Organosilicon composition

Abstract

When the composition of this disclosure, comprising a specific polyether-modified polysiloxane and a silicone hydrophobic agent, is used as an admixture for the overall hydrophobicization of cement-based materials, the water repellency is significantly improved without significantly reducing the strength, particularly the compressive strength, of the hardened cement-based material, an effect that cannot be obtained when using conventional silicone hydrophobic agents.

Description

[Technical Field]

[0001] This disclosure relates to water-repellent materials, and in particular to the use of organosilicon compositions for the overall hydrophobicization of cement-based materials. [Background technology]

[0002] Inorganic building materials such as concrete and mortar have many micropores and capillaries that allow moisture and water to easily penetrate, causing damage such as steel corrosion, deterioration due to freeze-thaw cycles, and alkali-aggregate reaction, which seriously affects their lifespan. Therefore, it is necessary to apply waterproof protection to the surface of buildings. Organosilicon compounds have been used for many years to protect buildings due to their excellent impregnation effect that repels water and dirt, their environmental friendliness, and their physiological tolerance.

[0003] Organosilicon compounds have long been used for protecting buildings due to their excellent water and dirt-repellent impregnation properties, environmental friendliness, and physiological tolerance.

[0004] Commonly used impregnating materials include alkoxysilanes having hydrophobic alkyl groups, with C8 alkyl groups being particularly widely used, especially the n-octyl group or the 1,4,4-trimethylpentyl group. Typical examples of such hydrophobic silanes are n-octyltriethoxysilane and 1,4,4-trimethylpentyltriethoxysilane.

[0005] Most commercially available compositions for hydrophobicizing building materials contain not only the silanes mentioned above, but also further organosilicon compounds, particularly methyl silicone resins, linear dimethylsiloxanes, or other linear dimethylsiloxanes modified with amino groups, etc. The corresponding mixtures can be applied as stock solutions, in organic solvents, or as aqueous emulsions.

[0006] In principle, there are two distinct application methods. Firstly, existing structures such as concrete bridges, house facades, and roof tiles are hydrophobic afterward using coating compounds. Here, the coating agent can also impregnate the substrate, at least if it is a porous building material, thus providing at least some effect to the deeper layers. In contrast to paints and varnishes that are applied solely to the surface, minor surface damage does not inevitably lead to the loss of hydrophobic protection. However, in the case of materials that are only surface-impregnated, larger damage or edges cut or broken by drills, cuts, or saws will result in a loss of protection in the affected area.

[0007] While post-processing surface hydrophobicity is generally the only practical method for impregnating existing structures, hydrophobic agents can also be added before the setting reaction in the manufacture of hydraulic binder-based components such as concrete and fibrocement. This in-situ hydrophobicity, also known as overall hydrophobicity, has the advantage of providing water-repellent protection to the entire volume of the component, not just the surface. In other words, the protective effect is not lost if the component is damaged, intentionally cut, or drilled. Furthermore, in-situ hydrophobicity eliminates the additional step of coating cured components afterward.

[0008] Chinese Patent Application Publication No. 112939512 discloses a waterproof, dry powder material that hydrophobicizes cement-based materials collectively when added before cement curing, and includes polyethertrisiloxane to improve the dispersibility of stearate. However, its hydrophobic effect is not sufficient compared to that of silane waterproofing agents.

[0009] Chinese Patent No. 1106363 discloses a method for producing a fully waterproofed concrete, wherein a hydrolyzable aqueous emulsion containing an organosilicon compound is added to a ready-mix concrete mixture prepared from water, an inorganic component, and optionally an organic component, before curing. The emulsion contains at least one alkoxysilane and optionally an organosilicon compound acting as a surfactant.

[0010] While these organosilicon compounds exhibit excellent overall hydrophobicity, they slow down the hydration reaction of concrete, thus reducing concrete strength with higher concentrations. To balance this with concrete strength, it is necessary to reduce the amount of organosilicon compounds used in cement-based materials. However, this also means that the waterproofing effect does not function at an optimal level. There is a lack of silicone-based hydrophobic agents on the market that can ensure the strength of building materials such as cement and mortar while dramatically improving waterproofing.

[0011] Due to its amphiphilic nature, polyether-modified polysiloxane is used in a wide range of applications as a surfactant, but there is no research or application of polyether-modified polysiloxane as a hydrophobic agent. Polyether-modified silane is described as a surfactant for silicone waterproof emulsions in Chinese Patent No. 1106363. Chinese Patent Application Publication No. 111620659 discloses a self-leveling cement waterproof mortar consisting of organosilicon compounds and polysiloxane. Chinese Patent Application Publication No. 114787100 discloses the use of polyether-modified polysiloxane as a crushed clinker for cement production, but does not mention its use in waterproofing. Chinese Patent No. 106116692 discloses a water-repellent emulsion containing polyether-modified polysiloxane and octylethoxysilane, in which the polyether-modified polysiloxane is used as a coemulsifier. [Overview of the Initiative]

[0012] The term "cementitious material" refers to a material that hardens, continues to cure, and increases in strength through a hydration reaction. Cement, which is known as the main hydraulic material, includes Portland cement, alumina cement, sulfoaluminate cement, fluoroaluminate cement, and ferroaluminate cement. In one embodiment of the present invention, the cement accounts for at least 70% by weight, for example at least 80% by weight, at least 90% by weight, at least 95% by weight, and even 100% by weight of the total weight of the cementitious material.

