Silicone compositions and their uses as additives for reducing water absorption and improving compressive strength in the cement industry

Abstract

The additive composition for improving compressive strength and reducing water absorption comprises an alkylsilane, or a hydrolysate thereof, or a mixture thereof, including a silicone resin comprising a unit of formula (Ia), together with an additive composition and an antifoam composition, which is used before or during the grinding process in a cement plant to not only reduce energy consumption during grinding, but also eliminate further addition of hydrophobic additive materials to provide hydrophobicity with improved compressive strength of the constructed structure. Such hydrophobicity with improved compressive strength of the constructed structure is achieved even when the composition is used after the grinding process.

Description

Detailed Description of the Invention

[0001] [Field of the Invention] The present invention relates to an additive composition comprising an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, with a silicone resin, which provides improved compressive strength and reduced water absorption. The additive may be added to a cement composition to improve its compressive strength and hydrophobicity.

[0002] [Background of the invention] The total cement produced annually worldwide is around 4 billion metric tons (World Production and Capacity Table by US Geological Survey at the link https: / / pubs.usgs.gov / periodicals / mcs2020 / mcs2020-cement.pdf). There are nearly 3300 cement producing facilities or plants across the world. India alone has more than 560 cement plants producing around 545 million tons annually making India the second largest producer in the world after China. In India, the cement sector is classified based on the products and processes related to seven sub-sectors - Portland Pozzolana Cement (PPC), Portland Composite Cement (PCC), Ordinary Portland Cement (OPC), Portland Slag Cement (PPC), Wet Process Plants, White Plants, Grinding Plants and Clinkerisation Plants. In the construction industry, a major problem that needs to be addressed for all construction materials is to adequately protect the structure from moisture, as moisture leads to a shortened life span of all construction materials. There are various approaches that are chosen to keep construction materials away from moisture. Coating the desired structure, such as painting, or weather coat, to prevent moisture from coming into direct contact with its outer surface after the construction is completed. Another approach to prevent moisture is by premixing the material with the basic elements of construction, such as cement, small aggregates and / or large aggregates, which form a water repellent effect on the surface after the formation of the desired structure. Another approach is to modify the inherent properties of the raw materials of the construction material, so that no separate additives need to be used to obtain the maximum desired protection from moisture without compromising any other properties of the material. One of the major problems of using or adding hydrophobic additive materials to cement is that the compressive strength of mortar, plaster or concrete prepared with cement mixed with such additives is significantly reduced.Therefore, there is a need to obtain a desired cement additive composition that maintains the desired compressive strength and provides hydrophobicity in mortar, plaster or concrete.

[0003] In the cement industry, another important problem faced by manufacturing units is energy consumption. In India, the reported total energy consumption of 85 designated consumers is about 15.01 MTOE (Million Tons of Oil Equivalent by Bureau of Energy Efficiency, https: / / beeindia.gov.in / node / 166). The total electrical energy consumption for cement production is about 100 kWh / tonne of cement, with roughly two-thirds being used for particle size reduction. About 65% of the total electrical energy used in a cement plant is utilized for grinding of coal, raw materials, and clinker. In the cement industry, hydraulic cement, an inorganic material, has the ability to react with water under ambient conditions to form a hardened, water-resistant product, which is a very important and widely used cement. The production of such hydraulic cement requires a process of calcining a mixture of clayey and calcareous materials to produce sintered clinker. Portland cement is the most widely used hydraulic cement, which is produced by sintering calcareous and argillaceous materials to form a clinker, which is then ground with gypsum (3-3.5%) to obtain the desired setting characteristics. Small amounts of other materials are also added during the grinding of the clinker materials. One of the most common additions of such materials is grinding aids, which improve the efficiency of the grinding operation, thereby reducing the power required for such grinding processes, reducing capital investments or improving throughput.

[0004] Numerous grinding aid compositions are known in the prior art, which are added back to the cement as separate additives, which would generate additional costs and therefore be less competitive.

[0005] For example, materials such as glycols, alkanolamines, aromatic acetates, etc. have been shown to reduce the amount of energy required and thereby improve the efficiency of clinker grinding, but there is no such composition that can be added as a grinding aid and that not only maintains the desired mechanical properties, such as the compressive strength of the concrete, plaster, or mortar that is subsequently formed, but also imparts water repellency properties to the material that is constructed.

[0006] In US3333776A entitled "Hydrophobic silica as a grinding aid", paragraph 1, lines 48-53, it is stated that silica powder rendered hydrophobic by treatment with a hydrophobic organosilicon causes a significant improvement in the grinding process (faster and finer grinding) than grinding without silica or in the presence of untreated hydrophilic silica. The composition is referred to as hydrophobic, but this does not have the desired effect on the hydrophobicity of the cement or the final structure.

[0007] WO2000039047A1 is entitled Silicon containing grinding aides for clinker. In this reference, grinding aids are added to cement clinker to reduce the energy consumed during grinding and / or to improve the hydrophobicity of the cement product. The grinding aids can be cyclic siloxanes, functionalized polydiorganosiloxanes, or mixtures thereof. It is also mentioned that in addition to monomeric alkoxysilanes, oligomeric products from partial hydrolysis and condensation of alkoxysilanes can also be used in the compositions of this invention. The compositions refer to silicone compositions, but do not provide the desired combination of hydrophobicity and compressive strength for the cement or final structure.

[0008] WO2000039046A1 entitled Silicon containing grinding aids for slag discloses grinding aids for slag and slag / clinker raw material mixtures. The grinding aids are any silicone containing fluids or mixtures thereof. In addition to monomeric alkoxysilanes, it is stated that oligomeric products of partial hydrolysis and condensation of alkoxysilanes can also be used in the compositions of this invention. Although the compositions refer to silicone compositions, they do not provide the desired combination of hydrophobicity and compressive strength for the cement or final structure.

[0009] In GB1112018A, entitled "process for the production of finely divided materials," the production of finely divided materials is achieved by mixing (a) 10 parts by weight of a particulate, non-malleable, brittle solid, (b) 0.1 to 2 parts by weight of silica powder having a surface area of ​​at least 20 square meters per gram, the surface of which is reacted with organo- and haloorgano-silazanes, organo- and haloorgano-siloxanes, and hydroxyl-reactive organo- and haloorgano-silanes. (c) milling a composition consisting of 5 to 20 parts by weight of a volatile, inert liquid that is not a solvent for (a) in a ball mill, wherein the mixture of (a), (b) and (c) is a free-flowing slurry throughout the milling process. The composition refers to a silicone composition, but does not impart hydrophobicity to the cement or the final structure.

[0010] In US6635109 entitled "process of making cements with silicon containing grounding aid", in the abstract, a grinding aid is added to the cement clinker before it is ground in (iii). The grinding aid is uncalcined direct process residual gel, which is a hydrolysis product of alkylhalodisilane produced as a by-product in the manufacture of alkylhalosilanes. Although the composition refers to a silicone composition, it does not provide the desired hydrophobicity to the cement or the final structure. Furthermore, the presence of halogen groups increases the corrosion reaction with the iron bars present in the concrete.

