement-based material or coating agent, the composition of the present disclosure preferably does not contain component (D).

[0144] In principle, the compositions of the present disclosure may also contain other organosilicon compounds different from formulas (I), (II), (IV), (VI), (VIII), (IX) or (X), such as methyl polysiloxanes, particularly polydimethylsiloxanes. However, considering that polydimethylsiloxanes are incompatible with most surfactant systems, the compositions of the present disclosure preferably do not contain polydimethylsiloxanes.

[0145] In the present invention, the phrase “does not contain XX” means that the content of a specific component is less than 1% by weight of the total weight of the composition, for example, less than 0.5% by weight, or even less than 0.1% by weight.

[0146] In an embodiment of the present invention, the composition is

[0147] (a) 0.1 wt% to 90 wt% of at least one organopolysiloxane of the first embodiment of the present disclosure (i) and / or (ii),

[0148] (d) 0.01 wt% to 5 wt% of at least one additive,

[0149] (c) at least one polyether in an amount of 5% to 98% by weight, and

[0150] Optionally

[0151] (d) 0 to 50 weight percent of at least one hydrocarbon oil

[0152] Includes

[0153] In a preferred embodiment of the present invention, the composition is

[0154] (a) 0.5 wt% to 20 wt% of at least one organopolysiloxane of the first embodiment of the present disclosure (i) and / or (ii),

[0155] (d) 0.01 wt% to 2 wt% of at least one additive,

[0156] (c) 50 weight% to 98 weight% of at least one polyether, and

[0157] Optionally

[0158] (d) 0 to 50 weight percent of at least one hydrocarbon oil

[0159] Includes

[0160] A third aspect of the present disclosure provides a powder formulation comprising the composition of the second aspect of the present disclosure and a solid carrier. The composition as an active ingredient is adsorbed onto the solid carrier.

[0161] Suitable solid carriers are generally porous materials including, but not limited to, treated or untreated silica fume or precipitated silica, amorphous, colloidal or crystalline silica, diatomite, clay, bentonite, attapulgite, talc, zeolite powder, activated carbon, silicates such as calcium silicate, carbonates such as calcium carbonate, sodium carbonate, sodium bicarbonate, sulfates, phosphates, sugar alcohols or sugars such as sorbitol, mannitol or maltodextrin, starch or modified starch or derivatives thereof, polyethylene glycol, gum arabic, gum tragacanth, carrageenan, and cellulose derivatives.

[0162] In a preferred embodiment of the present invention, silica fume is used as a solid carrier. "Silica fume" is a fine particle material comprising at least 85 weight percent amorphous silicon dioxide (see standard GB / T27690-2011) obtained as a product during the production of ferrosilicon or industrial silicon.

[0163] The method for preparing the powder formulation is not particularly limited as long as the composition and the solid carrier of the second embodiment of the present disclosure are well mixed. The composition and the solid carrier are suitably mixed in a mass ratio of less than 1:1, preferably less than 1:2, for example, 1:3. In an embodiment of the present invention, the mass ratio of composition to solid carrier is 2: (1-15), for example, 2: (3-10).

[0164] A fourth aspect of the present disclosure provides a use of the composition of the second aspect of the present disclosure or the powder formulation of the third aspect of the present disclosure as an antifoaming agent.

[0165] The composition or powder formulation can be used as an antifoaming agent in cement-based materials, for example, the aforementioned dry mixtures containing cement and fluid mixtures containing cement, coating agents, adhesives, water-miscible cooling lubricants, textiles, personal hygiene products, cosmetics, and inks.

[0166] When the composition or powder formulation is used as an antifoaming agent in cement-based materials or coatings, foam formed during the manufacture of the cement-based materials or coatings will be rapidly removed. The method of use is not particularly limited. The composition may suitably be added during the manufacture of cement-containing fluid mixtures or coatings, such as pastes, mortars, grouts, and concrete. The powder formulation may suitably be added during the manufacture of cement-containing dry mixtures, particularly dry mortars, or powder coatings.

[0167] A fifth aspect of the present disclosure provides an antifoaming agent comprising the composition of the second aspect of the present disclosure or the powder formulation of the third aspect of the present disclosure. Specific details for implementing the invention

[0168] The present invention is further explained by the following examples, but the scope of the invention is not limited thereto. In the following examples, experimental methods without specific conditions were selected according to conventional methods and conditions or product specifications.