[0013] Cementitious materials include dry mixtures. The dry mixture (e.g., dry mortar) may contain one or more aggregates, polymers, and admixtures in addition to cement. Admixtures include, but are not limited to, starch ether, water repellent, anticoagulant, retarder, superplasticizer, and defoamer.

[0014] Cementitious materials include fluid mixtures. Examples of fluid mixtures include, but are not limited to, slurry materials obtained by mixing cement or a mixture of cement and other materials with water, such as paste, mortar, grout, and concrete. Paste is generally a mixture containing cement, admixtures, and water. Mortar is generally a mixture containing cement, sand, polymers, admixtures, and water. Grout is generally a mixture containing cement, sand, stones, admixtures, and water. Polymers are generally added in an amount exceeding 1% by weight based on the total weight of the cement. Admixtures are generally added in an amount less than 3% by weight based on the total weight of the cement.

[0015] "Silica fume" is a particulate material containing at least 85% by weight of amorphous silicon dioxide, obtained as a by-product during the production of ferrosilicon or industrial silicon (see GB / T 27690-2011).

[0016] "Silicone hydrophobing agent" refers to any material containing silicone-based components, mainly used to minimize water absorption and ensure the water repellent effect on the cleaned surface.

[0017] "Overall hydrophobicity" refers to the process of mixing a waterproofing agent into a cement-based material before the cement curing process, distributing the waterproofing agent within the cement-based material, and achieving overall waterproofing. This is also known as internal waterproofing or comprehensive hydrophobicity, and is distinct from immersion or coating. In this disclosure, water repellency, waterproofing, and hydrophobicity are synonymous.

[0018] "Strength reduction" refers to the decrease in the strength of the cement-based material after hardening compared to a blank that does not contain a hydrophobic agent. Strength reduction = Blank strength - Experimental sample strength. Reducing strength reduction improves strength retention.

[0019] "Reduction in water absorption rate" refers to a decrease in the water absorption rate of the cement-based material after hardening compared to a blank that does not contain a hydrophobic agent. The reduction in water absorption rate = water absorption rate of the blank - water absorption rate of the experimental sample. A greater reduction in water absorption rate indicates a higher waterproofing effect.

[0020] "Hardened cement-based material" refers to a cement-based material that has undergone a hardening reaction and become solid or nearly solid. Here, "hardening" essentially corresponds to the hydration (or setting) of cement or a cement-containing mixture. In this disclosure, hardened cement-based material does not need to be completely hardened, but rather refers to a material that is partially or completely hydrated to the extent that it can obtain a certain degree of mechanical strength. Fully hardened cement-based material refers to a material that is 100% hydrated.

[0021] The inventors discovered that a synergistic effect exists between the polyether-modified polysiloxane and the silicone hydrophobic agent of this disclosure in the overall hydrophobicization of cement-based materials, significantly improving waterproofing without significantly increasing the decrease in strength of the silicone hydrophobic agent in hardened cement materials.

[0022] A significant improvement in the water repellency of hardened cement-based materials is achieved when the composition of the present disclosure, comprising a specific polyether-modified polysiloxane and a silicone hydrophobic agent, is used as an admixture for the overall hydrophobicization of the cement-based material, and unlike conventional silicone hydrophobic agents, there is no significant decrease in strength, particularly compressive strength. [Modes for carrying out the invention]

[0023] A first aspect of this disclosure provides a composition comprising a silicone hydrophobic agent (1) and a polyether-modified polysiloxane of formula (I) (2). [ka]

[0024] In formula (I), R is independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms, more preferably a monovalent alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group. R' is independent of R or R * This represents, R * R 3 -[(C2H4O)x(C3H6O)y]R 4 And, R 3 The molecule is -(CH2)pO- (where p is selected from 2 to 10, preferably 2, 3, 4, 5, 6, more preferably 3 or 4), R 4 is hydrogen, alkyl, aralkyl, allyl, or RC(O)-, preferably hydrogen, methyl, acetyl, more preferably hydrogen and methyl. x is selected from 1 to 60, preferably 1 to 40, more preferably 1 to 20. y is selected from 0 to 60, preferably 0 to 40, more preferably 0 to 20. The value of x+y is selected from 2 to 60, preferably 3 to 40, and more preferably 10 to 30. n is selected from 0 to 20, preferably 0 to 15, more preferably 0 to 10. m is selected from 1 to 20, preferably 5 to 20, more preferably 5 to 15, when n = 0, the value of n + m is selected from 3 to 40, preferably 5 to 30, more preferably 10 to 20, provided that at least one R’ is selected from R *

[0025] The silicone hydrophobizing agent of the component (1) contains a silane of formula (II), and / or a silane hydrolyzate of formula (II), and / or a silane oligomer of formula (II). R 1 R 2 i -Si-(OR 2 ) 3-i (II)