[0011] In US7160384B2 a method is disclosed for introducing into a grinding mill, cement clinker is ground to provide cement powder, a diamine such as tetrahydroxylethylethylene diamine, and an alkanolamine such as triethanolamine or triisopropanolamine. The combination of diamine and alkanolamine provides superior grinding efficiency compared to the diamine or alkanolamine added individually. This composition does not mention the final hydrophobicity and compressive strength properties of the composition.

[0012] In CN108840597A, the composition of this reference is related to a kind of modified triethanolamine grinding aid, that is, the first modified triethanolamine, the second modified triethanolamine, molasses, silicone emulsion, sodium pyrophosphate, water. The kind of modified triethanolamine grinding aid of the present invention is that the grinding aid is absorbed on the solid particle surface, changes the structural characteristics of the particle surface, inhibits particle aggregation, improves the fluidity of the material, can effectively inhibit the closure of newborn crackles, accelerates the expansion of material crackles, can quickly eliminate or weaken the aggregation and adhesion between particles, increase the mill efficiency by more than 12%, and the strength increase after 3 days is ≧5MPa, the strength increase after 28 days is ≧6MPa, the preset period is ≧200 minutes, and the final setting time is ≦300 minutes.

[0013] This is a different composition and does not provide the desired hydrophobicity, strength and reduction in grinding energy. Here, triethanolamine is present at 30 parts and the siloxane (in the siloxane emulsion) is 25% of 4 parts, or 1 part, therefore the ratio of triethanolamine to siloxane is 90:3, which is not effective for the desired results of both compressive strength and water absorption.

[0014] In US9028609B2, the additive composition comprises at least one retarder as well as grinding aids selected from glycols, monocarboxylic acids having 1 to 4 carbon atoms, and comb polymers, which can be used during the process of grinding cement clinker and cause slight browning of the ground cement in the processed state.

[0015] In US8470925B2, where an aqueous emulsion of silicone resin is used as a solid coating and as a top coating to provide water resistance / repellency and improve weather protection, this composition is different in that 1.7 mol% of the R groups are octyl groups and the rest are methyl, and therefore may not provide water resistance / repellency properties when used in a bulk composition, and may not provide sufficient compressive strength properties.

[0016] Thus, although there are references discussing hydrophobicity and grinding aids, there remains a need for stable compositions as additive compositions that reduce energy consumption in cement plants along with the desired rendering of bulk hydrophobicity and better compressive strength of construction products.

[0017] It is preferable to add minimal amounts of additives to basic construction materials such as cement, so that other important properties such as strength and durability are not compromised. It is important to optimize the price of cement by controlling the minimum amount of additives added during the manufacture of cement. The cement market is highly price competitive. Therefore, the present invention seeks to provide additives for the processing of cement, which have the desired strength and durability and are also competitive, with minimal amounts added during the manufacture of cement.

[0018] [Objective of the Invention] One of the objectives of the present invention is to minimize the use of admixtures or the addition of additive materials to construction materials, particularly but not exclusively, cement.

[0019] Another object of the present invention is the reduction of process energy in construction material plants, particularly but not exclusively in grinding processes in cement plants. Another object of the present invention is to achieve the final hydrophobicity of the constructed structure without the addition of any further additives and without compromising the compressive strength.

[0020] [Summary of the Invention] In one aspect, the present invention provides a method for producing an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, including a silicone resin comprising a unit of formula (Ia), and providing an additive composition for improving compressive strength and reducing water absorption, comprising: (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) In the formula, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having at least 4 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, In more than 50 percent of all units of formula (Ia), b is less than c, and either in each unit or on average, a, b, and c are the same or different and are whole or fractional numbers.

[0021] In another aspect, the present invention provides a method for producing a pharmaceutical composition comprising: An alkylsilane, or a hydrolyzate thereof, or a mixture thereof, comprising a silicone resin (or oligomer) containing a unit of formula (Ia): A self-dispersing mixed additive composition for improving compressive strength and reducing water absorption, comprising: (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having more than 4 carbon atoms, in particular 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, In more than 50 percent of all units of formula (Ia), b is less than c, and either in each unit or on average, a, b, and c are the same or different and are whole or fractional numbers.

[0022] In a further aspect, the present invention provides a method for producing a method for the treatment of a cancer a) 0.01 to 5% by weight of an additive composition for improving compressive strength and reducing water absorption, comprising an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, comprising a silicone resin (or oligomer) comprising a unit of formula (Ia); (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, in more than 50 percent of all units of formula (Ia), b is less than c, and either in each unit or on the average unit, a, b, and c are the same or different and are whole numbers or fractions; b) 15% to 35% pozzolanic material; c) 60% to 80% clinker; The present invention provides a cement composition having improved compressive strength and reduced water absorption, comprising:

[0023] As defined by the American Concrete Institute, pozzolans are siliceous, or siliceous and aluminous materials which have little or no cementitious value in themselves, but which, in finely divided form and in the presence of moisture, will chemically react with calcium hydroxide at ambient temperatures to form compounds which have cementitious properties.

[0024] It is therefore classified as a cementitious material. Both natural pozzolans (ACI 232.1R) and artificial pozzolans (fly ash ACI 232.2R, and silica fume ACI 234R) exist. Non-limiting descriptions of, and standards for, the various types of pozzolans are given in ASTM C618 and ASTM C1240.

[0025] Clinker is defined as (1) the partial melt of a kiln that is ground to produce cement, or (2) other vitrified or calcined materials. Concrete, on the other hand, is a mixture of hydraulic cement, aggregate, and water, with or without admixtures, fibers, or other cementitious materials.

[0026] In a further aspect, the present invention relates to a cement mortar or concrete composition comprising: I) a) 0.01 to 100% of an additive composition for improving compressive strength and reducing water absorption, comprising an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, comprising a silicone resin comprising a unit of formula (Ia); (R 1 O)a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, in more than 50 percent of all units of formula (Ia), b is less than c, and either in each unit or on the average unit, a, b, and c are the same or different and are whole numbers or fractions; b) (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or an NR″2-, or an R″2N-R′″-NR″-, or an R″N═NR″ group, where R″, R′″ are C1 to C 20 an optionally substituted aromatic or aliphatic hydrocarbon group having a group, or a mixture thereof; c) 0-30% of an antifoam composition selected from silicone antifoam compositions, and non-silicone antifoam compositions, and mixtures thereof; A cement composition comprising 0.01 to 5 wt.% of a cement additive composition comprising: II) a silica composition; Including, The present invention provides a cement mortar or concrete composition which, in the concrete or mortar, improves the compressive strength measured according to DIN EN 12390-3 or DIN EN 196-1, respectively, in the range of 10-30% and reduces the water absorption according to ASTM C1585 in the range of 10-40%.

