CN107955173B - Concrete defoaming agent and synthetic method thereof - Google Patents
Concrete defoaming agent and synthetic method thereof Download PDFInfo
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- CN107955173B CN107955173B CN201711170483.XA CN201711170483A CN107955173B CN 107955173 B CN107955173 B CN 107955173B CN 201711170483 A CN201711170483 A CN 201711170483A CN 107955173 B CN107955173 B CN 107955173B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/50—Defoamers, air detrainers
Abstract
The invention provides a novel concrete defoamer and a synthesis method thereof, the obtained concrete defoamer is polyether, acrylate containing glycosyl and siloxane block polymer with low hydrogen content, hydrophilic polyether group and glycosyl are used for endowing the polymer with water solubility, and hydrophobic polysiloxane and acrylate chain segment are used for endowing the polymer with hydrophobicity, and the two are matched in a certain proportion to synthesize a nonionic surfactant, so that the concrete defoamer is easy to dissolve and emulsify, is acid-base resistant, has good compatibility with other concrete additives, and has obviously better performance than other defoamers when being applied to the field of concrete.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a concrete defoamer and a synthetic method thereof.
Background
Nowadays, the rate of increase of the amount of concrete used is much higher than 40 years ago. The annual consumption of concrete in the world is estimated to be 110 hundred million tons, and the concrete becomes the building material with the widest application range at present. Concrete is a structural material, is not as strong as steel, is not as rigid as steel, but has the cheapest material (the main components for preparing concrete, namely aggregate, water and portland cement, are low in cost and can be easily obtained in most regions of the world), has the strongest plasticity (concrete can easily prepare various concrete members with different sizes), and has the best advantage of water resistance, so that the concrete is outstanding in building materials.
The concrete is a multiphase material and consists of three items of solid, liquid and gas. Under mechanical agitation, the solid in the concrete enters the liquid, wherein insoluble gas enters the liquid and is separated into heterogeneous systems by the liquid, so that a large number of gas-liquid interfaces and gas-solid interfaces are formed. Since the density of the gas phase < the density of the liquid phase < the density of the solid phase, there is a phenomenon that the gas phase moves toward the liquid surface with the buoyancy, and two-phase foam or three-phase foam is generated. The quality of the surface layer needs to be controlled by adopting a proper method, if the control is not good, the surface defects of cracks, holes, honeycombs, pitted surfaces and the like are easy to form on the surface of the concrete, the durability of the concrete and the aesthetic effect of the concrete veneer are seriously influenced, and the process is a disadvantage process that the concrete is deep from the outside to the inside and gradually. Domestic and foreign researches show that the quality of the concrete surface layer (the apparent quality and the surface layer performance of cement mortar and concrete materials within 30mm from the concrete surface layer) is closely related to the content and the effective diameter of bubbles in a concrete system, and the surface layer performance of the concrete can be improved to a certain extent by using the defoaming agent.
In practical building engineering application, harmful bubble distribution is reduced through a defoaming agent, the content of bubbles is controlled, and the diameters of the bubbles are reduced, so that the workability of concrete is improved, and the frost-resistant fusion durability of the concrete is improved through micro bubbles reserved in the later stage.
The defoaming agents currently used in the concrete field in the market generally include non-silicon type and organic silicon defoaming agents and polyether modified organic silicon type defoaming agents. From the development process of the defoaming agent, four stages are mainly divided.
The first type of defoaming agent is mainly composed of various organic substances, such as: fatty acids, mineral oils, fatty amides, lower alcohols, and the like. Most of the defoaming agents are natural substances, so that the environmental pollution is low and the price is low. As the defoaming property is weak, the production requirement cannot be met under the condition of a large amount of foams.
The second type is polyether defoaming agent, and the molecular general formula is as follows: CnH (2n +1) O (EO) a (PO) bH, the polyoxyethylene segment (EO) being a hydrophilic group; the polyoxypropylene segment (PO) is a lipophilic group. The defoaming agent is non-toxic, non-irritant, good in dispersibility and good in foam inhibition effect, but the defoaming effect is not obvious.
