Organopolysiloxane, composition and powder formulation containing same, and use thereof as an antifoaming agent

Abstract

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

Description

[Technical Field]

[0001] The present disclosure relates to organopolysiloxanes, compositions and powder formulations containing same, and their use as antifoam agents. [Background technology]

[0002] Cementitious slurries, which contain solid and liquid components, often tend to foam due to the continuous stirring required to keep the solid components of the slurry in suspension and due to additives such as cellulose ethers incorporated into the cementitious slurry. If the formed bubbles are not able to dissipate in time, they will have a significant impact on the appearance and strength of the set cementitious slurry. Therefore, antifoaming agents are essential components of cementitious slurries.

[0003] Although polydimethylsiloxane-based defoamers are known, polydimethylsiloxanes are incompatible with most surfactant systems and tend to precipitate, which is highly undesirable. Polyethersiloxanes have been reported to be used as defoamers due to their good compatibility. However, the defoaming and / or defoaming effect of polyethersiloxanes themselves is usually not ideal, so polyethersiloxanes are often used in combination with silica and / or MQ silicone resins, or with large amounts of polydimethylsiloxanes and / or organic oils.

[0004] CN101802103A discloses an antifoam composition that can be used as a liquid wetting agent, washing or cleaning agent, which comprises a base oil, i.e., a polyether-modified silicone oil, silica and / or MQ silicone resin, and optionally a polypropylene glycol and / or a hydrocarbon oil.

[0005] US3984347A discloses an antifoam emulsion, which contains polypropylene glycol as a base oil, polydimethylsiloxane as a base oil, a foam control agent composed of silica and an MQ silicone resin, and a polyether-modified silicone oil for dispersing the foam control agent in the base oil.

[0006] US8536109B discloses a silicone foam control agent for liquid detergent systems, which includes a silicone antifoaming agent composed of an aryl-containing silicone oil, an MQ silicone resin and silica, a dispersant which is a polyether-containing MQ silicone resin in which polyether groups are bonded to silicon atoms via Si-C bonds, and optionally a crosslinked siloxane having polyether groups and an organic oil.

[0007] No. 3,746,653 A discloses foam control agents useful for jet dyeing of textiles, which comprise a linear siloxane glycol copolymer, a polydimethylsiloxane, a polyether-containing MQ silicone resin in which the polyether groups are bonded to the silicon atom via Si-C or Si-O bonds, silica, and an MQ silicone resin.

[0008] These antifoaming agents or foam control agents are mostly liquid, which makes them inconvenient to store, transport, and use. Also, they are not suitable for use in cementitious slurries. In recent years, some efforts have been reported on solid antifoaming agents. However, the antifoaming and / or defoaming efficiency of these solid antifoaming agents still needs to be improved.

[0009] US6129906A discloses a powdered antifoaming agent for denture cleansers, which comprises 50% to 99% of a water-soluble carrier and 3% to 35% of a hydrophobic silicone oil dispersed in 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 organosilicone antifoaming agent, which includes methylsilicone oil, dimethylsiloxane hydrolyzate, fumed silica, polyether-modified silicone oil, emulsion adjuvant, surface modifier and carrier.

[0011] CN106746889A discloses a solid defoamer for gypsum-based potting materials, which is composed of defoamer particles and a soluble polymer film wound thereon, and the defoamer particles include polyether-modified silicone oil, fumed silica, an emulsifier, and a carrier. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Chinese Patent Application Publication No. 101802103 [Patent Document 2] U.S. Patent No. 3,984,347 [Patent Document 3] U.S. Patent No. 8,536,109 [Patent Document 4] U.S. Patent No. 3,746,653 [Patent Document 5] U.S. Patent No. 6,129,906 [Patent Document 6] Chinese Patent No. 103028275 [Patent Document 7] Chinese Patent Application Publication No. 106746889 Summary of the Invention

[0013] The present disclosure aims to provide a polyether-containing organopolysiloxane, as well as an antifoam composition and a powder antifoam agent containing the same. Such an antifoam composition has superior antifoam and / or defoaming performance to those containing polyether-containing silicone oils. Furthermore, the active ingredient of the antifoam composition can be adsorbed onto a solid carrier and used as a powder antifoam agent to rapidly eliminate foam formed in the preparation of cement-based materials or coatings.

[0014] The term "cementitious material" should be understood to include cement, dry mixtures containing cement, and flowable mixtures containing cement. Known cements, primarily hydraulic materials, are Portland cement, aluminate cement, sulfoaluminate cement, fluoroaluminate cement, and ferroaluminate cement.

[0015] A "dry mix" generally includes cement and optional supplemental cementitious materials, and may further include one or more of aggregates, polymers, and admixtures. As used herein, cement typically refers to ordinary Portland cement. Supplemental cementitious materials herein refer to materials that set, continue to harden, and gain strength through a hydration process, such as cement, including, but not limited to, fly ash, silica fume, ground granulated blast furnace slag (also known as slag), cinders, and pozzolans, as well as non-hydraulic cementitious materials that set in air, such as limestone and gypsum. Aggregate broadly refers to several different types of both coarse-grained and fine-grained materials, including, but not limited to, sand, gravel, and crushed stone. Fine aggregate generally refers to aggregates with a particle size less than 4.75 mm. Polymers typically include polymers (or (co)polymers) based on one or more ethylenically unsaturated monomers, such as acrylic acid copolymers and ethylene-vinyl acetate copolymers. Admixtures include, but are not limited to, cellulose ethers, water reducers, water repellents, anti-setting agents, retarders, and superplasticizers. In the context of this disclosure, dry mixes include dry mortars as referred to in the literature. Dry mortars are mixtures generally comprising cement, fine aggregates, and admixtures, and optionally supplemental cementitious materials and / or polymers.