[0026] In formula (II), R 1 is a monovalent hydrocarbon group having 1 to 16 carbon atoms bonded to SiC, optionally substituted, which may be interrupted by a hetero atom and / or a carbonyl group. Examples of R 1 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and tert-pentyl group, hexyl groups such as n-hexyl group, octyl groups such as n-octyl group and isooctyl groups such as 2,2,4-trimethylpentyl group, nonyl groups such as n-nonyl group, decyl groups such as n-decyl group, and dodecyl groups such as n-dodecyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, cycloheptyl group, norbornyl group, and methylcyclohexyl group. Examples of R 1 include alkenyl groups such as vinyl group, allyl group, n-5-hexenyl group, 4-vinylcyclohexyl group, and 3-norbornylenyl group. R 1 ​Examples include aryl groups such as phenyl, biphenylyl, naphthyl, anthryl, and phenanthryl groups; alkaryl groups such as o-, m-, and p-tolyl groups; xylyl and ethylphenyl groups; and aralkyl groups such as benzyl, α-phenylethyl, and β-phenylethyl groups. R 1 Examples include alkyl groups substituted with fluorine, chlorine, bromine, and iodine atoms, such as 3,3,3-trifluoron-propyl, 2,2,2,2',2',2'-hexafluoroisopropyl, and heptafluoroisopropyl groups, i.e., alkyl groups substituted with halogen atoms. 1 Examples include aryl halides such as o-chlorophenyl, m-chlorophenyl, and p-chlorophenyl groups. R 1 Preferably, it is a hydrocarbon group having 3 to 16 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms, such as an octyl group or a butyl group.

[0027] R 2 Each of these is independently a monovalent, optionally substituted, SiC-bonded hydrocarbon group having 1 to 8 carbon atoms, wherein the hydrocarbon group may be interrupted by a heteroatom and / or a carbonyl group. R 2 Preferably, the hydrocarbon group having 1 to 8 carbon atoms is an alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and tert-pentyl group, a hexyl group such as an n-hexyl group, an octyl group such as an n-octyl group, and an octyl group such as an isooctyl group such as a 2,2,4-trimethylpentyl group, more preferably a methyl group, ethyl group, n-propyl group, and isopropyl group.

[0028] Ure 2Examples of such groups include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups, pentyloxy groups such as n-pentyloxy, or hexyloxy groups such as n-hexyloxy. Ethoxy and methoxy groups are particularly preferred. Alkoxy groups may be substituted with halogen atoms, but this is not preferred.

[0029] i is selected from 0 to 3, preferably 0 or 1, more preferably 0.

[0030] The above silane hydrolysates usually react with water or steam to form the OR of the silane of formula (II). 3 It is formed when a portion of the group is eliminated and an OH group bonded to silicon is formed.

[0031] The above silane oligomers are usually produced by the elimination of some of the OH groups attached to the silicon in the hydrolysis product of silane of formula (II), and the OH groups and OR 3 It may contain a base.

[0032] The silicone hydrophobic agent of component (1) above may be any of the commercially available general silicone waterproofing agents that contain silane, silane hydrolysate, silane oligomer, polysiloxane, or a mixture thereof.

[0033] In one embodiment, the silicone hydrophobic agent of component (1) is butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, octylmethyldimethoxysilane, octylmethyldiethoxysilane, isooctylmethyldimethoxysilane, isooctylmethyldi Ethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, propyltriisopropoxysilane, propyltriisobutoxysilane, hexyltriisopropoxysilane, hexyltriisopropoxysilane, n-octyltriisopropoxysilane, n-octyltriisopropoxysilane, n-octylmethyldiisopropoxysilane, n-octyltriisoprop Poxysilane, n-octyltriisopropoxysilane, n-octylmethyldiisopropoxysilane, n-octylmethyldiisopropoxysilane, n-octyltriisopropoxysilane, n-octyltriisobutoxysilane, n-octyltriisobutoxysilane, n-octylmethyldiisobutoxysilane, n-octylmethyldiisobutoxysilane, n-decyltriisopropoxysilane, n-decylmethyldiisopropoxysilane, n- Alkoxysilanes comprising decyltriisobutoxysilane, n-decylmethyldiisobutoxysilane, dodecyltriisopropoxysilane, dodecylmethyldiisopropoxysilane, dodecyltriisobutoxysilane, dodecylmethyldiisobutoxysilane, cetyltriisopropoxysilane, cetylmethyldiisopropoxysilane, cetyltriisobutoxysilane, cetylmethyldiisobutoxysilane, or alkoxysilanes selected from the group consisting of these. In this embodiment, the alkoxysilane may also comprise partial hydrolysates or oligomers of the silanes described above.

[0034] The alkoxysilane is preferably selected from the group consisting of butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, octylmethyldimethoxysilane, octylmethyldiethoxysilane, isooctylmethyldimethoxysilane, isooctylmethyldiethoxysilane, n-octyltriisopropoxysilane, isooctyltriisopropoxysilane, n-octylmethyldiisopropoxysilane, isooctylmethyldiisopropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, and partial hydrolysates or oligomers thereof.

[0035] The alkoxysilane is more preferably selected from the group consisting of butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, n-octyltriisopropoxysilane, isooctyltriisopropoxysilane, and partial hydrolysates or oligomers thereof. Even more preferably, it includes a silane oligomer selected from the group consisting of butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isooctyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, and oligomers of isooctyltriethoxysilane.

[0036] The silane oligomer described above preferably has a viscosity of 3 to 1000 mm at 25°C. 2 Viscosity of 3-500 mm / second, more preferably at 25°C. 2 Viscosity of 3 to 300 mm / second, more preferably at 25°C. 2 It is per second.