[0027] The present invention has surprisingly found a cement additive composition that improves compressive strength and reduces water absorption, comprising an alkylalkoxysilane of formula (Ib), or a hydrolyzate thereof, or a mixture thereof, together with an organic / organosilicone additive, and / or an antifoam composition, which is used before and during the grinding process in a cement plant, not only reducing energy consumption during grinding, but also eliminating the further addition of hydrophobic additive materials to impart hydrophobicity with improved compressive strength to the constructed structure. Such an additive composition will reduce water absorption and improve compressive strength even if added after the grinding process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] [Detailed Description] The additive composition for improving compressive strength and reducing water absorption comprises: comprising an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, including a silicone resin (or oligomer) comprising a unit of formula (Ia): (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3are the same or different and are monovalent alkyl having 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, In more than 50 percent of all units of formula (Ia), b is less than c, and either in each unit or on average, a, b, and c are the same or different and are whole or fractional numbers.

[0029] wherein the alkylsilane is of formula (Ib) or its hydrolysate or a mixture thereof, (X) 4-n SiR' n (Ib) In the formula, n is an arbitrary number from 1 to 3, X is the same or different and is a halide (fluoride, chloride, bromide, iodide) or an alkoxide (-OR), and R is the same or different and is a C1 to C 20 R' is the same or different and is a C1-C 20 It is based on

[0030] In one embodiment, the additive composition may further comprise an antifoam composition selected from a silicone antifoam composition, and a non-silicone antifoam composition, and mixtures thereof.

[0031] In another embodiment, the additive composition comprises (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or an NR″2-, or an R″2N-R′″-NR″-, or an R″N═NR″ group, where R″, R′″ are C1-C 20 The compound may further comprise an organic additive selected from a molecule having the formula:

[0032] In one of the embodiments, the ratio of the alkylsilane hydrolysate or mixture, the additive, and the antifoam composition is (100-20):(80-0):(20-0).

[0033] In one embodiment, the additive composition is an alkylsilane of formula (Ib), or a hydrolysate thereof, or a mixed composition of formula (1a), emulsified or in a solvent. Suitable solvents may include acetone, acetonitrile, alcohol, formaldehyde, ether, ethyl acetate, aromatic solvents (toluene, xylene, etc.), halogenated organic solvents (methylene chloride, chloroform, carbon tetrachloride, etc.), hydrocarbons (hexane, gasoline, kerosene, white spirits). It may also include organic solvents, for example, including aromatic solvents such as benzene, xylene, toluene, ethylbenzene, n-butylbenzene, t-butylbenzene, and isopropylbenzene, lower ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and methyl propionate, and ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone. A solvent may be used in combination with another. A solvent may be preferably used in an amount such that the content of the silane and its hydrolysate in the slurry will be in the range of 5 to 95 weight percent. The glycol ether includes, but is not limited to, di(oxypropylene) glycol-t-butyl ether (DPTB), di(oxypropylene) glycol-n-butyl ether (DPNB), or mixtures thereof. The solvent may additionally include low molecular weight glycols, such as di(oxypropylene) glycol (DPG), di(oxyethylene) glycol (DIEG), or mixtures thereof. It may also be a hydrocarbon solvent, such as benzene, turpentine, pine oil, rosin, or an aliphatic solvent, such as petroleum ether or gasoline.

[0034] In one embodiment, the self-dispersing mix additive composition for improving compressive strength and reducing water absorption comprises: The silicone resin (or oligomer) comprises a unit of formula (Ia), comprising a hydrolyzate of an alkylsilane, or a mixture thereof, (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, In more than 50 percent of all units of formula (I), b is less than c, and either in each unit or on average, a, b, and c are the same or different and are whole numbers or fractions.

[0035] In another embodiment, the self-dispersing mix additive composition further comprises an antifoam composition selected from a silicone antifoam composition and a non-silicone antifoam composition, and mixtures thereof.

[0036] In one embodiment, the self-dispersing mixed additive composition comprises (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or an NR″2-, or an R″2N-R′″-NR″-, or an R″N═NR″ group, where R″, R′″ are C1-C 20 The compound further comprises an organic additive selected from a molecule having the formula:

[0037] In one embodiment, the cement composition that improves compressive strength and reduces water absorption comprises: a) 0.01 to 5 wt. % of an additive composition for improving compressive strength and reducing water absorption, comprising a silicone resin comprising a unit of formula (Ia), a hydrolyzate of an alkylsilane, or a mixture thereof; (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, in more than 50 percent of all units of formula (I), b is less than c, and either in each unit or on the average unit, a, b, and c are the same or different and are whole numbers or fractions; b) 15% to 35% pozzolanic material; c) 60% to 80% clinker; Includes.

[0038] In another embodiment, the cement composition comprises an organic additive comprising a diamine, or an alkanolamine, or a mixture thereof. The cement mortar or concrete composition comprises I) a) an additive composition for improving compressive strength and reducing water absorption by 0.01 to 100%, the additive composition comprising a hydrolyzate of an alkylsilane, or a mixture thereof, containing a silicone resin containing a unit of formula (Ia); (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, in more than 50 percent of all units of formula (I), b is less than c, and either in each unit or on the average unit, a, b, and c are the same or different and are whole numbers or fractions; b) 0-69.99% of an additive selected from (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or a molecule having the group NR''2-, or R''2N-R''''-NR''-, or R''N=NR'', where R'', R''' are optionally substituted aromatic or aliphatic hydrocarbon groups having C1 to C20 groups, or a mixture thereof; c) 0-30% of an antifoam composition selected from silicone antifoam compositions, and non-silicone antifoam compositions, and mixtures thereof; A cement composition comprising 0.01 to 5% by weight of a cement additive composition comprising: II) a silica composition; Including, The concrete or mortar composition improves the compressive strength, measured according to DIN EN 196-1, in the range of 10-30% and reduces the water absorption according to ASTM C1585 in the range of 10-40% in concrete or mortar.

[0039] In another embodiment, the cement additive composition further comprises from 0 percent to less than 50 percent of a silane composition of formula (II): (R 4 O) 4-n-m SiR 5 n R 6 m (II) In the formula, n is any number from 0 to 3, m is any number from 1 to 3, and R 5 are the same or different and are monovalent alkyl groups having 1 to 4 carbon atoms; R 6 are the same or different and are monovalent alkyl having 1 to 20 carbon atoms.

[0040] In one embodiment of the additive composition, the silicone resin comprises more than 50% RSiO 3 / 2 The silicone resin is 10 percent to 100 percent of a mixture of a silicone resin (having 40 percent or more octyl groups, preferably 50 percent or more octyl groups in the silane composition) and is preferably 20 percent to 100 percent of a mixture of a silicone resin (having 40 percent or more octyl groups, preferably 50 percent or more octyl groups) and a silane composition.