[0016] "Fluid mixture" refers to a slurry material obtained by mixing cement and optional supplemental cementitious materials with water, such as, but not limited to, paste, mortar, grout, and concrete. Paste generally refers to a mixture containing cement, admixtures, and water. Mortar generally refers to a mixture containing cement, sand, admixtures, and water. Grout generally refers to a mixture containing cement, sand, polymer, admixtures, and water. Concrete generally refers to a mixture containing cement, sand, coarse aggregate, admixtures, and water. The aforementioned paste, mortar, grout, and concrete may optionally contain supplemental cementitious materials, and generally, the addition of admixtures is less than 3% by weight, and the addition of polymers is more than 1% by weight and less than 50% by weight, based on the total weight of the cement and supplemental cementitious materials. In the context of the present disclosure, the fluid mixture may also be understood as a cementitious slurry.

[0017] As used herein, "T resin" refers to a trifunctional siloxane unit RSiO 3 / 2 (T), where R is a monovalent, optionally substituted, SiC-bonded organic group, and each oxygen atom is bonded at one end to a silicon atom and at the other end to either a silicon atom or a monovalent, optionally substituted organic group.

[0018] [ka] are all 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 expression "consisting essentially of trifunctional siloxane units" means that the silicone resin contains at least 50 mol%, for example, 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 number of moles of siloxane units.

[0019] A first aspect of the present disclosure provides an organopolysiloxane comprising at least 50 mole % trifunctional siloxane units and at least one trifunctional siloxane unit having a polyether group selected from the following: (i) a polysiloxane comprising units of formula (I) R 1 a (R 2 O) b R 3 c SiO (4-a-b-c) / 2 (I) [In the formula, R 1 is independently in each occurrence a monovalent optionally substituted SiC-bonded hydrocarbon radical; R 2 is independently in each occurrence hydrogen or a monovalent optionally substituted hydrocarbon group; R 3 independently in each occurrence the expression -OR a -(OR b ) j -OR c where R a is a divalent optionally substituted hydrocarbon group, and R b is independently in each occurrence a divalent optionally substituted hydrocarbon group; R c is hydrogen, a monovalent organic group, or

[0020] [ka] a structural fragment of R * is independently in each occurrence R 1 , OR 2 or O-, and j is an integer of 1 to 200, preferably an integer of 20 to 200; a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; c is 0, 1 or 2; with the proviso that in at least 50 mole % of all units of formula (I), a is 1 and the sum b+c is 0, 1 or 2, and in at least one of these units c is different from 0; or (ii) a polysiloxane comprising units of formula (II) R 1’ d R 3’ e SiO (4-d-e) / 2 (II) [In the formula, R 1’ is independently in each occurrence a monovalent optionally substituted SiC-bonded hydrocarbon radical; R 3’ independently in each occurrence, the formula -R a ’ -(OR b ’ ) j ’ -OR c ’ where R a ’ is a divalent optionally substituted hydrocarbon group, and R b ’ is independently in each occurrence a divalent optionally substituted hydrocarbon group; R c ’ is hydrogen, a monovalent organic group, or

[0021] [ka] wherein R *’ is independently in each occurrence R 1’ or O-, r is an integer of 1 to 6, and j' has a structural fragment in which j' is an integer of 1 to 200, preferably an integer of 20 to 200; d is 0 or 1, e is 0 or 1; provided that in at least 50 mol % of all units of formula (II), the sum d+e is 1, and in at least one of these units, e is different from 0.

[0022] The expression "at least one trifunctional siloxane unit having a polyether group" refers in the context of the present disclosure to "at least one polyether-T unit." The polyether-T unit is also the R 1 a (R 2 O) b R 3 c SiO (4-a-b-c) / 2 (wherein a is 1, the sum b+c is 0, 1 or 2, and in at least one unit, c is different from 0), and R 1’ d R 3’ e SiO (4-d-e) / 2 where the sum d+e is 1, and in at least one unit e is different from 0.

[0023] base R 1 Examples of substituted groups R are alkyl groups such as 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 groups such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl, alkenyl groups such as vinyl, 1-propenyl and 2-propenyl, aryl groups such as phenyl and naphthyl, alkaryl groups such as o-, m-, p-tolyl, xylyl and ethylphenyl, and aralkyl groups such as benzyl, α- and β-phenylethyl. 1 Examples of are hydrocarbon groups substituted with organosilyl groups such as trimethylsilylethylene, and also hydrocarbon groups substituted with organosiloxanyl groups.

[0024] Preferably, the group R 1is an alkyl group having 1 to 18 carbon atoms or an aromatic group having 6 to 9 carbon atoms, particularly preferably methyl, n-hexyl, n-heptyl, n-octyl, phenyl and ethylphenyl, in particular methyl.

[0025] base R 2 Examples of R are hydrogen or a group R 1 are examples given for, with preference given to hydrogen and hydrocarbon groups having 1 to 4 carbon atoms, in particular methyl and ethyl.

[0026] base R a is preferably a hydrocarbon group having 1 to 10 carbon atoms, such as -CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)CH2-, -CH2-CH2-CH4- and -CH2-CH(CH3)-CH4-, in particular -CH2-CH(CH3)- and -CH2-CH2-CH2-.

[0027] base R b Examples 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)-.