[0037] A composition comprising the polyether-modified polysiloxane of formula (I) of component (2) described above. [ka]

[0038] In formula (I), R is independently a monovalent hydrocarbon group having 1 to 30 carbon atoms. Examples of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and tert-pentyl group, hexyl group such as n-hexyl group, n-octyl group, octyl group such as isooctyl group such as 2,2,4-trimethylpentyl group, nonyl group such as n-nonyl group, decyl group such as n-decyl group, dodecyl group such as n-dodecyl group, cyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, cycloheptyl group, norbornyl group, and cycloalkyl group such as methylcyclohexyl group. Examples include aryl groups such as phenyl, biphenylyl, naphthyl, anthryl, and phenanthryl groups; alkaryl groups such as o-, m-, and p-tolyl groups, xylyl, and ethylphenyl groups; and aralkyl groups such as benzyl, α-phenylethyl, and β-phenylethyl groups. Examples of R include alkyl groups substituted with fluorine, chlorine, bromine, and iodine atoms, such as 3,3,3-trifluoron-propyl, 2,2,2,2',2'-hexafluoroisopropyl, and heptafluoroisopropyl groups, i.e., alkyl groups substituted with halogen atoms. 1 Examples include aryl halides such as o-chlorophenyl, m-chlorophenyl, and p-chlorophenyl groups. R is preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms, and more preferably a monovalent alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group.

[0039] R' is independent of R or R * This represents, R* R 3 -[(C2H4O)x(C3H6O)y]R 4 And, R 3 The molecule is -(CH2)pO- (where p is selected from 2 to 10, preferably 2, 3, 4, 5, 6, more preferably 3 or 4), R 4 is hydrogen, alkyl, aralkyl, allyl, or RC(O)-. R 4 Examples include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, hexyl group, decyl group, dodecyl group, 2-phenylethyl group, phenyl group, acetyl group, preferably hydrogen, methyl group, acetyl group, and more preferably hydrogen and methyl group.

[0040] x is selected from 1 to 60, preferably 1 to 40, more preferably 1 to 20, for example, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17.

[0041] y is selected from 0 to 60, preferably 0 to 40, more preferably 0 to 20, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. y is selected from 0 to 10, preferably 0 to 5, and more preferably 0.

[0042] The value of x+y is selected from 2 to 60, preferably 3 to 40, more preferably 10 to 30, for example, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26.

[0043] The value of y / x is selected from 0 to 3, preferably 0 to 1, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and more preferably 0.

[0044] n is selected from 0 to 20, preferably 0 to 15, more preferably 0 to 10, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0045] m is selected from 1 to 20, preferably 5 to 20, more preferably 5 to 15, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15.

[0046] The value of n+m is such that if n=0, at least one R' is R * Subject to being selected from the following, the number is 3 to 40, preferably 5 to 30, more preferably 10 to 20, for example, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0047] Preferably, the polyether-modified polysiloxane of component (2) described above is selected from polyether-modified polysiloxanes of formula (III) or (IV). [ka] [ka]

[0048] In the formula, R, R * n and m are as defined in equation (I), and n is greater than 0.

[0049] The polyether-modified polysiloxane of formula (I) of component (2) described above has a viscosity of 50-700 mm at 25°C. 2 Viscosity of 100-500 mm / second, more preferably at 25°C. 2 Viscosity of 150-400 mm / second, more preferably at 25°C. 2 It is per second.

[0050] In this disclosure, the composition comprising component (1) a silicone hydrophobic agent and component (2) a polyether-modified polysiloxane of formula (I) should be understood to have component (1) a silicone hydrophobic agent and component (2) a polyether-modified polysiloxane of formula (I) as the main components of the composition. The composition may contain components for dissolving or stably dispersing them, or components as dispersion media for them, but these components are not considered main components. Here, the main components can also be understood to mean that component (1) a silicone hydrophobic agent and component (2) a polyether-modified polysiloxane of formula (I) account for at least 20% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, for example 55%, 60%, 65%, 70%, 75%, or 80% of the total weight of the composition.

[0051] The weight ratio of component (2) to component (1) is 0.01 to 80, for example, 0.02 to 80, 0.02 to 70, 0.02 to 60, 0.02 to 50, 0.02 to 40, 0.02 to 30, preferably 0.02 to 20, for example, 0.03 to 10, 0.03 to 5, 0.03 to 3, 0.03 to 2, more preferably 0.03 to 1.5, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4.

[0052] The composition comprises 20-80% by weight of component (1) and 20-80% by weight of component (2), preferably 30-70% by weight of component (1) and 30-70% by weight of component (2), and more preferably 40-60% by weight of component (1) and 40-60% by weight of component (2).

[0053] A second aspect of this disclosure provides a waterproof emulsion comprising the above-described composition, water, and an emulsifier.

[0054] The composition may be a self-dispersing system containing the above-mentioned components (1) and (2), particularly an emulsion containing the same components. Here, "self-dispersing system" means that components (1) and (2) are dispersed or suspended in an emulsifier, water, an organic solvent such as ethanol or an alkanol such as glycerin, or a non-solvent liquid carrier. The term "emulsion" includes simple direct emulsions (oil-in-water), reverse emulsions (water-in-oil), or multiple emulsions (W / O / W type, O / W / O type).

[0055] In one embodiment of the present disclosure, components (1) and (2) are used as a mixture in the form of an emulsion for the overall hydrophobicization of a cement-based material. The emulsion comprises components (1) and (2), an emulsifier (3), and water (4). The content of components (1) and (2) in the emulsion is not particularly limited, but is preferably 20 to 60% by weight, more preferably 30 to 55% by weight, and more preferably 35 to 50% by weight.

[0056] The emulsifier (3) may be any emulsifier conventionally used to produce silane dispersions, such as anionic, cationic, nonionic, and amphoteric surfactants or mixtures thereof, preferably nonionic emulsifiers. Examples of suitable nonionic emulsifiers include fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, ethylene oxide-propylene oxide copolymers, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, pentaerythritol fatty acid esters, glycerol fatty acid esters, and mixtures thereof. Preferably, fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, and mixtures thereof, having 10 to 20 carbon atoms. The nonionic emulsifier preferably includes at least one nonionic emulsifier with an HLB value of 12 or higher.