[0041] According to one embodiment of the present invention, the silane or its hydrolysate (silicone resin) provides hydrophobicity to the porous product, preferably dry cement, while the non-ionic emulsifier contributes to dispersing the silane or its hydrolysate (silicone resin) in a polar solvent, which helps to apply a coating of the silane or hydrolysate to the cement particles uniformly in the bulk of the cement or plaster. The hydrophobization of the bulk is advantageous in that the entire volume of the component, and not just its surface, obtains hydrophobicity, which is maintained in the concrete or the final structure formed thereafter, together with compressive strength, even if the hydrophobic surface is scraped off. Therefore, both components, alkylsilane or its hydrolysate or their mixture, including silicone resin, and optionally the defoamer composition, and further optionally the additive composition with or without an emulsifier, act synergistically to provide the desired hydrophobicity while maintaining compressive strength. A very surprising phenomenon of this composition is that it also helps to reduce the power or electricity consumption and shorten the time of the grinding process when added before or during grinding.

[0042] In one embodiment, the cement additive composition comprising the alkylalkoxysilane of formula (Ib), or its hydrolysate, or the mixed composition, is emulsified or present in a solvent or as a mixture.

[0043] In one embodiment, the cement additive composition comprises a silicone antifoam composition comprising a silicone polymer, a filler, a surfactant, and water. The dispersion of the present invention is 20 to 1000 m 2 The fillers may include silicon dioxide (silicic acid), titanium dioxide or aluminum oxide, preferably having a BET surface area of ​​50 to 800 m / g, a particle size preferably less than 10 pm, and an agglomerate size preferably less than 100 pm. 2 / g BET surface area. These silicic acids may be pyrogenic or precipitated silicic acids. In particular, pretreated silicic acids, such as, for example, commercially available, fully or partially hydrophobized silicic acids, may be used as fillers.

[0044] In one embodiment, the cement additive composition includes an organic additive comprising a diamine, or an alkanolamine, or a hyperbranched polycarboxylate polymer, or a mixture thereof.

[0045] In one embodiment, the cement additive composition for improving compressive strength and reducing water absorption comprises: a) a self-dispersing mixed additive comprising an alkylalkoxysilane of formula (I), or a hydrolyzate thereof, or a mixture thereof; (RO) 4-n SiR' n (I) In the formula, n is an arbitrary number from 1 to 3, R is the same or different, C1 to C 20 It is based on R' may be the same or different, and is C1 to C 20 It is based on The hydrolysis products of the alkylalkoxysilanes of formula (I) are oligomeric, oligomeric, or mixtures thereof. b) an organic additive selected from (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or a molecule having the group NR''2-, or R''2N-R''''-NR''-, or R''N=NR'', where R'', R''' are optionally substituted aromatic or aliphatic hydrocarbon groups having C1 to C20 groups, or a mixture thereof; c) a silicone defoamer composition, in which the ratio of the self-dispersing mixture, the organic additive, and the silicone defoamer composition is (100-20):(80-0):(20-0); Includes.

[0046] In one embodiment, the cement additive composition, including the self-dispersing mixed additive composition, further includes a protic solvent to form an emulsion. US2018282234 describes a cement additive composition having the formula (RO) 4-n SiR' n or a hydrolyzate thereof, or a mixture thereof, wherein R is the same or different and has a C1-C20 group, and R′ is the same or different and has a C1-C20 group.

[0047] In one embodiment, the cement composition preferably comprises 0.01% to 2% by weight of the cement additive composition. In one embodiment, the cement composition includes an organic additive composition comprising a diamine, or an alkanolamine, or a hyperbranched polycarboxylate polymer, or a mixture thereof.

[0048] According to another aspect of the invention, the alkylalkoxysilane of formula (I) is an alkylalkoxysilane selected from trialkylmonoalkoxysilanes, dialkyldialkoxysilanes, alkyltrialkoxysilanes, and tetraalkoxysilanes. In another embodiment, the alkylsilane of formula (I) is an alkyltrialkoxysilane.

[0049] According to another aspect of the invention, the aminosiloxane (or silicone) is represented by the formula XR2Si (OSiAR) n (OSiR2) m OSiR2X (I) where A is a group of formula -R 1 -[NR 2 -R 3 -] X NR 2 or the protonated amino form of the amino group A; X is R or A or a hydroxyl group or an alkoxy group; R is a monovalent hydrocarbon group having 1 to 18 carbon atoms; R 1is a C1-C6 alkylene group, preferably a group of the formula -CH2CH2CH2- or -CH2CH(CH3)CH2-, R 2 is a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom; R 3 is a C1-C6 alkylene group, preferably a group of formula -CH2CH2-, m+n is a number ranging from 50 to about 500, preferably about 50 to 300, and x is 0 or 1. The mole percent of amine functionality ranges from about 0.3 to about 8%. Examples of aminosilicones useful in the silicone component of the compositions of the present invention include trialkylsilyl end-capped aminosilicones or amodimethicones, amodimethiconols. In another embodiment, the trialkylsilyl end-capped aminosilicones may have several parts by weight of hydroxypolysiloxanes or hydroxypolysiloxanes. The most preferred aminosilicones are reactive amino fluids having a viscosity of 700-1300 mPa·s at 25°C (using a Brookfield LVT, spindle no2, rpm6) and an amine value of 15-20 mgKOH / g.

[0050] In one of the embodiments, the amine value is measured by acid-base titration using a potentiometer [manufacturer: Veego, model: VPT-MG]. 0.6 g of sample is taken in a 500 ml beaker, a 1:1 mixture of toluene-butanol is added, stirred to ensure the sample is thoroughly mixed, and the sample solution is titrated with 0.1 (N) HCl solution. The amine value is calculated according to the formula (56.11 x V x N) / W mg KOH / g of sample, where V = volume of HCl required in ml, N = normality of HCl i.e. 0.1 N, W = weight of sample taken in grams.

[0051] The viscosity of the fluids, their mixtures, and the emulsions prepared with the fluids were also measured at 25° C. using an Anton Paar rheometer, model MCR101, single gap cylinder: CC27 spindle and a shear rate of 1 s-1 , CP25-6 spindle and shear rate 1s -1 , may be measured by

[0052] According to another aspect of the present invention, (A) an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, comprising a silicone resin containing units of formula (Ia): (R 1 O) a R 2 b R 3 c SiO (4-a-b-c) / 2 (Ia) During the ceremony, R 1 are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R 2 are the same or different, monovalent alkyl groups having 1 to 3 carbon atoms, R 3 are the same or different and are monovalent alkyl having 4 to 20 carbon atoms; a is 0 to 3, b is between 0 and 3, c is between 0 and 3, With the condition a+b+c≦3, SiO of formula (Ia) 3 / 2 in more than 50 percent of all units of, b is less than c, and either in individual units or in an average unit, a, b, and c may be identical or different and may be whole numbers or fractions, Optionally, one or more nonionic emulsifiers having an HLB value of 8 to 20 are mixed with the mixture, and then a group of organic compounds from diamines and alkanolamines is mixed with the alkylsilanes, or their hydrolysates, or their mixtures; (B) optionally an organic additive selected from (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or a molecule having an NR''2-, or R''2N-R''-NR''-, or R''N=NR'' group, where R'', R''' are optionally substituted aromatic or aliphatic hydrocarbon groups having C1 to C20 groups, or a mixture thereof; mixing an emulsion comprising A process for preparing a mixed additive composition is provided, comprising:

[0053] A silicone antifoam composition may then be added, where the ratio of the self-dispersing mixture, the organic additive, and the silicone antifoam composition is such that a cement composition having improved compressive strength and reduced water absorption is obtained.