[0028] base R c Examples of R are hydrogen or a group R 1 Examples shown for -C(O)-R d - is a group, and R d is a group that is alkyl, preferably hydrogen, methyl, allyl, butyl and acetyl. c When the group R is one of the aforementioned groups, one end of the polyether chain is attached to the siloxane via an Si—O bond and the other end is free. c Examples of

[0029] [ka] and R *is, independently in each occurrence, R as defined above 1 OR 2 or -O-, and preferably

[0030] [ka] or

[0031] [ka] where Me represents methyl and Et represents ethyl. In such cases, both ends of the polyether chain are bonded to the siloxane via Si-O bonds to form a crosslinked structure.

[0032] In certain embodiments herein, the group R3 is of formula (III). -O-(CH2) x -(OC2H4) m -(OC3H6) n -OR c (III) [wherein x is an integer of 1 to 10, preferably an integer of 2 to 6, particularly 3; m is an integer of 0 to 200, preferably an integer of 0 to 100, particularly an integer of 0 to 50; n is an integer of 0 to 200, preferably an integer of 5 to 100, particularly an integer of 20 to 80; The sum m+n is an integer between 1 and 200, R c is hydrogen, C1 to C 30 Alkyl, C1-C 30 Alkenyl, or C(O)-R d is a group of R d is C1~C 20 a group which is alkyl or

[0033] [ka] Structural fragment of (where R * independently in each occurrence, C1 to C 18alkyl, C6-C9 aryl, hydroxyl, C1-C4 alkoxy or -O-, in particular methyl, hydroxyl, methoxy, ethoxy or -O-, c is preferably hydrogen, methyl, allyl, butyl, acetyl, or

[0034] [ka] or

[0035] [ka] where Me represents methyl and Et represents ethyl, The units (OC2H4) and (OC3H6) may be present in random distribution or as blocks in the group of formula (III).

[0036] In one embodiment herein, the organopolysiloxane (i) is 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) [In the formula, the group R 1 , R 2 , R 3 is as defined above, the sum of z+t is greater than 0, and preferably, the number of moles of x units (R 1 SiO 3 / 2) is in an amount of 10 mol % to 95 mol %, for example, 10 mol % to 60 mol %, and the y units (R 1 (R 2 O)SiO 2 / 2 ) and z units (R 1 R 3 SiO 2 / 2 ) is in an amount of 5 mol % to 90 mol %, for example, 20 mol % to 70 mol %, and the sum of the 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 the above is 5 mol % to 30 mol %. The molar content can be determined by a method well known in the art, for example, 29 It can be measured by Si NMR.

[0037] base R 1’ , R a ’ , R b ’ are examples of groups R 1 , R a and R b The group R c ’ Examples of are hydrogen or the group R 1’ For the example shown, or -C(O)-R d ’ (where R d ’ is alkyl.) and preferably hydrogen, methyl, allyl, butyl and acetyl. c ’ When R is one of the aforementioned groups, one end of the polyether chain is attached to the siloxane via a Si-C bond and the other end is free. c ’ Examples of

[0038] [ka] Structural fragment of (where R *’ is, independently in each occurrence, R as defined above. 1’or —O—, and r is an integer of 1 to 6.)

[0039] [ka] In such cases, both ends of the polyether chain are bonded to the siloxane via Si-C bonds to form a crosslinked structure.

[0040] In certain embodiments herein, the group R 3’ is of formula (V), -(CH2) x’ -(OC2H4) m’ -(OC3H6) n’ -OR c ’ (V) [wherein x' is an integer of 1 to 10, preferably an integer of 2 to 6, particularly 3; m' is an integer of 0 to 200, preferably an integer of 0 to 100, particularly an integer of 0 to 50; n' is an integer of 0 to 200, preferably an integer of 5 to 100, particularly an integer of 20 to 80, The sum m'+n' is an integer between 1 and 200, R c ’ is hydrogen, C1 to C 30 Alkyl, C1-C 30 Alkenyl, or C(O)-R d ’ is a group of R d ’ is C1~C 20 a group which is alkyl or

[0041] [ka] a structural fragment of R *’ independently in each occurrence, C1 to C 18 alkyl, C6-C9 aryl, or -O-, in particular methyl or -O-, and r is an integer from 1 to 6; R c ’is preferably hydrogen, methyl, allyl, butyl, acetyl, or

[0042] [ka] (r is an integer of 1 to 6), The units (OC2H4) and (OC3H6) can be present in random distribution or as blocks in the group of formula (V).

[0043] The organopolysiloxane of the present disclosure may contain 5 wt % to 95 wt %, for example, 10 wt % to 50 wt %, of R based on the total weight of the organopolysiloxane. 3 or R 3’ The weight content can be determined by methods well known in the art, for example, 1 It can be measured by 1 H NMR.

[0044] The organopolysiloxanes of the present disclosure may also contain monofunctional siloxane units R in addition to the trifunctional siloxane units defined by the foregoing conditions. 1 3SiO 1 / 2 (M), bifunctional siloxane unit R 1 2SiO 2 / 2 (D) and tetrafunctional siloxane units SiO 4 / 2 (Q) (wherein the group R 1 is as defined above.) The molar ratio of the other siloxane units can be less than 50 mol%, for example, less than 40 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, or even less than 5 mol%, based on the total number of moles of siloxane units.