[0169] Characterization of molecular structure

[0170] The structure of the resin was determined using a Bruker Avance III HD 400 spectrometer equipped with a 5 mm BBO probe head. 1 H NMR and 29 It was analyzed by Si NMR.

[0171] Characterization of molecular weight and its distribution

[0172] The molecular weight of the resin and its distribution were analyzed by PSS SECcurity gel permeation chromatography using an Agilent PLgel 5 μm MiniMIX-C column with toluene as the solvent and an oven temperature of 45°C.

[0173] Evaluation of anti-foaming properties / vesicle effects

[0174] Preparation of foaming solution: 8 g of sodium allyl sulfonate was dissolved in 192 mL of water and mixed well to obtain 200 mL of foaming solution.

[0175] In each case, the defoaming agent composition was added to 200 mL of foaming solution prepared in the amounts specified in Tables 2 and 4, and then stirred for 1 minute at 1000 rpm using a bee stirrer. The initial foam height and the change in foam height over time were recorded using an optical sensor to collect foam height-time curves. The initial foam height reflects the defoaming properties of the composition. Furthermore, the lower the initial height, the better the anti-foaming performance. The integral area enclosed by the height-time curve, the height axis, and the time axis—that is, the integral area of ​​the curve from the initial height to zero height (more precisely, the minimum foam height detectable by the optical sensor, generally a value very close to zero)—is called the AKZ (Activity Value). The AKZ comprehensively reflects the anti-foaming properties and defoaming rate of the composition. Additionally, the smaller the AKZ value, the better the overall anti-foaming / defoaming performance.

[0176] Determination of air content

[0177] This was performed according to the standard JC / T 601-2009 method for determining air content in cement mortar.

[0178] Determination of liquidity

[0179] This was performed according to the standard GB / T 2419-2005 test method for the fluidity of cement mortar.

[0180] The details of the raw materials used in the examples and comparative examples were as follows.

[0181] A2: 29 PO3O-((CH3)2SiO) when determined by Si NMR, representing a polyether group having 30 propoxy radicals. 2 / 2 ) 15 - Chemical formula of PO30 and 1 Polyether-modified silicone oil having a polyether content of 76 wt% as determined by H NMR.

[0182] A3: 29 30.5 mol% of CH3SiO as determined by Si NMR3 / 2 Unit, 46.3 mol% of C2H5O(CH3)SiO 2 / 2 Units and 20.3 mol% of (C2H5O)2(CH3)SiO 1 / 2 CH3SiO having units 3 / 2 , C2H5O(CH3)SiO 2 / 2 and (C2H5O)2(CH3)SiO 1 / 2 Alkoxy-T resin essentially composed of units.

[0183] B1: Fumed Silica, Trade Name HDK ® H2000, provided by Wacker Chemie AG.

[0184] B2: Fumed Silica, Trademark HDK ® H15, provided by Wacker Chemie AG.

[0185] C1: Hydroxy-terminated polypropylene glycol, trade name PPG 2000, commercially available.

[0186] C2: Hydroxy-terminated polypropylene glycol, trade name PPG 1000, commercially available.

[0187] C3: Hydroxy-terminated polypropylene glycol, trade name PPG 350, commercially available.

[0188] D1: Hydrogenated light distillate (petroleum), commercially available.

[0189] F1: Silica fume: Implementation standard GB / T27690-2011, commercially available.

[0190] F2: Precipitated silica, trade name Evonik sipernat ® 22, provided by Evonik.

[0191] Cement (Grade 42.5): Benchmark cement for concrete admixture investigation, implementation standard GB8076-2008, commercially available.

[0192] Sand: ISO standard sand, implementation standard GB / T1761-1999, commercially available.

[0193] Redispersible polymer powder: Trade name VINNAPAS ® 5010 N, provided by Wacker Chemie AG.

[0194] Cellulose ether: Trademark name Tylose ® MH 10007 P4, provided by Shin-Etsu.

[0195] Reducer: Brand name MELMENT ® F10, provided by BASF.