[0057] Since emulsifiers may reduce the strength of hardened cement-based materials, it is preferable to use them in the minimum amount that can stabilize the emulsion, for example, 0.01 to 5% by weight based on the total weight of the emulsion, and more preferably 0.1 to 3% by weight, more preferably 0.1 to 2% by weight, and more preferably 0.1 to 1% by weight.

[0058] The water content in the emulsion is not particularly limited, but it is suitable to be 35-75% by weight, preferably 40-65% by weight, and more preferably 45-60% by weight.

[0059] The emulsion may further contain appropriate amounts of other optional components such as pH adjusters, antifreezes, and preservatives, as long as they do not hinder the implementation of the present invention.

[0060] The emulsion preferably does not contain water-immiscible solvents, nanofillers, other hydrophobic components, and other silicon compounds. "Water-immiscible solvents" refer to solvents that are soluble in water at 20°C and a pressure of 101 kPa at a concentration of 1 g / L or less, such as benzene, toluene, xylene, hexane, and cyclohexane. Examples of nanofillers include, but are not limited to, nanoaluminum oxide, nanoaluminum hydroxide, nanocalcium oxide, and nanozinc oxide. Examples of other hydrophobic components include, but are not limited to, stearic acid, calcium stearate, zinc stearate, aluminum stearate, dodecanol, cetyl alcohol, stearyl alcohol, butyltrimethoxysilane, butylethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, n-decyltrimethoxysilane, and n-decyltriethoxysilane. Other silicon compounds refer to compounds containing silicon atoms other than alkoxysilanes or alkoxysiloxanes (a), polysiloxanes (d), and aminosilanes (e), such as bis(γ-trimethoxysilylpropyl)amine, bis(γ-triethoxysilylpropyl)amine, and polysiloxanes that do not contain aminoalkyl groups.

[0061] An emulsion containing the above-described composition can be prepared by methods known to those skilled in the art.

[0062] A third aspect of this disclosure provides a waterproof powder comprising the above composition and a solid carrier.

[0063] In this disclosure, components (1) and (2) may be adsorbed on a solid carrier as a powdered mixture for the overall hydrophobicization of the cement-based material. Since it is difficult to directly adsorb the silicone hydrophobic agent of component (1) and the polyether-modified polysiloxane of formula (I) of component (2) onto the cement-containing cement material, it is preferable to first adsorb these components onto a solid carrier (6) and then mix them into the cement-based material. Suitable solid carriers (6) are generally porous materials and include, but are not limited to, silica fume, silica, alumina, activated carbon, talc, zeolite powder, calcium carbonate, calcium silicate, diatomaceous earth, and clay.

[0064] The above powder comprises component (1), component (2), and solid carrier (6). The content of component (1) and component (2) in the emulsion is not particularly limited, but 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 20 to 30% by weight is suitable.

[0065] The content of the solid carrier (6) in the powder is not particularly limited, but 50 to 90% by weight, preferably 60 to 85% by weight, and more preferably 70 to 80% by weight is suitable.

[0066] The above powder contains water in an amount of less than 1% by weight of the total weight of the powder, preferably less than 0.5% by weight or less than 0.2% by weight, and more preferably less than 0.1% by weight or less than 0.01% by weight.

[0067] A fourth aspect of the present disclosure provides the use of the above composition, emulsion, or powder for the overall hydrophobicization of cement-based materials, particularly to reduce strength reduction.

[0068] In this disclosure, a composition comprising the above-mentioned silicone hydrophobic agent component (1) and the above-mentioned polyether-modified polysiloxane of formula (I) as component (2) is mixed into the cement-based material for overall hydrophobicity in an amount of active ingredients of 0.1 to 3%, preferably 0.1 to 2%, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, and particularly 0.1 to 1%, relative to the total weight of the cement, in the form of active ingredients. If the amount is too low, the water repellency of the cement-based material is undesirable. If the amount is too high, there may be no further improvement in water repellency, and it may result in increased costs and a decrease in the strength of the hardened cement-based material. In this disclosure, the active ingredients comprise component (1) a silicone hydrophobic agent and component (2) a polyether-modified polysiloxane of formula (I). Preferably, component (1) the silicone hydrophobic agent and component (2) the polyether-modified polysiloxane of formula (I) constitute at least 95% by weight, more preferably at least 98% by weight, and more preferably at least 99% by weight of the total weight of the active ingredients. When component (1) the silicone hydrophobic agent and component (2) the polyether-modified polysiloxane of formula (I) are used as an emulsion mixture, the dosage is calculated as a percentage of the weight of component (1) the silicone hydrophobic agent and component (2) the polyether-modified polysiloxane of formula (I) relative to the total weight of the cement.

[0069] The method for overall hydrophobicizing cement-based materials is not particularly limited, as long as the above composition is well mixed with the cement-based material as a water-repellent mixture before setting or hardening. The water-repellent mixture may be added during the preparation or post-treatment stage of the cement-based material, or during the post-treatment stage of the raw materials for preparing the cement-based material. Specifically, the water-repellent mixture may be added during the post-treatment stage of the cement-based material, such as by adding it to treat the prepared cement. Specifically, the water-repellent mixture may be added during the preparation stage of a dry mixture or fluid mixture containing cement, such as by adding it during the preparation stage of paste, mortar, grout, or concrete. Furthermore, the water-repellent mixture may be incorporated during the post-treatment stage of raw materials for preparing cement-based materials, such as aggregates including sand, stone, polymers, and admixtures.