[0045] The organopolysiloxane (i) of the present disclosure is a polysiloxane comprising units of formula (VI): R 1 f (R 2 O) g SiO (4-f-g) / 2 (VI) [In the formula, the group R 1 and R 2is as defined above, 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 in at least one unit thereof, g is different from 0; and Polyether compounds of formula (VII) R 4 -(OR 6 ) k -OR 5 (VII) [In the formula, R 4 is hydrogen or a monovalent organic group, R 5 is hydrogen or C1-C3 alkyl, R 6 is independently in each occurrence a divalent optionally substituted hydrocarbon group; k is an integer of 1 to 200, preferably an integer of 10 to 200.] It is derived from the reaction of a mixture containing

[0046] This reaction is typically a condensation reaction, which can be catalyzed by a catalyst conventionally used in the art, for example, an acidic catalyst such as sulfuric acid, trifluoromethanesulfonic acid, fluorine-containing carboxylic acid, solid acid (for example, acid-activated clay, macroporous cation exchange resin), phosphorus dichloronitrile (phosphonitrile chloride) and its oligomer, a basic catalyst such as potassium hydroxide, preferably a solid acid catalyst.

[0047] The reaction is suitably carried out at a temperature of 80° C. to 120° C., preferably for 0.5 to 4 hours. The reaction is advantageously carried out under reduced pressure to extract the small molecule alcohol produced therefrom to facilitate condensation.

[0048] The group -OR in polysiloxane (VI) 2 is condensed to form the group -OR in the polyether (VII). 4 and / or -OR 5with the result that the polyether chain is connected to the siloxane via an Si—O bond.

[0049] In certain embodiments herein, the polysiloxane (VI) is of formula (VIII): (R 1 SiO 3 / 2 ) o (R 1 (R 2 O)SiO 2 / 2 ) p (R 1 (R 2 O)2SiO 1 / 2 ) q (VIII) [In the formula, the group R 1 and R 2 is as defined above, o is a number greater than or equal to 0, p is a number greater than 0, q is a number greater than or equal to 0.]

[0050] Preferably, the o units (R 1 SiO 3 / 2 ) is in an amount of 0 mol % to 80 mol %, for example, 5 mol % to 50 mol %, and p units (R 1 (R 2 O)SiO 2 / 2 ) is in an amount of 5 mol % to 90 mol %, and the 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.

[0051] Polysiloxane (VI) or (VIII) may further comprise less than 50 mole %, e.g., less than 40 mole %, less than 30 mole %, less than 20 mole %, less than 10 mole %, or less than 5 mole %, based on the total number of moles of siloxane units, of other siloxane units, e.g., units R 1 3SiO 1 / 2 (M), siloxane unit R 1 2SiO 2 / 2(D) and units of SiO 4 / 2 (Q)(Group R 1 is as defined above.

[0052] The polyether (VII) is preferably a compound of the following formula: R 4 -(OC2H4) s -(OC3H6) t -OR 5 [In the formula, R 4 are hydrogen atoms, C1 to C 30 Alkyl groups, C1-C 30 Alkenyl group or -C(O)-R d (where R d is hydrogen, C1 to C 20 alkyl, preferably hydrogen, methyl, allyl or butyl; R 5 is hydrogen or C1-C3 alkyl, preferably hydrogen or methyl; s is an integer of 0 to 200, preferably an integer of 0 to 100, particularly an integer of 0 to 50; t is an integer of 0 to 200, preferably an integer of 5 to 100, particularly an integer of 20 to 80; The sum s+t is an integer between 10 and 200, The units (OC2H4) and (OC3H6) may be present in random distribution or as blocks in the polymer of formula (VII).

[0053] The organopolysiloxane (ii) of the present disclosure is a polysiloxane comprising units of formula (IX): R 1 h H i SiO (4-h-i) / 2 (IX) [In the formula, the group R 1 is as defined above, h is 0 or 1; i is 0 or 1, provided that in at least 50 mol % of all units of formula (IX), the sum h+i is 1, and in at least one unit, i is different from 0; and Polyether compounds of formula (VII') R 4’ -(OR 6’ ) k’ -OR 5’ (VII') [In the formula, R 4’ is C1~C 30 Alkenyl, C1-C 30 alkyl or hydrogen, preferably allyl, methyl or butyl; R 5’ is C1~C 30 alkenyl, preferably allyl; R 6’ is independently in each occurrence a divalent optionally substituted hydrocarbon group; k' is an integer of 1 to 200, preferably an integer of 10 to 200. It is derived from the reaction of a mixture containing

[0054] The reaction conditions can refer to those of conventional hydrosilylation reactions in the art. The hydrogen atoms in the polysiloxane (IX) react with the alkenyl groups in the polyether (VII') by addition, so that the polyether chain is connected to the siloxane via a Si-C bond.

[0055] A second aspect of the present disclosure is to provide a composition comprising: (a) at least one organopolysiloxane (i) and / or (ii) of the first aspect of the present disclosure, and (b) at least one additive selected from the following: (b1) filler particles and / or (b2) Organopolysiloxane resin containing units of formula (X): R 7 u (R 8 O) v SiO (4-u-v) / 2 (X) [In the formula, R 7 is independently in each occurrence hydrogen or a monovalent optionally substituted SiC-bonded hydrocarbon radical; R 8 is independently in each occurrence hydrogen or a monovalent optionally substituted hydrocarbon group; u is 0, 1, 2 or 3; v is 0, 1, 2 or 3; provided that the sum u+v is ≦3, and the sum u+v is 2 in less than 50 mol% of all units of formula (X) in the organopolysiloxane resin.]