[0196] Synthesis Example 1 Polyether-T Resin

[0197] Alkoxy-T resin A3 and polypropylene glycol C1 were mixed with an effective amount of acid-activated clay catalyst and a very small amount of water. The mass ratio of alkoxy-T resin A3 to polypropylene glycol C1 was controlled to (1-3):1, and the mass ratio of alkoxy-T resin A3 to water was (4×10 3 Up to 6x10 3 The temperature was controlled to 1. The resulting mixture was heated to a maximum of 80°C to 100°C and stirred for 50 to 80 minutes at 80°C to 100°C for condensation. Afterward, the distillate (mainly ethanol) was distilled at 80°C to 100°C by applying a vacuum (100 to 300 mbar). After the vacuum step, the mixture was continuously stirred at 80°C to 100°C for 20 to 40 minutes. Subsequently, an appropriate amount of sodium carbonate and water was added and thoroughly mixed under stirring at 80°C to 100°C for 50 to 80 minutes. The vacuum (100 to 200 mbar) was maintained until the distillate plus decreased. Afterward, the resulting mixture was cooled, and the solid was subsequently filtered out.

[0198] The generated reaction product is 1It was determined by H NMR to have a polyether content of 31.63 mol% (equivalent to 33.00 wt% when calculated by weight). The raw material polypropylene glycol C1 1 Compared with H NMR results, it was found that approximately 74.56 mol% of hydroxyls from polypropylene glycol C1 reacted with alkoxy-T resin A3, which indicates that most of the charged polypropylene glycol C1 participated in the condensation reaction and was bonded to alkoxy-T resin A3 via Si-O bonds, and that some of the polypropylene glycol C1 was condensed via hydroxyl radicals at only one end, while some was condensed via hydroxyl radicals at both ends. Hereinafter, this reaction product will be referred to as polyether-T resin A1.

[0199] Polyether-T resin A1 is 29 By Si NMR (CH3SiO 3 / 2 ) x (C2H5O(CH3)SiO 2 / 2 ) y (PO30(CH3)SiO 2 / 2 ) z ((C2H5O)(PO3O)(CH3)SiO 1 / 2 ) t ((C2H5O)2(CH3)SiO 1 / 2 ) w It was determined to have the chemical formula, where x was 36.3 mol%, the sum of y+z was 49.5 mol%, the sum of t+w was 14.2 mol%, and PO30 represented a polyether group having 30 propoxy radicals.

[0200] As measured by PSS SECcurity gel permeation chromatography, the raw material alkoxy-T resin A3 had a weight-average molecular weight (Mw) of 3,548 g / mol (using polystyrene standards) and a polydispersity index Mw / Mn of 3.65; the reaction product polyether-T resin A1 had a weight-average molecular weight (Mw) of 13,020 g / mol (using polystyrene standards) and a polydispersity index Mw / Mn of 8.15.

[0201] Antifoaming agent compositions of Examples 1 to 4 and Comparative Examples 1 to 3

[0202] An antifoaming agent composition was obtained by thoroughly mixing the components of each example listed in Table 1.

[0203] weight part Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 A1 5.74 5.74 5.74 5.74 / / / A2 / / / / 5.74 / / A3 / / / / / 5.74 / B1 0.18 0.18 0.18 0.18 0.20 0.16 / B2 0.18 0.18 0.18 0.18 0.20 0.16 / C1 93.90 / / 69.30 93.87 93.90 100 C2 / 93.90 / / / / / C3 / / 93.90 / / / / D1 / / / 24.6 / / /

[0204] Table 2 shows the evaluation results for each defoaming agent composition of Examples 1 to 4 and Comparative Examples 1 to 3. The defoaming agent compositions of Examples 1 to 4 exhibited overall good anti-foaming / defoaming performance with an AKZ value of less than 400. Comparing Example 1 with Comparative Example 1, it was found that the overall anti-foaming / defoaming performance of the defoaming agent composition containing polyether-T resin was significantly better than that of the defoaming agent composition containing polyether-modified silicone oil. Furthermore, comparing Example 1 with Comparative Example 2, it was found that when polyether-T resin was combined with polypropylene glycol and fumed silica, it had clearly better anti-foaming / defoaming performance than when alkoxy-T resin and polypropylene glycol were physically mixed.

[0205] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Amount of antifoaming agent composition / μl 200 200 200 200 200 200 200 AKZ 10 205 362 155 912 577 9999* Initial height / mm 15 35 76 55 76 76 90

[0206] *: 9999 means that the measured AKZ is too large and exceeds the range of the optical sensor.

[0207] Antifoaming agent compositions of Example 5 and Comparative Examples 4 to 5

[0208] An antifoaming agent composition was obtained by thoroughly mixing the components of each example listed in Table 3.