[0054] In one embodiment, the silicone defoamer (or deformer) composition comprises: Formula (A) R 7 a (R 8 O) b R 9 c SiO (4-a-b-c) / 2 (III) At least one organosilicon compound containing units of In the formula, R 7 represents a methyl group, R 8 are the same or different and each represents a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group; R 9 represents a phenyl group or a monovalent, optionally substituted, hydrocarbon group bonded to the silicon atom via a carbon ring atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, and c is 0, 1, 2 or 3. The defoamer composition may further comprise silica, a surfactant, and water.

[0055] In one particular embodiment, the structure of the silicone polymer in the antifoam agent is as follows: R7(SiOR8R9)R10 In the formula, R7 and R 10 are the same group or a mixture. R7 and R 10 R is H, OH, or an alkyl group, and the alkyl chain can be 1 to 12. R and R are the same group or a mixture. R and R 10 is an alkyl group, or an aryl group, or a mixture thereof. The alkyl chain may be 1 to 12, and the aryl group may have 6 to 20 carbon atoms. The silica may be precipitated, or fumed, or a mixture thereof, and is 400 m 2 / gm surface area. Defoamers are available from Wacker under trade names such as Wacker Silfoam, Wacker NE, Wacker Finish, Wacker Powersoft, Wacker SE, and others.

[0056] In another embodiment, the non-silicone antifoam agent is selected from mineral oil, vegetable oil derived antifoams, silica, and the like. According to another aspect of the present invention, there is provided an emulsion comprising a self-dispersing mixed additive composition and a protic solvent.

[0057] In another embodiment, additives are added to any porous product, preferably dry cement, particularly but not limited to, to provide uniform and long-lasting bulk hydrophobicity to the final product while at the same time maintaining compressive strength from the porous product.

[0058] The solvent comprises a protic, particularly a polar protic solvent. Suitable examples of polar protic solvents include water, propanol, ethanol and forming acids. In one embodiment, the self-dispersing mixed additive composition is preferably free of water.

[0059] In one embodiment, the alkylsilane is an alkylalkoxysilane, preferably the same or different alkyltrialkoxysilanes, or hydrolysates thereof, or mixtures thereof, are from 1 to 99 weight percent of the composition, preferably from 50 to 90 weight percent of the composition. The alkylalkoxysilanes may be prepared by reacting silicon metal with an alcohol to form an alkoxysilane, or by reacting and directly hydrolyzing a chlorosilane to obtain the desired silane, or hydrolysate thereof, with a silicone resin.

[0060] The alkyl silane is selected from propyltrimethoxysilane, propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, or mixtures thereof.

[0061] Hydrocarbons R, R', R 1 Examples of the alkyl groups include methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl groups; hexyl groups such as n-hexyl, heptyl groups such as n-heptyl, octyl groups such as n-octyl, and isooctyl groups such as 2,2,4-trimethylpentyl; nonyl groups such as n-nonyl, decyl groups such as n-decyl, dodecyl groups such as n-dodecyl, and n-alkyl groups such as n-alkyl. octadecyl groups such as -octadecyl; alkenyl groups such as vinyl and allyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; aryl groups such as phenyl, naphthyl, anthryl, and phenanthryl; alkaryl groups such as o-, m-, and p-tolyl, xylyl, and ethylphenyl; and aralkyl groups such as benzyl, phenylethyl, or caprylyl. 2 R is an alkyl group such as methyl, ethyl, n-propyl, isopropyl, etc. 3are alkyl groups such as 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl groups; hexyl groups such as n-hexyl group; heptyl groups such as n-heptyl 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; dodecyl groups such as n-dodecyl group; and n-octyl groups such as n-octyl group. octadecyl groups such as octadecyl groups; alkenyl groups such as vinyl and allyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl groups; aryl groups such as phenyl, naphthyl, anthryl, and phenanthryl groups; alkaryl groups such as o-, m-, and p-tolyl groups, xylyl groups, and ethylphenyl groups; and aralkyl groups such as benzyl, phenylethyl, or caprylyl groups. Most preferred R, R 1 , R 2 is a methyl group, and R', R 3 is preferably derived from CC, and is preferably, but not limited to, an n-propyl, n-octyl, isooctyl group.

[0062] In one embodiment, the nonionic emulsifier or mixtures thereof are from 99 to 1 weight percent of the composition, and preferably from 50 to 10 weight percent of the composition. In another embodiment of the present invention, the nonionic emulsifier is selected from polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, and polyoxyalkylene sorbitan esters. Some useful emulsifiers having an HLB value of 8 to 20 are polyethylene glycol octyl ether, polyethylene glycol lauryl ether, polyethylene glycol tridecyl ether, polyethylene glycol cetyl ether, polyethylene glycol mixed alkyl ethers, polyethylene glycol cetyl oleyl ether, polyethylene glycol stearyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol dodecyl phenyl ether, polyethylene glycol cetyl phenyl ether, polyethylene glycol stearyl phenyl ether, polyethylene glycol sorbitan monostearate, and polyethylene glycol sorbitan monooleate.

[0063] The self-dispersing mixed additive composition is dispersed in an aprotic solvent, preferably an aqueous solvent, which is preferably water. The composition according to the present invention is an oil-in-water emulsion. In an emulsion, one liquid (dispersed phase) is dispersed in the other (continuous phase). According to the oil-in-water emulsion of the present invention, the self-dispersing mixed additive composition (dispersed phase) is dispersed in the continuous aqueous phase. The emulsion may be a microemulsion or a macroemulsion. In one particular embodiment, the active content of the emulsion is between 10 and 90 percent, preferably between 30 and 80 percent.

[0064] HLB values ​​usually refer to values ​​at room temperature (25°C). As temperature changes, the HLB value of a surfactant / emulsifier will also change. The calculation of the HLB value of a non-ionic surfactant / emulsifier is calculated by the equation: HLB=(E+P) / 5, where E=weight percentage of oxyethylene content, P=weight percentage of polyhydric alcohol (glycerol, sorbitol, etc.) content, provided by the terms of the HLB system of emulsifier classification introduced by Griffin, WC, “Calculation of HLB Values ​​of non-ionic Surfactants”, Journal of COSMETIC SCIENCE, Vol. 5, No. 4, January 1954, pp. 249-256 (1954).