[0056] Component (b1) is preferably powdered, more preferably powdered and hydrophobic. Examples of component (b1) include, but are not limited to, silicon dioxide (silica), titanium dioxide, aluminum oxide, metal soap, quartz powder, PTFE powder, and finely divided hydrophobic polyurethane.

[0057] Component (b1) is preferably 20 to 1000 m 2 / g, especially 50-400m 2 / g BET specific surface area.

[0058] Component (b1) preferably has a particle size of less than 10 μm, particularly from 10 nm to 5 μm.

[0059] As component (b1), silica, especially 50 to 800 m 2 Particularly preferred are silicas having a BET specific surface area of ​​1 / g. These silicas can be fumed or precipitated silicas. Hydrophobic silicas are advantageous for the desired effectiveness of the composition as an antifoaming agent. Methods for hydrophobizing silica are well known.

[0060] Component (b2) is preferably an organopolysiloxane resin in which the sum u+v is 2 in 0 to 30 mol %, more preferably 0 to 5 mol %, of all units.

[0061] base R 7 Examples of groups include the group R 1 and is preferably an alkyl group having 1 to 4 carbon atoms or phenyl, especially methyl.

[0062] base R 8 Examples of groups include the group R 2 and preferably an alkyl group having 1 to 4 carbon atoms, in particular methyl or ethyl.

[0063] Component (b2) is particularly preferably R 7 3SiO 1 / 2 (M) units and SiO 4 / 2 (Q) units, wherein R 7 has the same meaning as above, and these resins are also called MQ resins. The molar ratio of M units to Q units is preferably in the range of 0.5 to 2.0, particularly in the range of 0.6 to 1.0. These silicone resins may also contain up to 10% by weight of free hydroxy or alkoxy groups. Here, R 7 is preferably methyl.

[0064] The mass ratio of component (a) to component (b) is preferably (5-30):1, for example, (10-30):1.

[0065] The compositions of the present disclosure preferably further comprise: (c) a polyether compound of formula (XI) R 9 -(OR 10 ) k -OR 9 (XI) [In the formula, R 9 is independently in each occurrence hydrogen or a monovalent organic group; R 10 is independently in each occurrence a divalent optionally substituted hydrocarbon group; k is an integer from 1 to 200.

[0066] The polyether (XI) is preferably a compound of formula (XII). R 9 -(OC2H4) s -(OC3H6) t -OR 9 [In the formula, R9 is independently in each occurrence hydrogen, C1 to C 30 Alkyl, C1-C 30 Alkenyl or C(O)-R d is a group of the formula R d is C1~C 20 is a radical which is alkyl, preferably hydrogen, methyl, allyl or butyl, in particular hydrogen, s is an integer of 0 to 200, preferably an integer of 0 to 100, particularly an integer of 0 to 50; t is an integer of 0 to 200, preferably an integer of 5 to 100, particularly an integer of 20 to 80; The sum s+t is an integer between 10 and 200, The units (OC2H4) and (OC3H6) may be present in random distribution or as blocks in the polymer of formula (XII).

[0067] Polyethers of formula (XII) in which s is 0 and t is an integer from 20 to 200 are preferred.

[0068] 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.

[0069] The mass ratio of component (a) to component (c) is preferably 1:(0.1 to 100), more preferably 1:(5 to 30), for example 1:(8 to 25).

[0070] The composition of the present disclosure may further comprise (d) at least one hydrocarbon oil, such as mineral oil, natural oil, isoparaffin, polyisobutylene, fatty acid ester, or fatty alcohol. Component (d) may also be a commercially available hydrotreated light distillate (petroleum). Component (d) is preferably used in an amount of 0 to 50 parts by weight, particularly 0 to 30 parts by weight, based on 100 parts by weight of the antifoam composition. Considering the possibility of oil precipitation when a composition containing component (D) is applied to a cement-based material or coating, the composition of the present disclosure preferably does not comprise component (D).

[0071] In principle, the compositions of the present disclosure may also contain other organosilicon compounds different from those of formula (I), (II), (IV), (VI), (VIII), (IX) or (X), such as methylpolysiloxanes, especially polydimethylsiloxanes. However, given that polydimethylsiloxanes are incompatible with most surfactant systems, the compositions of the present disclosure preferably do not contain polydimethylsiloxanes.

[0072] As used herein, the expression "free of XX" means that the content of a particular component is less than 1% by weight, for example, less than 0.5% by weight, or even less than 0.1% by weight of the total weight of the composition.

[0073] In certain embodiments herein, the composition comprises: (a) 0.1% to 90% by weight of at least one organopolysiloxane (i) and / or (ii) according to the first aspect of the present disclosure; (d) 0.01% to 5% by weight of at least one additive; (c) 5% to 98% by weight of at least one polyether; and optionally (d) 0% to 50% by weight of at least one hydrocarbon oil.

[0074] In a preferred embodiment herein, the composition comprises: (a) 0.5% to 20% by weight of at least one organopolysiloxane (i) and / or (ii) according to the first aspect of the present disclosure; (d) 0.01% to 2% by weight of at least one additive; (c) 50% to 98% by weight of at least one polyether; and optionally (d) 0% to 50% by weight of at least one hydrocarbon oil.

[0075] 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, wherein the composition is adsorbed as an active ingredient onto the solid carrier.

[0076] 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, diatomaceous earth, 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, cellulose derivatives.

[0077] In a preferred embodiment herein, silica fume is used as the solid carrier. "Silica fume" is a finely divided material containing at least 85% by weight of amorphous silicon dioxide obtained as a by-product in the production of ferrosilicon or industrial silicon (see Chinese National Standard GB / T Standard 27690-2011).