[0070] In one embodiment, a composition containing component (1) a silicone hydrophobic agent and component (2) a polyether-modified polysiloxane of formula (I) is added as a water-repellent mixture during the preparation of a fluid mixture, after which the well-mixed fluid mixture undergoes a setting or curing reaction to become a solid or nearly solid. When the above composition is used as an emulsion mixture, the emulsion is mixed in water, and the resulting wet mixture is added to a dry mixture containing cement-based materials and mixed thoroughly. When the above composition is used as a powder mixture, the powder is mixed into the cement-based materials and other dry materials, and then water is added and mixed thoroughly.

[0071] A fifth aspect of this disclosure provides a cement-based material comprising the above composition, the waterproof emulsion, or the waterproof powder in an amount of active ingredients of 0.1 to 3% by weight, preferably 0.1 to 2% by weight, relative to the total weight of cement, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, preferably 0.1 to 1%, wherein the active ingredients comprise the silicone hydrophobic agent of component (1) and the polyether-modified polysiloxane of formula (I) of component (2), and preferably the active ingredients comprise only the silicone hydrophobic agent of component (1) and the polyether-modified polysiloxane of formula (I) of component (2).

[0072] The cement-based materials of this disclosure have high water repellency, with a 24-hour water absorption rate reduction rate higher than 72% compared to a blank without hydrophobic admixtures, for example, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, preferably higher than 75%, and more preferably higher than 80% (tested in accordance with JGT / T70-2009).

[0073] The cement-based materials of this disclosure have a small strength degradation, with a 28-day compressive strength retention rate higher than 80% relative to a blank without hydrophobic mixtures, for example, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, preferably higher than 83%, more preferably higher than 85% (tested in accordance with JGT / T70-2009). [Examples]

[0074] Silicone hydrophobic agent 1: Octyltriethoxysilane oligomer (99% purity), viscosity at 25°C 130-300 mmHg 2 / second (tested in accordance with DIN 51562-1) Silicone hydrophobic agent 2: Octyltriethoxysilane (99% purity) Polyether-modified polysiloxane 1: As shown in formula (a), it belongs to formula (I) above, with n=4, m=10, and a viscosity of 327 mm at 25°C. 2 / second (tested in accordance with DIN 51562-1) (99% purity) [ka] Polyether-modified polysiloxane 2: As shown in formula (b), it belongs to formula (I) above, with n=0, m=15, and a viscosity of 200 mm at 25°C. 2 / second (tested in accordance with DIN 51562-1) (99% purity) [ka] Polyether-modified polysiloxane 3: A mixture as shown in formula (c), where the molar ratio of n=4.5, m=70 to n=8, m=42 is 2:1, with a viscosity of 800 mmHg at 25°C. 2 / second (tested in accordance with DIN 51562-1) (99% purity) [ka] Polyether-modified polysiloxane 4: Belongs to the above formula (I), but n=1, m=0, viscosity at 25°C is 10-25 mm². 2 / second (tested in accordance with DIN 51562-1) (99% purity) [ka] The above substance was supplied by Wacker Chemie AG. All viscosity data in this disclosure were measured in accordance with DIN 51562-1. Oleic acid: Commercially available, 99% purity. Cement: Standard cement for testing concrete mixtures, GB8076-2008 Appendix A standard specification Sand: ISO standard sand, GB / T1761-1999 implementation standard Composition: Prepared by mixing the above-mentioned silicone hydrophobic agent and / or polyether-modified polysiloxane or oleic acid, and comprising a self-assembled structure formed by the silicone hydrophobic agent and the polyether-modified polysiloxane. The structure is formed in the form of an oil mixture, emulsion, or powder after mixing the above-mentioned substances, but is not limited to these forms.

[0075] The method for preparing the waterproof emulsion is as follows: Add 0.5-3g of emulsifier and 0.5-5g of water to the container, switch on the homogenizer (T25 type, with 25F stator and rotator), start operation at a speed of 1500rpm, add 0-50g of silicone hydrophobic agent to the container in several batches at 2000rpm, homogenize at 2000rpm for 3 minutes after each addition, add 0-50g of polyether-modified polysiloxane to the container in several batches at 2000rpm, homogenize at 2000rpm for 3 minutes after each addition, add 47.5g of water to the container in several batches at 2000rpm, homogenize at 2000rpm for 3 minutes after each addition until the emulsion is homogenized and stable.

[0076] The method for preparing the waterproof powder is as follows: Add 75g of silica fume to the container, turn on the mixer, and add 0-25g of silicone hydrophobic agent to the container in several batches at a speed of 300rpm, mixing at 300rpm for 3 minutes after each addition. Add 0-25g of polyether-modified polysiloxane to the container in several batches, mixing at 300rpm for 3 minutes after each addition, and then stir thoroughly to obtain a freely flowing powdered water repellent.

[0077] The method for preparing mortar is as follows: Referring to the formulations in Tables 1-3, place the composition, water, and cement in a bowl, secure the bowl to the mixer, and begin mixing at low speed (140 rpm) for 30 seconds. Then, gradually add the sand over 30 seconds, switch the mixer's mixing speed to high speed (285 rpm), and continue mixing for another 30 seconds. Then stop the mixer for 90 seconds. During the first 30 seconds, use a rubber scraper to remove any mortar adhering to the walls and bottom of the bowl and move it to the center of the bowl, then continue mixing at high speed (285 rpm) for 60 seconds (according to ISO EN196-1). After preparing the mortar, fill the mold with the mortar to obtain a cube measuring 70.7 × 70.7 × 70.7 mm.