[0065] For ionic surfactants / emulsifiers, the HLB value of an individual surfactant / emulsifier molecule can be calculated by applying the Davies equation as described in Davies JT (1957), “A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent”, Gas / Liquid and Liquid / Liquid Interface (Proceedings of the International Congress of Surface Activity): 426-38.

[0066] Emulsifier mixtures with HLB values ​​between 10 and 16 are suitable to make the emulsion process simpler. When two emulsifiers A and B with known HLB are mixed for use, the HLB Mix is said to be the required HLB for the mixture. This is expressed by the equation (W A HLB A +W B HLB B ) / (W A +W B )=HLB Mix , where W A = the amount (by weight) of the first emulsifier (A) used, and WB = amount (by weight) of second emulsifier (B), HLB A ,HLB B = HLB values ​​assigned to emulsifiers A and B, HLB Mix = HLB of the mixture, as indicated by:

[0067] A non-ionic emulsifier having an HLB value between 8 and 20, preferably at least one emulsifier or mixture of emulsifiers having an HLB value between 10 and 16 in one embodiment, is very important in the present invention to make the process simpler. In another embodiment, the emulsifier is most preferably a mixture of non-ionic emulsifiers. In another embodiment, cationic or anionic emulsifiers may be selected as emulsifiers.

[0068] In another embodiment of the present invention, the organic additive has the generic structure NR″3, R″2N-R′″-NR″2, R″N=NR″, where R″ is a C1-C 20 R''' is a monovalent hydrocarbon group having a C1-C 20 The organic additive may be, but is not limited to, ethylenediamine of the general formula R1R2N(CH2)2NR3R4, or R1N=NR2 and

[0069] [ka]

[0070] wherein R1, R2, R3 and R4=-H, -CH3, -C2H5, -C3H7, -C4H9, -C2H4OH, -CH(CH2OH)C2H5, phenyl, and X, Y and Z are -H, -NR1R2, and

[0071] [ka]

[0072] wherein R', R'', and R''' are -H, -Me, -Et or -Pr, -NR1R2, or an alkanolamine of the general formula NHmR5OH(3-m), where R5 is an alkylene group having a carbon chain of 1 to 6 and m=0 to 2, or a mixture thereof.

[0073] In another embodiment of the present invention, the organic additive may be selected from the group consisting of, but not limited to, tetrahydroxyethylethylenediamine (THEED), diethylene glycol (DIEG), 1,1-dimethylethylenediamine, 1,2-dimethylethylenediamine, ethambutol, tetrakis(dimethylamino)ethylene (TMEDA), dimethyl-4-phenylenediamine, N,N'-di-2-butyl-1,4-phenylenediamine, 4,4'-diaminobiphenyl, 1,8-diaminonaphthalene, o-phenylenediamine (OPD), m-phenylenediamine (MPD), p-phenylenediamine (PPD), 2,5-diaminotoluene, o-xylenediamine (Xylenediamine), 1,2-dimethylethylene ... The ethylenediamines or derivatives thereof, such as ethylenediamine (OXD), m-xylylenediamine (MXD), p-xylylenediamine (PXD), 1,2-diaminopropane, diphenylethylenediamine, 1,2-diaminocyclohexane, 1,3-diaminopropane, putrescine, cadaverine, and the like, and alkanolamines, such as triethanolamine (TEA), diisopropanolamine (DIPA), diethanolisopropanolamine (DEIPA), triisopropanolamine (TIPA), triethanolamine acetate (TEAA), N,N-bis(2-hydroxyethyl)-2-propanolamine, and the like.

[0074] In one of the other embodiments, the amine organic additive is a mixture of diamine and alkanolamine. In one of the preferred compositions, the ratio of diamine:alkanolamine is 99.5:0.5 to 0.5:99.5, more preferably 95:5 to 5:95. The dosage by weight to the cement can range from 0.001%S / s to 0.5%S / s, with a preferred range of 0.01% to 0.1%S / s.

[0075] In another embodiment of the present invention, the organic additive is selected from, but not limited to, hyperbranched polycarboxylates having an anionic backbone and several non-ionic pendant chains, usually including polyalkylene glycols, or hyperbranched carboxylates constructed from linear polyalkyleneamines and a hyperbranched polyglycerol backbone that is terminally carboxymethylated. The average molecular weight is always greater than 2000 gm / mol.

[0076] Formula (I) alkylalkoxysilane, or its hydrolysate, or mixture thereof, and aminopolysiloxane are combined. The ratio of formula (I) alkylalkoxysilane, or its hydrolysate, or mixture thereof, and aminopolysiloxane is 99:1 to 1:99, preferably 80:20 to 20:80, and most preferably 60:40 to 40:60. Aminopolysiloxane can be derivatized with dimethylcyclosiloxane, polydimethylsiloxane, or fluid via cracking (polymeric LGS). Modified with diethylenetriamine, 2-aminoethyl)-3-aminopropyl, 2-aminoethyl-3-aminopropylmethyl, 3-aminopropyl, etc.

[0077] Dosing of the test compositions: PORTLAND cement (Class C) is used as the base cement. It is used in three different scenarios to test the hydrophobicity and strength of the final composition: (a) Measure the energy requirements and additive distribution before grinding (b) After the grinding process is completed, the grinding aid composition is mixed for final hydrophobicity and strength comparison testing. (c) After the slag is mixed with the ground cement, a grinding aid composition is mixed in for final hydrophobicity and strength comparison testing. The mixture is treated with a composition of the present invention or a non-present invention by mixing with.

[0078] The grinding test may be carried out in a ball mill and the energy required is measured by an external energy measuring device. The energy consumption may be determined by the power consumption of the mill and the fixed operating time. The power used by the ball mill is calculated by multiplying the current and the voltage measured by an ammeter and a voltmeter connected to the electrical cabinet of the ball mill. The properties of the final ground cement may be measured according to the measurement of the fineness after grinding (DIN EN 196-6) and the surface area test of the solid (DIN ISO 9277).