[0078] The method for preparing the powder formulation is not particularly limited, as long as the composition of the second aspect of the present disclosure and the solid carrier are well mixed. The composition and the solid carrier are appropriately mixed at a mass ratio of less than 1:1, preferably less than 1:2, for example, 1:3. In some embodiments of the present specification, the mass ratio of the composition to the solid carrier is 2:(1-15), for example, 2:(3-10).

[0079] A fourth aspect of the present disclosure provides the 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.

[0080] The compositions or powder formulations can be used as defoamers in cementitious materials, such as the aforementioned dry mixes containing cement and flowable mixes containing cement, coatings, adhesives, water-miscible cooling lubricants, textiles, personal care, cosmetics, and inks, for example.

[0081] When the composition or powder formulation is used as an antifoaming agent in a cement-based material or coating, bubbles formed during the preparation of the cement-based material or coating are quickly removed. The method of use is not particularly limited. The composition can be suitably added during the preparation of a fluid mixture containing cement, such as paste, mortar, grout, and concrete, or a coating. The powder formulation can be suitably added during the preparation of a dry mixture containing cement, particularly dry mortar, or a powder coating.

[0082] A fifth aspect of the present disclosure provides a defoamer comprising the composition of the second aspect of the present disclosure or the powder formulation of the third aspect of the present disclosure. [Example]

[0083] The present invention will be further illustrated by the following examples, but is not limited in scope. Any experimental methods in the following examples that do not specify conditions are selected according to conventional methods and conditions or product specifications.

[0084] Characterization of molecular structure The structure of the resin was analyzed using a Bruker Avance III HD 400 spectrometer equipped with a 5 mm BBO probe head. 1 H NMR and 29 The results were analyzed by Si NMR.

[0085] Characterization of molecular weight and its distribution The molecular weight and distribution of the resin was analyzed by PSS SECcurity gel permeation chromatography using toluene as the solvent and an Agilent PLgel 5 um MiniMIX-C column at an oven temperature of 45°C.

[0086] Evaluation of antifoam and / or defoaming effects Preparation of foaming liquid: 8 g of sodium allyl sulfonate was dissolved in 192 mL of water and mixed well to give 200 mL of foaming liquid.

[0087] In each case, the antifoam composition was added to 200 mL of foaming liquid prepared in the amounts specified in Tables 2 and 4, and then stirred for 1 minute at 1000 rpm with a double-rod stirrer. The initial foam height and the change in foam height over time were recorded with an optical sensor, and a foam height-time curve was collected. The initial foam height reflects the antifoaming properties of the composition. The lower the initial height, the better the antifoaming performance. The integrated area bounded by the height-time curve, the height axis, and the time axis, i.e., the integrated area of ​​the curve from the initial height to a height of zero (more precisely, the minimum foam height that the optical sensor can detect, generally a value very close to zero), is called the AKZ (activity value). The AKZ comprehensively reflects the antifoaming properties and defoaming speed of the composition. A smaller AKZ value indicates better overall antifoaming / defoaming performance.

[0088] Air content measurement This was carried out according to the (Chinese National Standard) JC / T Standard 601-2009, Method for Determining Air Content in Cement Mortar.

[0089] Measuring Liquidity This was carried out according to GB / T standard 2419-2005, test method for fluidity of cement mortar.

[0090] Details of the raw materials used in the examples and comparative examples are as follows. A2: 29 PO30-((CH3)2SiO) measured by Si NMR 2 / 2 ) 15 -PO30, where PO30 represents a polyether group having 30 propoxy groups, and the polyether content is 1 Polyether modified silicone oil, 76 wt% as determined by H NMR.

[0091] A3:CH3SiO 3 / 2 Units: C2H5O(CH3)SiO 2 / 2 Units and (C2H5O)2(CH3)SiO 1 / 2 It consists essentially of units, 29 30.5 mol% CH3SiO determined by Si NMR 3 / 2 Units, 46.3 mol% C2H5O(CH3)SiO 2 / 2 units and 20.3 mol% of (C2H5O)2(CH3)SiO 1 / 2 Alkoxy T resin having units.

[0092] B1: Fumed silica, trade name HDK(R)H2000, manufactured by Wacker Chemie AG.

[0093] B2: Fumed silica, trade name HDK(R)H15, manufactured by Wacker Chemie AG.

[0094] C1: Hydroxy-terminated polypropylene glycol, trade name PPG2000, commercially available.

[0095] C2: Hydroxy-terminated polypropylene glycol, trade name PPG1000, commercially available.

[0096] C3: Hydroxy-terminated polypropylene glycol, trade name PPG350, commercially available.

[0097] D1: Hydrotreated light distillates (petroleum), commercially available.

[0098] F1: Silica fume, implemented GB / T standard 27690-2011, commercially available.

[0099] F2: Precipitated silica, trade name Evonik sipernat® 22, manufactured by Evonik.

[0100] Cement (42.5 grade): benchmark cement for concrete admixture testing, implementation GB standard 8076-2008, commercially available.

[0101] Sand: ISO standard sand, implemented GB / T standard 1761-1999, commercially available.

[0102] Redispersible polymer powder: trade name VINNAPAS® 5010N, manufactured by Wacker Chemie AG.

[0103] Cellulose ether: trade name Tylose(R) MH10007 P4, manufactured by Shin-Etsu Co., Ltd.

[0104] Water reducer: The product name MELMENT(R) F10 is manufactured by BASF.