[0078] The mortar inside the formwork is maintained at a relative humidity (RH) of 90% and a temperature of (20±2)°C for 24 hours. After that, the sample is removed from the formwork and returned to a room with a relative humidity (RH) of 90% and a temperature of (20±2)°C, and left for another 27 days.

[0079] After 28 days, the water absorption rate and compressive strength were measured (in accordance with JGJ / T 70-2009), and Tables 1-3 show the 24-hour water absorption rate (%) and 28-day compressive strength (MPa).

[0080] The 24-hour water absorption rate (%) refers to the water absorption rate of the mortar after immersion in water for 24 hours. (In accordance with JGJ / T 70-2009)

[0081] The 28-day compressive strength refers to the compressive strength of the mortar at 28 days of age. (In accordance with JGJ / T 70-2009)

[0082] [Table 1]

[0083] The percentage decrease in water absorption rate relative to the blank (%) = (decrease in 24-hour water absorption rate) / 24-hour water absorption rate of the blank = (24-hour water absorption rate of the blank - 24-hour water absorption rate of the example) / 24-hour water absorption rate of the blank Retention rate of compressive strength relative to the blank (%) = (decrease in 28-day compressive strength) / 28-day compressive strength of the blank = (28-day compressive strength of the blank - 28-day compressive strength of the example) / 28-day compressive strength of the blank

[0084] The results for the blank and Comparative Examples 1-2 in Table 1 show that when only the conventional silicone hydrophobic agent 1 was used as the composition, the 24-hour water absorption rate was significantly reduced. However, when the amount of silicone hydrophobic agent 1 was further increased, the 24-hour water absorption rate decreased even more, but this was accompanied by a significant reduction in compressive strength.

[0085] In Comparative Examples 5 and 6, compositions containing only polyether-modified polysiloxane reduced the 24-hour water absorption rate to some extent, but fell far short of the waterproofing required for practical use.

[0086] The compositions of Examples 3-4, which contain silicone hydrophobic agent 1 and polyether-modified polysiloxanes 1-2, can significantly reduce the 24-hour water absorption rate compared to using only the conventional silicone hydrophobic agent 1, while maintaining strength without a significant decrease. These compositions are useful for the overall hydrophobicization of cement-based materials, achieving a 24-hour water absorption rate reduction of more than 72% and a compression strength retention rate of 80% relative to the blank.

[0087] [Table 2]

[0088] The percentage decrease in water absorption rate relative to Comparative Example 1 (%) = (decrease in 24-hour water absorption rate) / 24-hour water absorption rate of Comparative Example 1 = (24-hour water absorption rate of Comparative Example - 24-hour water absorption rate of the Example in Question) / 24-hour water absorption rate of Comparative Example 1 Retention rate of compressive strength relative to Comparative Example 1 (%) = (decrease in 28-day compressive strength) / 28-day compressive strength of Comparative Example 1 = (28-day compressive strength of Comparative Example 1 - 28-day compressive strength of the example in question) / 28-day compressive strength of Comparative Example 1

[0089] Comparative Examples 7-8 in Table 2 show that when polysiloxanes 3-4, which are not within the scope of this application, are added, there is no significant decrease in the water absorption rate due to the silicone hydrophobic agent 1 in the mortar compared to Comparative Example 1, where only the conventional silicone hydrophobic agent 1 was used as a composition in the mortar, but there is no significant reduction in compressive strength.

[0090] In Comparative Example 9, when oleic acid was added to silicone hydrophobic agent 1, the water absorption rate decreased more significantly compared to Comparative Example 1, but the decrease in compressive strength was also more severe, with the retention rate of 28-day compressive strength being only 68%.

[0091] The mortars of Examples 3 and 4 have a composition containing a silicone hydrophobic agent 1 and polyether-modified polysiloxanes 1 and 2. Compared to Comparative Example 1, the reduction in 24-hour water absorption rate is higher than 10%, and the retention rate of compressive strength compared to Comparative Example 1 is 90%.

[0092] [Table 3]

[0093] Examples 10-15 in Table 3 show that the polyether-modified polysiloxane of this application can be used with various silicone hydrophobic agents to hydrophobize the mortar as a whole, significantly improving water repellency.

Claims

1. Component (1): Silicone hydrophobic agent, and Component (2): Polyether-modified polysiloxane of the following formula (I), 【Chemistry 1】 (In the formula, Each R is independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms, and more preferably a monovalent alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group. R' is independently R or R ＊ This represents, R ＊ R ３ - [(C ２ H ４ O) x (C ３ H ６ O)y]R ４ And, R ３ is -(CH ２ )pO-(where p is selected from 2 to 10, preferably 2, 3, 4, 5, 6, more preferably 3 or 4). R ４ This is hydrogen, alkyl, aralkyl, allyl, or R-C(O)-, preferably hydrogen, methyl, acetyl, more preferably hydrogen and methyl. x is selected from 1 to 60, preferably 1 to 40, more preferably 1 to 20. y is selected from 0 to 60, preferably 0 to 40, more preferably 0 to 20. The value of x + y is selected from 2 to 60, preferably 3 to 40, and more preferably 10 to 30. n is selected from 0 to 20, preferably 0 to 15, more preferably 0 to 10. m is selected from 1 to 20, preferably 5 to 20, more preferably 5 to 15. The value of n+m is such that if n=0, at least one R' is R ＊ (Selected from 3 to 40, preferably 5 to 30, more preferably 10 to 20, provided that it is selected from the above.) A composition containing the following:

2. The composition according to claim 1, wherein component (2) is selected from polyether-modified polysiloxanes of formula (III) or (IV). 【Chemistry 2】 【Transformation 3】 (In the formula, R, R ＊ n and m are as defined in equation (I), where n is greater than 0.