[0079] The following examples serve to illustrate the invention in more detail and should not be construed as limiting. EXAMPLES

[0080] [Preparation] (a) Preparation of hydrolyzed n-octyltriethoxysilane: n-Octyltriethoxysilane: 3300g Concentrated sulfuric acid: 7.2g Water: 108g is introduced into the reactor and refluxed at a temperature of 85°C, finally distilling off all volatile substances (yield: 92%), which is then neutralized with triethanolamine to obtain hydrolyzed n-octyltriethoxysilane (also called oligomeric silane), which has more than one unit. (b) Preparation of Silicone Resin Composition (Composition of the Present Invention): 70% n-octyltriethoxysilane (and 30% n-methyltriethoxysilane): 3300g Concentrated sulfuric acid: 7.2g Water: 108g (c) Preparation of Silicone Resin Composition (Non-Inventive Composition): 30% n-octyltriethoxysilane (and 70% n-methyltriethoxysilane): 3300g Concentrated sulfuric acid: 7.2g Water: 108g The above compositions (a), (b) and (c) are introduced into a reactor and refluxed at a temperature of 85°C, finally distilling off all volatile substances (yield: 92%), and then neutralized with triethanolamine to obtain a silicone resin (or hydrolyzed alkoxysilane). The silicone resin has more than one siloxy unit with a viscosity of 12-17 mPas at 25°C. The silicone resin may be defined as a methyl-octyl-methoxy resin, where every Si atom is bonded to exactly one octyl or methyl group with the above-mentioned methyl-octyl ratio, and every Si atom is bonded to 0-3 methoxy groups. A continuous method of synthesis is described in Wacker Chemie patent US7339069 entitled continuous process for preparing SiOC-containing compound, further incorporated by reference. Some applications are also further described in Wacker's published application US20210130550, the use of alkyl silicone resin as additive for hydrophilizing fiber, which is also further incorporated by reference.

[0081] d) Mixed compositions of silicone resins (both inventive and non-inventive) are mixed with silane compositions to form mixed compositions for the experiments. e) The oil-in-water emulsions of the present invention (and also comparative) are formed by adding a silicone resin, the composition (dispersed phase) being dispersed in a continuous water phase. In one other embodiment, a catalyst may be incorporated into the emulsion to react the resin, although such compositions must be used immediately as they react, crosslink and harden to no further activity. A) Performance test Comparative performance tests were conducted on mortars prepared with the compressive strength improving and water absorption reducing cement additive composition of the present invention, which also acts as a grinding aid composition, blank Portland cement, and a reference sample (without additive). Mortar Test: Preparation of specimens with composition: 1200g sand, 400g cement, 240g water. The control and test mix materials and moulds for the specimens shall be conditioned for at least 24 hours before use. Conditioning shall be done by placing them in an enclosure maintained at (20±2)°C and (65±5)% relative humidity.

[0082] The mixture of mortar shall be as described in EN 480-1. Mortar specimens (40 x 40 x 160) mm shall be prepared as described in EN 196-1, except that the mould shall not be oiled.

[0083] When tested at equal w / c ratios, the water content of the admixture shall be taken into account in calculating the required water content of the mortar. If the test mixture has the same consistency as the control or reference mixture, this shall be measured by using a workability meter according to EN 413-2. To carry out the test, the following equipment is considered: Tonimix mixture from Germany (Zwick Rolle).

[0084] [Hydrophobicity test] [Hydrophobicity of cement composition] Preparations are made for comparative data with similar % dosage of silicone composition in the final cement mix. Dry cement blocks are prepared and the produced cement is compressed into a Petri dish (90 x 15 mm) and flushed with a smooth glass rod. Five drops of water are then placed on the cement surface using a disposable dropper (Tarson 940050 LDPE Pasteur pipette) and a stopwatch is started. The time it takes for the drop to disappear is recorded, which is an indication of water repellency or hydrophobicity, and a beading time test is performed to record the time it takes for the drop to disappear in Table 1.

[0085] [Measurement of water absorption rate of mortar composition] The mortar shall be as described in EN 480-1. Mortar specimens (40 x 40 x 160) mm shall be prepared as described in EN 196-1. To test the hydrophobicity, evaluate the water absorption as specified in ASTM C1585 for 24 or 96 hours.

[0086] [Compressive strength (CS) test] The CS is measured according to the DIN EN 12390-3 (for concrete) or DIN EN 196-1 (for mortar) standards and is recorded in Table 2 in MPa after 1 day, 14 days and 28 days, respectively, for comparison with the prior art on mortar specimens prepared as described in EN 196-1, if necessary. The tests were carried out on mortar compositions, but are not limited to mortars, but are also applicable to concrete, or plaster and its final composition.

[0087] [Table 1] TIFF2024523259000004.tif236169TIFF2024523259000005.tif236169TIFF20245232590 00006.tif236169TIFF2024523259000007.tif236169TIFF2024523259000008.tif121169

[0088] [Table 2]

[0089] [Insights from the experiment] In Table 1, the experiments of the present invention are seen, where Experiments No. 8 and 9 show that by dosing or mixing the compressive strength improving and water absorption reducing cement additive composition of the present invention into the PPC cement, the compressive strength is increased by 14% [(42.06-36.8) / 36.8=14%] for Experiment 9 versus a non-inventive normal hydrophobic octylsilane cement composition of Experiment No. 2, both Experiments 2 and 9 are comparable in hydrophobicity, which is significantly improved versus the non-inventive reference of Experiment No. 1, i.e., the reference without additive.

[0090] Additionally, Reference+ Antifoam ** Non-inventive run 10 containing emulsion has CS values ​​of 37.85 and 44.45 respectively, but the hydrophobicity value is almost the same as run 1 (reference cement) at 0 min, thereby indicating that the defoamer has no effect on hydrophobicity and also on strength enhancement.

[0091] Even in experiments 5, 6, 7, 11 and 12, the addition of organic additives including alkylsilanes or hydrolyzed alkylsilanes and the addition of defoamers including alkylsilanes or hydrolyzed alkylsilanes in a solvent or in emulsion form do not provide optimal improvements in compressive strength and high hydrophobicity values.

[0092] Surprisingly, synergistic improvements in compressive strength and hydrophobicity values ​​were observed when the composition of the present invention comprising alkylsilane or hydrolyzed alkylsilane with organic additive and antifoaming agent was added to cement, as demonstrated in Experiments 8, 9, 19, 20, 32, 33, 38 and 39, respectively. Similarly, in Experiments 4 and 29, the addition of organic additive did not provide optimal improvements in compressive strength and hydrophobicity in mortar, but surprisingly, synergistic improvements were observed in compressive strength and hydrophobicity when the composition of the present invention comprising alkylsilane or hydrolyzed alkylsilane, organic additive and silicone antifoaming agent was added in cement grinding, in Experiments 8, 9, 19, 20, 32, 33, 35, 40-43.

[0093] Therefore, the compositions of the present invention act as grinding aids before or during grinding and also significantly increase the hydrophobicity of cement, plaster and mortar compositions, thus maintaining the compressive strength of the compositions.

Claims

1. An additive composition that improves compressive strength and reduces water absorption, comprising an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, and a silicone resin containing units of formula (Ia), (R １ O) ａ R ２ ｂ R ３ ｃ SiO （４－ａ－ｂ－ｃ）／２ (Ia) In the formula (Ia), R １ is the same or different and is a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R ２ is the same or different and is a monovalent alkyl group having 1 to 3 carbon atoms, R ３ is the same or different and is a monovalent alkyl having at least 4 carbon atoms, a is 0 or more and 3 or less, b is 0 or more and 3 or less, c is 0 or more and 3 or less, under the condition that a + b + c ≦ 3, in more than 50 percent of all the units of the formula (Ia), b is smaller than c, and a, b, and c are the same or different, integers or fractions, either in each unit or in the average unit, Additive composition.