[0105] Synthesis Example 1 Polyether-T Resin 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 weight ratio of Alkoxy T Resin A3 to polypropylene glycol C1 was (1-3):1, and the weight ratio of Alkoxy T Resin A3 to water was (4×10 3 ~6×10 3 The temperature was controlled at 80-100°C (100-300 mbar). The resulting mixture was heated to 80-100°C and stirred for 50-80 minutes for condensation. A vacuum (100-300 mbar) was then applied to remove the distillate (mainly ethanol) at 80-100°C. After the vacuum step, the mixture was stirred for 20-40 minutes at 80-100°C. An appropriate amount of sodium carbonate and water was then added, and the mixture was thoroughly mixed with stirring at 80-100°C for 50-80 minutes. The vacuum (100-200 mbar) was maintained until the distillate flux decreased. The resulting mixture was then cooled, followed by filtration of the solid.

[0106] The resulting reaction product is 1 It was determined by H NMR to have a polyether content of 31.63 mol % (calculated by weight, equivalent to 33.00 wt %). 1Comparing with the H NMR results, it was found that approximately 74.56 mol% of the hydroxyl groups from polypropylene glycol C1 reacted with alkoxy-T resin A3, indicating that most of the charged polypropylene glycol C1 participated in the condensation reaction and bonded to alkoxy-T resin A3 via Si-O bonds, with some of the polypropylene glycol C1 condensing via the hydroxyl group at only one end and some condensing via the hydroxyl groups at both ends. Hereinafter, this reaction product will be referred to as polyether T resin A1.

[0107] Polyether-T Resin A1 is 29 Si NMR revealed that (CHSiO 3 / 2 ) x (C2H5O(CH3)SiO 2 / 2 ) y (PO30(CH3)SiO 2 / 2 ) z ((C2H5O)(PO30)(CH3)SiO 1 / 2 ) t ((C2H5O)2(CH3)SiO 1 / 2 ) w 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 groups.

[0108] As measured by PSS SECcurity gel permeation chromatography, the raw 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, and 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.

[0109] [Antifoaming Agent Compositions of Examples 1 to 4 and Comparative Examples 1 to 3] The components of each example listed in Table 1 were thoroughly mixed to obtain a defoamer composition.

[0110] [Table 1]

[0111] Table 2 shows the evaluation results of each defoaming agent composition of Examples 1 to 4 and Comparative Examples 1 to 3. The defoaming agent compositions of Examples 1 to 4 had AKZ values ​​of less than 400, demonstrating good overall defoaming / defoaming performance. A comparison of Comparative Example 1 with Comparative Example 2 revealed that the overall defoaming / 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. Furthermore, a comparison of Example 1 with Comparative Example 2 revealed that the polyether-T resin blended with polypropylene glycol and fumed silica had significantly better defoaming / defoaming performance than a physical mixture of alkoxy-T resin and polypropylene glycol.

[0112] [Table 2]

[0113] [Antifoaming agent compositions of Example 5 and Comparative Examples 4 to 5] The components of each example listed in Table 3 were thoroughly mixed to obtain a defoamer composition.

[0114] [Table 3]

[0115] Table 4 shows the evaluation results of each of the defoaming agent compositions of Example 5 and Comparative Examples 4 to 5. Table 4 shows that the polyether-T resin blended with fumed silica has clearly better defoaming / defoaming performance than the polyether-modified silicone oil blended with fumed silica and polypropylene glycol, and the alkoxy-T resin blended with fumed silica.

[0116] [Table 4]

[0117] [Example 6 and Comparative Examples 6 to 7: Powdered Antifoaming Agents] In each example listed in Table 5, components A to D were mixed well and then combined with component F to obtain a powder defoamer.

[0118] [Table 5]

[0119] Application example: Use of powder defoamer in dry mortar The powdered defoamer in each case listed in Table 6 was added to cement, which was then thoroughly mixed with sand, redispersible polymer powder, cellulose ether, and water-reducing agent to obtain dry mortar. Dry mortar without powdered defoamer was used as a blank control.

[0120] Then, 200 parts by weight of water was mixed with the dry mortar obtained in each case, and the mixture was allowed to harden and set to obtain hardened mortar discs. During the mixing and hardening process, no oil precipitation was observed with the powdered defoamers of Example 6 and Comparative Example 7, but oil precipitation occurred with the powdered defoamer of Comparative Example 6.

[0121] [Table 6]

[0122] Table 7 summarizes the air content and fluidity of each application example and the 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. Also, the dry mortar containing the powdered defoamer of the present invention was superior in air content and fluidity to that containing the non-invention powdered defoamer.

[0123] [Table 7]

Claims

1. An organopolysiloxane containing at least 50 mole percent trifunctional siloxane units, At least one of the trifunctional siloxane units has a polyether group, and the at least one trifunctional siloxane unit having a polyether group is a polysiloxane (i) of formula (IV): Organopolysiloxane. (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) ２ SiO １／２ ) ｗ (IV) [In the formula, The sum of z+t is greater than 0, Based on the total number of moles of siloxane units, x units (R １ SiO ３／２ ) is in an amount of 10 mol % to 60 mol %, and the y units (R １ (R ２ O) SiO ２／２ ) and z units (R １ R ３ SiO ２／２ ) is in an amount of 20 mol % to 70 mol %, and the sum of the t units (R １ (R ２ O)R ３ SiO １／２ ) and w units (R １ (R ２ O) ２ SiO １／２ ) is in an amount of 5 mol % to 30 mol %; R １ is independently in each occurrence a monovalent optionally substituted SiC-bonded hydrocarbon radical; R ２ is independently in each occurrence hydrogen or a monovalent optionally substituted hydrocarbon group; R ３ represents, independently in each occurrence, a group of the formula -O-R ａ - (OR ｂ ) ｊ -O-R ｃ where R ａ is a divalent optionally substituted hydrocarbon group, and R ｂ is independently in each occurrence a divalent optionally substituted hydrocarbon group; R ｃ is hydrogen, a monovalent organic group, or 【Chemistry 1】 A structural fragment of the formula: ＊ independently in each occurrence, R １ , OR ２ or O—, and j is an integer from 1 to 200.]