[0209] weight part Example 5 Comparative Example 4 Comparative Example 5 A1 94.15 / / A2 / 77.50 / A3 / / 94.70 B1 2.93 2.66 2.61 B2 2.93 2.66 2.61 C1 / 17.20 /

[0210] Table 4 shows the evaluation results for each of the defoaming agent compositions of Example 5 and Comparative Examples 4 and 5. From Table 4, it was found that the combination of fumed silica and polyether-T resin had clearly better anti-foaming / defoaming performance than the polyether-modified silicone oil combined with fumed silica and polypropylene glycol, and the alkoxy-T resin combined with fumed silica.

[0211] Example 5 Comparative Example 4 Comparative Example 5 Amount of antifoaming agent composition / μl 12 15 12 AKZ 255 1515 937 Initial height / mm 84 83 81

[0212] Powder defoamers in Examples 6 and Comparative Examples 6 to 7

[0213] In each of the examples listed in Table 5, components A to D were thoroughly mixed and then combined with component F to obtain a powder defoamer.

[0214] weight part Example 6 Comparative Example 6 Comparative Example 7 A1 1.44 / / B1 0.04 / / B2 0.04 / / C1 23.48 46.20 66.00 D1 / 19.80 / F1 75.00 / / F2 / 34.00 34.00

[0215] Example of application: When using powder defoaming agents in dry mortar

[0216] In each case listed in Table 6, powdered defoaming agents were added to the cement and then thoroughly mixed with sand, redispersible polymer powder, cellulose ether, and a water-reducing agent to obtain dry mortar. Dry mortar without powdered defoaming agents was used as a blank control.

[0217] Subsequently, the dry mortar obtained in each case was mixed with 200 parts by weight of water, cured, and hardened to obtain a hardened mortar disc. During the mixing and curing process, no oil sedimentation was observed in the powdered defoamers of Example 6 and Comparative Example 7, but oil sedimentation occurred in Comparative Example 6.

[0218] weight part Application Example 1 Comparative Application Example 1 Comparative Application Example 2 Blank control group cement 1080 1080 1080 1080 sand 1255.2 1255.2 1255.2 1255.2 redispersible polymer powder 48 48 48 48 Cellulose ether 2.4 2.4 2.4 2.4 Suppressant 4.8 4.8 4.8 4.8 Powdered defoamer of Example 6 4.8 / / / Powdered antifoaming agent of Comparative Example 6 / 4.8 / / Powdered antifoaming agent of Comparative Example 7 / / 4.8 /

[0219] Table 7 summarizes the air content and fluidity of each application example and blank control. The dry mortar containing the powdered defoamer of the present invention had a significantly reduced air content and improved fluidity compared to the blank control. In addition, the dry mortar containing the powdered defoamer according to the present invention was superior to the dry mortar containing the non-inventive powdered defoamer in terms of air content and fluidity.

[0220] Application Example 1 Comparative Application Example 1 Comparative Application Example 2 Blank control group air content 3.00% 4.2% 3.4% 18.2% liquidity 22.85% 21.85% 3.4% 21.55%