3. The composition according to claim 1 or 2, wherein the value of y / x is selected from 0 to 3, preferably 0 to 1, more preferably 0, and / or y is selected from 0 to 10, preferably 0 to 5, more preferably 0.

4. The composition according to any one of claims 1 to 3, wherein the silicone hydrophobic agent of component (1) comprises a silane of formula (II) and / or a hydrolysate of a silane of formula (II) and / or an oligomer of a silane of formula (II). R １ R ２ ｉ -Si-(OR ２ ) ３－ｉ (II) (In the formula, R １ This is a monovalent, optionally substituted, SiC-bonded hydrocarbon group having 1 to 16 carbon atoms, the hydrocarbon group may be interrupted by a heteroatom and / or a carbonyl group, preferably a hydrocarbon group having 3 to 16 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms such as an octyl group or a butyl group. R ２ Each is independently a monovalent, optionally substituted, SiC-bonded hydrocarbon group having 1 to 8 carbon atoms, the hydrocarbon group may be interrupted by a heteroatom and / or a carbonyl group, preferably an alkyl group having 1 to 8 carbon atoms, more preferably R ２ This is a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. i is selected from 0 to 3, preferably 0 or 1, more preferably 0.

5. The silicone hydrophobic agent of component (1) comprises a silane oligomer, and the silane oligomer is Preferably, the oligomer of a silane selected from the group consisting of butylmethoxysilane, butylethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltriethoxysilane, and isooctyltriethoxysilane. and / or, Viscosity at 25°C: 3 to 1000 mm ２ Viscosity of 3 to 500 mm / second, more preferably at 25°C. ２ Viscosity of 3 to 300 mm² at 25°C, more preferably at 25°C. ２ The composition according to any one of claims 1 to 4, wherein the silane oligomer is in the range of / second.

6. The composition comprises 20 to 80% by weight of component (1) and 20 to 80% by weight of component (2), preferably 30 to 70% by weight of component (1) and 30 to 70% by weight of component (2), and more preferably 40 to 60% by weight of component (1) and 40 to 60% by weight of component (2). And / or, the weight ratio of component (2) to component (1) is 0.01 to 80, preferably 0.02 to 20, more preferably 0.03 to 1.

5. and / or the composition according to any one of claims 1 to 5, wherein component (1) is a silicone hydrophobic agent and component (2) is a polyether-modified polysiloxane of formula (I) that accounts for at least 20% by weight, preferably at least 40% by weight, more preferably at least 50% by weight of the total weight of the composition, for example, 55%, 60%, 65%, 70%, 75%, and 80% based on 100% weight of the composition.

7. The above component (2) has a viscosity of 50 to 700 mm at 25°C. ２ viscosity of 100 to 500 mm² at 25°C, more preferably at 25°C. ２ viscosity of 150 to 400 mm² at 25°C, more preferably at 25°C. ２ The composition according to any one of claims 1 to 6, wherein the value is per second.

8. 20 to 60% by weight of the composition according to any one of claims 1 to 7, 35 to 75% by weight of water, and 0.1 to 5% by weight of an emulsifier, Preferably 30 to 55% by weight of the composition according to any one of claims 1 to 7, 40 to 65% by weight of water, and 0.1 to 5% by weight of an emulsifier. More preferably, 35 to 50% by weight of the composition according to any one of claims 1 to 7, 40 to 65% by weight of water, and 0.1 to 5% by weight of an emulsifier. A waterproof composition comprising the following.

9. A composition according to any one of claims 1 to 7 in an amount of 10 to 50% by weight, and a solid carrier in an amount of 50 to 90% by weight. Preferably, 15 to 40% by weight of the composition according to any one of claims 1 to 7, and 60 to 85% by weight of a solid carrier. More preferably, 20 to 30% by weight of the composition according to any one of claims 1 to 7, and 70 to 80% by weight of a solid carrier. A waterproof composition comprising the following.

10. Use of the composition according to any one of claims 1 to 9 for the overall hydrophobicization of cement-based materials.

11. Use of the composition according to any one of claims 1 to 9 for overall hydrophobization of cement-based materials to reduce strength reduction.

12. A waterproof cement-based material comprising the composition according to any one of claims 1 to 9 in an amount of the active ingredient such as 0.1 to 3% by weight, preferably 0.1 to 2% by weight, preferably 0.1 to 1%, relative to the total mass of the cement, wherein the active ingredient comprises the silicone hydrophobic agent of component (1) and the polyether-modified polysiloxane of formula (I) of component (2).

13. The waterproof cement-based material according to claim 12, wherein the silicone hydrophobic agent of component (1) and the polyether-modified polysiloxane of formula (I) of component (2) constitute at least 95% by weight, preferably at least 98% by weight, and more preferably at least 99% by weight of the total mass of the active ingredient.

14. The waterproof cement-based material according to claim 12 or 13, wherein, when tested in accordance with JGT / T70-2009, the 24-hour reduction rate of water absorption is higher than 72% and the retention rate of 28-day compressive strength is higher than 80%, relative to a blank without a water-repellent additive.

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