2. group R ３ is of formula (III): -O-(CH ２ ) ｘ -(OC ２ H ４ ) ｍ -(OC ３ H ６ ) ｎ -O-R ｃ (III) wherein 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 m+n is an integer from 1 to 200, R ｃ is hydrogen, C １ ~C ３０ Alkyl, C １ ~C ３０ Alkenyl, or C(O)—R ｄ is a group of the formula R ｄ is C １ ~C ２０ a group which is alkyl or 【Chemistry 2】 A structural fragment of the formula: ＊ independently in each occurrence, C １ ~C １８ Alkyl, C ６ ~C ９ Aryl, Hydroxyl, C １ ~C ４ having a structural fragment that is alkoxy or —O—; Units (OC ２ H ４ ) and (OC ３ H ６ ) may be present in random distribution or as blocks in the group of formula (III).

2. The organopolysiloxane according to claim 1 ,

3. 3. The organopolysiloxane of claim 2, characterized by formula (III) where x is 3, m is 0, and n is an integer from 5 to 100.

4. R ３ The organopolysiloxane according to any one of claims 1 to 3, wherein the content of is 5 to 95% by weight based on the total weight of the organopolysiloxane.

5. Polysiloxane (i) is a polysiloxane comprising units of formula (VI): R １ ｆ (R ２ O) ｇ Yes （４－ｆ－ｇ）／２ (VI) [In the formula, R １ is independently in each occurrence a monovalent optionally substituted SiC-bonded hydrocarbon radical; R ２ is independently in each occurrence hydrogen or a monovalent optionally substituted hydrocarbon group; 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 in at least one unit thereof, g is different from 0; and Polyether compounds of formula (VII) R ４ -(OR ６ ) ｋ -O-R ５ (VII) [In the formula, R ４ is hydrogen or a monovalent organic group, R ５ is hydrogen or C １ ~C ３ is alkyl, R ６ is independently in each occurrence a divalent optionally substituted hydrocarbon group; k is an integer from 1 to 200.

5. The organopolysiloxane according to claim 1, which is derived from the reaction of a mixture comprising:

6. A composition comprising: (a) at least one organopolysiloxane according to 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 containing units of formula (X): R ７ ｕ (R ８ O) ｖ SiO （４－ｕ－ｖ）／２ (X) [In the formula, R ７ is independently in each occurrence hydrogen or a monovalent optionally substituted SiC-bonded hydrocarbon radical; R ８ is independently in each occurrence hydrogen or a monovalent optionally substituted hydrocarbon group; u is 0, 1, 2 or 3; v is 0, 1, 2 or 3; provided that the sum u + v ≦ 3, and the sum u + v is 2 in less than 50 mol% of all units of formula (X) in the organopolysiloxane resin.

7. 7. The composition of claim 6, further comprising: (c) a polyether compound of formula (XI) R ９ -(OR １０ ) ｋ -O-R ９ (XI) [In the formula, R ９ is independently in each occurrence hydrogen or a monovalent organic group; R １０ is independently in each occurrence a divalent optionally substituted hydrocarbon group; k is an integer from 1 to 200.

8. 8. The composition of claim 7, wherein component (c) is of the following formula: R ９ -(OC ２ H ４ ) ｓ -(OC ３ H ６ ) ｔ -O-R ９ (XII) [In the formula, R ９ is independently in each occurrence hydrogen, C １ ~C ３０ Alkyl, C １ ~C ３０ Alkenyl or C(O)—R ｄ is a group of the formula R ｄ is C １ ~C ２０ is a group that is alkyl, s is an integer from 0 to 200; t is an integer from 0 to 200, the sum s+t is an integer between 10 and 200, Units (OC ２ H ４ ) and (OC ３ H ６ ) may be present in random distribution or as blocks in the polymer of formula (XII).

9. 9. The composition of claim 8, characterized by formula (XII), wherein s is 0 and t is an integer from 20 to 200.

10. The composition according to any one of claims 7 to 9, characterized in that the mass ratio of component (a) to component (c) is 1:(0.1 to 100).

11. The composition according to any one of claims 6 to 10, characterized in that the mass ratio of component (a) to component (b) is (5 to 30):

1.

12. The composition of any one of claims 6 to 11, comprising: (a) 0.1% to 90% by weight of at least one organopolysiloxane according to any one of claims 1 to 5; (d) 0.01% to 5% by weight of at least one additive; (c) 5% to 98% by weight of at least one polyether; and optionally (d) 0% to 50% by weight of at least one hydrocarbon oil.

13. A powder formulation comprising the composition of any one of claims 6 to 12 and a solid carrier.

14. 14. The powder formulation according to claim 13, characterized in that the mass ratio of the composition to the solid carrier is 2:(1-15).

15. Use of a composition according to any one of claims 6 to 12 or a powder formulation according to claim 13 or 14 as an antifoaming agent in cementitious materials or coatings.

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