2. The alkylsilane of formula (Ib), or a hydrolyzate thereof, or a mixture thereof, (X) ４－ｎ SiR’ ｎ (Ib) In the formula (Ib), n is any number from 1 to 3, X is the same or different and is a halide, -OR, R is the same or different and is a C １ ~C ２０ group, R’ is the same or different and is a C １ ~C ２０ which is a base, The additive composition according to claim 1.

3. The additive composition according to claim 1, further comprising an antifoaming agent composition selected from the group consisting of a silicone antifoaming agent composition, a non-silicone antifoaming agent composition, and mixtures thereof.

4. (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or NR’’ ２ -, or R’’ ２ N-R’’’-NR’’-, or R’’N=N R’’ groups, wherein R’’, R’’’ are optionally substituted aromatic or aliphatic hydrocarbon groups having a C １ ~C ２０ The additive composition according to claim 1, further comprising an organic additive selected from molecules having, or mixtures thereof.

5. Said R １ Said R ２ is methyl or ethyl, and said R ３ is octyl or iso-octyl group, the additive composition according to claim 1.

6. The alkylsilane containing a silicone resin containing the unit of formula (Ia), or its hydrolyzate, or the mixed composition is emulsified or in a solvent, the additive composition according to claim 1.

7. The alkylsilane of formula (Ib), or its hydrolyzate, or the mixed composition is emulsified or in a solvent, the additive composition according to claim 2.

8. The silicone antifoaming agent composition according to claim 3, comprising a silicone polymer, silica, a surfactant, and water.

9. The organic additive according to claim 4, comprising a diamine, or an alkanolamine, or mixtures thereof.

10. A self-dispersing mixed additive composition that improves compressive strength and reduces water absorption, comprising an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, and a silicone resin containing units of formula (Ia), (R １ O) ａ R ２ ｂ R ３ ｃ SiO （４－ａ－ｂ－ｃ）／２ (Ia) In the formula (Ia), R １ are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R ２ are the same or different and are a monovalent alkyl group having 1 to 3 carbon atoms, R ３ are the same or different and are a monovalent alkyl having 4 to 20 carbon atoms, a is 0 or more and 3 or less, b is 0 or more and 3 or less, c is 0 or more and 3 or less, under the condition that a + b + c ≦ 3, in more than 50 percent of all units of the formula (Ia), b is smaller than c, and a, b, and c are the same or different, integers or fractions, either in each unit or in the average unit, Self-dispersing mixed additive composition.

11. The self-dispersing mixed additive composition according to claim 10, which further comprises an antifoaming agent composition selected from the group consisting of a silicone antifoaming agent composition, a non-silicone antifoaming agent composition, and mixtures thereof, which improves compressive strength and reduces water absorption.

12. (a) aminosilane, (b) aminosiloxane, or (c) hyperbranched polycarboxylate polymer, or NR'' ２ -, or R'' ２An N—R‴—NR″— or R″N═NR″ group, where R″ and R″′ are optionally substituted aromatic or aliphatic hydrocarbon groups having a C １ ~C ２０ group, an organic additive selected from molecules having the same, or a mixture thereof, and further comprising an additive selected from the group consisting of: The self-dispersing mixed additive composition according to claim 10, which improves compressive strength and reduces water absorption. **Claim 13** An alkylsilane, or a hydrolyzate thereof, or a mixed composition comprising a silicone resin containing units of formula (Ia) is emulsified or in a solvent. The self-dispersing mixed additive composition according to claim 10, which improves compressive strength and reduces water absorption. **Claim 14** A cement composition that improves compressive strength and reduces water absorption, a) 0.01 to 5% by weight of an additive composition that improves compressive strength and reduces water absorption, comprising an alkylsilane, or a hydrolyzate thereof, or a mixture thereof, comprising a silicone resin containing units of formula (Ia); and (R １ O) ａ R ２ ｂ R ３ ｃ SiO （４－ａ－ｂ－ｃ）／２ (Ia) In the formula (Ia), R １ are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R ２ are the same or different and are a monovalent alkyl group having 1 to 3 carbon atoms, R ３ are the same or different and are a monovalent alkyl having 4 to 20 carbon atoms, a is 0 or more and 3 or less, b is 0 or more and 3 or less, c is 0 or more and 3 or less, under the condition that a + b + c ≤ 3, In more than 50 percent of all units of the formula (Ia), b is less than c, and in either each unit or the average unit, a, b, and c are the same or different and are integers or fractions. b) 15% to 35% of a pozzolanic material, c) 60% to 80% of clinker, A cement composition comprising the same.

15. The cement composition according to claim 14, wherein the organic additive comprises a diamine, or an alkanolamine, or a mixture thereof.

16. A cement mortar or concrete composition, I) a) An additive composition containing 0.01 to 100% of an alkyl silane, or a hydrolyzate thereof, or a mixture thereof, which contains a silicone resin containing units of the formula (Ia) and improves compressive strength and reduces water absorption, (R １ O) ａ R ２ ｂ R ３ ｃ SiO （４－ａ－ｂ－ｃ）／２ (Ia) In the formula (Ia), R １ are the same or different and are a hydrogen atom or a monovalent alkyl group having 1 to 4 carbon atoms, R ２ are the same or different and are a monovalent alkyl group having 1 to 3 carbon atoms, R ３ are the same or different and are a monovalent alkyl having 4 to 20 carbon atoms, a is 0 or more and 3 or less, b is 0 or more and 3 or less, c is 0 or more and 3 or less, Under the condition that a + b + c ≤ 3, In more than 50 percent of all units of the formula (Ia), b is less than c, and in either each unit or the average unit, a, b, and c are the same or different and are integers or fractions. b) (a) an aminosilane, (b) an aminosiloxane, or (c) a hyperbranched polycarboxylate polymer, or NR'' ２ -, or R'' ２ N-R'''-NR''-, or R''N=NR'' groups, wherein R'' and R''' are optionally substituted aromatic or aliphatic hydrocarbon groups having C １ ~ C ２０ groups, a molecule having, an organic additive selected from, or a mixture thereof, 0 to 69.99% of an additive selected from, and c) a silicone defoamer composition, and a non-silicone defoamer composition, and 0 to 30% of a defoamer composition selected from a mixture thereof, A cement composition comprising a cement additive composition of 0.01 to 5% by weight, II) a silica composition, and comprising, The concrete or mortar composition improves the compressive strength measured according to DIN EN 12390-3 or DIN EN 196-1 in the concrete or mortar in the range of 10 to 30% and reduces water absorption according to ASTM C1585 in the range of 10 to 40%. A cement mortar or concrete composition.

17. An additive composition for improving compressive strength and reducing water absorption according to any one of Claims 1 to 13, wherein the composition is an additive composition for a Portland cement composition. Additive composition.