Claims

Claim 1 An organopolysiloxane containing at least 50 mol% of trifunctional siloxane units, wherein at least one trifunctional siloxane unit has a polyether group, and the trifunctional siloxane unit having a polyether group is selected from polysiloxane (i) of formula (IV): (R 1 SiO 3 / 2 ) x (R 1 (R 2 O)SiO 2 / 2 ) y (R 1 R 3 SiO 2 / 2 ) z (R 1 (R 2 O)R 3 SiO 1 / 2 ) t (R 1 (R 2 O)2SiO 1 / 2 ) w (IV) Here, the sum of z+t is greater than 0; based on the total moles of siloxane units, x units (R 1 SiO 3 / 2 ) is an amount of 10 mol% to 60 mol%, and y units (R 1 (R 2 O)SiO 2 / 2 ) and z unit (R 1 R 3 SiO 2 / 2 The sum of ) is an amount of 20 mol% to 70 mol%, and in t units (R 1 (R 2 O)R 3 SiO 1 / 2 ) and w units (R 1 (R 2 O)2SiO 1 / 2 The sum of ) is an amount of 5 mol% to 30 mol%; R 1 In each case, are independently monovalent, optionally substituted, SiC-bonded hydrocarbon radicals, and R 2 In each case, is independently a hydrogen or a monovalent, optionally substituted hydrocarbon radical, and R 3 In each case, the chemical formula -OR is independently a -(OR b ) j -OR c It is a radical of, and in this chemical formula, R a is a divalent, selectively substituted hydrocarbon radical, and R b is independently a divalent, optionally substituted hydrocarbon radical in each case, and R c is hydrogen, a monovalent organic radical, or It has a structural fragment of, where R* is independently R in each case 1 , OR 2 Or -O-, and j is an integer from 1 to 200, an organopolysiloxane. Claim 2 In paragraph 1, radical R 3 is the chemical formula (III) and: Here, x is an integer from 1 to 10, m is an integer from 0 to 200, n is an integer from 0 to 200, the sum of m+n is an integer from 1 to 200, and R c is hydrogen, C1-C 30 Alkyl, C1-C 30 Alkenil, R d C1-C 20 -C(O)-R alkyl d or a radical It has a structural fragment of, where R* is independently C1-C in each case 18 Organopolysiloxanes that are alkyl, C6-C9 aryl, hydroxyl, C1-C4 alkoxy or -O-, and in which units (OC2H4) and (OC3H6) may exist in a random distribution or even as blocks in the radicals of formula (III). Claim 3 In paragraph 2, an organopolysiloxane in chemical formula (III) where x is 3, m is 0, and n is an integer from 5 to 100. Claim 4 In paragraph 1, R 3 An organopolysiloxane having a content of 5% to 95% by weight based on the total weight of the organopolysiloxane. Claim 5 In claim 1, the polysiloxane (i) is a mixture comprising a polysiloxane containing a unit of the formula (VI): Here, R 1 In each case, are independently monovalent, optionally substituted, SiC-bonded hydrocarbon radicals, and R 2 A mixture comprising a polysiloxane, wherein each is independently a hydrogen or a monovalent, optionally substituted hydrocarbon radical in each case, f is 0 or 1, g is 0, 1, 2 or 3, provided that in at least 50 mol% of all units of formula (VI), f is 1, and at least one unit g is different from 0; and a polyether compound of formula (VII): Here, R 4 is hydrogen or a monovalent organic radical, and R 5 is hydrogen or a C1-C3 alkyl, and R 6 An organopolysiloxane derived from the reaction of a polyether compound, wherein each is independently a divalent, optionally substituted hydrocarbon radical, and k is an integer from 1 to 200. Claim 6 A composition comprising (a) at least one organopolysiloxane of any one of claims 1 to 5, and (b) at least one additive selected from the following: (b1) filler particles and / or (b2) an organopolysiloxane resin comprising a unit of formula (X): Here, R 7 In each case, are independently hydrogen or a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, and R 8 A composition in which each is independently hydrogen or a monovalent, optionally substituted hydrocarbon radical, u is 0, 1, 2, or 3, v is 0, 1, 2, or 3, provided that the sum of u+v is 3 or less, and in all units of formula (X) less than 50 mol% in the organopolysiloxane resin, the sum of u+v is 2. Claim 7 In claim 6, (c) further comprises a polyether compound of formula (XI): Here, R 9 In each case, it is independently hydrogen or a monovalent organic radical, and R 10 A composition in which each is independently a divalent, optionally substituted hydrocarbon radical, and k is an integer from 1 to 200. Claim 8 In paragraph 7, component (c) is a compound of formula (XII): Here, R 9 In each case, independently hydrogen, C1-C 30 Alkyl, C1-C 30 Alkenyl or -C(O)-R d It is a radical of, where R d is C1-C 20 A composition in which alkyl, s is an integer from 0 to 200, t is an integer from 0 to 200, the sum of s+t is an integer from 10 to 200, and units (OC2H4) and (OC3H6) may exist in a random distribution or even as blocks in a polymer of formula (XII). Claim 9 In claim 8, a composition having the chemical formula (XII), where s is 0 and t is an integer from 20 to 200. Claim 10 A composition according to claim 7, wherein the mass ratio of component (a) : component (c) is 1 : (0.1 to 100). Claim 11 A composition according to claim 6, wherein the mass ratio of component (a) : component (b) is (5 to 30) :

1. Claim 12 A composition according to claim 6, comprising (a) at least one organopolysiloxane in an amount of 0.1 wt% to 90 wt%, (b) at least one additive in an amount of 0.01 wt% to 5 wt%, (c) at least one polyether in an amount of 5 wt% to 98 wt%, and optionally (d) at least one hydrocarbon oil in an amount of 0 wt% to 50 wt%. Claim 13 A powder formulation comprising the composition of claim 6 and a solid carrier. Claim 14 In paragraph 13, a powder formulation in which the mass ratio of composition to solid carrier is 2: (1 to 15). Claim 15 In claim 6, the composition is used as an antifoaming agent in cement-based materials or coating agents. Claim 16 delete Claim 17 delete

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