The third type is a silicone defoamer, which has better defoaming performance than the former two. Generally, silicone oil with a larger molecular weight is insoluble in a surfactant solution, whereas for small molecular weight silicone oil, it is easily solubilized by surfactant molecules, thereby changing the composition of the defoaming agent and weakening the defoaming performance. The defoaming agent has strong foam inhibition capability, greatly enhances the foam breaking effect, but has great problem of insolubility and harsh use conditions.
The fourth type of defoaming agent is a polyether modified silicone oil defoaming agent, the advantages of polyether and organic silicon are integrated, the polyether chain segment is introduced into the silicone oil chain segment, and the defoaming and foam inhibition performance is stronger, but in an actual product, due to the structural characteristics of the main defoaming component, the defoaming performance is good, the foam inhibition performance is limited, or the foam inhibition effect is good, the defoaming effect is not obvious, and the foam inhibition effect is difficult to generate while the defoaming is generated.
Disclosure of Invention
The invention aims to provide a concrete defoaming agent and a synthesis method thereof, which can eliminate large bubbles generated in concrete, inhibit the regeneration of bubbles, effectively relieve the adverse effect of foam on the concrete and improve the workability of the concrete.
In order to achieve the purpose, the invention adopts the technical scheme that:
the concrete defoamer is characterized in that: the silicone oil is prepared by taking low-hydrogen-content silicone or silicone derivatives, glycosyl acrylate compounds and allyl alcohol polyoxyethylene polyoxypropylene ether as raw materials and adopting hydrosilylation reaction, and the structural formula of the silicone oil is as follows:
wherein: a is an integer of 11-15, b is an integer of 11-17, x is an integer of 3-30, y is an integer of 7-30, z is an integer of 1-15, R1 is CH3 or H, and R2 is OH.
Further preferred scheme, a concrete defoaming agent, its characterized in that: the low-hydrogen siloxane or siloxane derivative contains 0.1-0.2% of hydrogen.
Further preferred scheme, a concrete defoaming agent, its characterized in that: the glycosyl acrylate compound is glucose oxyethyl acrylate or glucose oxyethyl methacrylate.
Further preferred scheme, a concrete defoaming agent, its characterized in that: the low hydrogen containing siloxane or siloxane derivative is a terminal siloxane.
A synthetic method of a concrete defoamer is characterized by comprising the following steps: the method comprises the following steps:
step 1: vacuum distilling low hydrogen content siloxane or siloxane derivative, allyl alcohol polyoxyethylene polyoxypropylene ether, and glycosyl acrylate compound;
step 2: adding siloxane or siloxane derivatives with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor into a three-necked bottle provided with a stirring pipe, a thermometer and a reflux condenser, heating to 50 ℃, adding a chloroplatinic acid catalyst, heating to 85-95 ℃, dropwise adding allyl alcohol polyoxyethylene polyoxypropylene ether and glycosyl acrylate compounds at a constant speed under stirring, dropwise adding for 1h, and continuing to react for 5h after dropwise adding;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid as a main monomer of the defoaming agent;
and 4, step 4: sequentially adding a main monomer of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a container, stirring for 5min at room temperature by using a high-shear disperser at a rotating speed of not less than 10000r/min to completely disperse the emulsifier uniformly, then adding hot water at 70-80 ℃ for 10min along the stirring direction, continuing stirring for 2min, then adding a thickening agent of carboxymethyl cellulose sodium aqueous solution to completely emulsify the defoaming agent, continuing stirring for 3min, and adjusting the pH value of the emulsion to be 7 by using NaOH aqueous solution to obtain the concrete defoaming agent emulsion.
Further preferred scheme, the synthetic method of concrete defoamer, characterized by: the mol ratio of the allyl alcohol polyoxyethylene polyoxypropylene ether dropwise added in the step 2 to the glycosyl acrylate compound is 1: 1-2.
Further preferred scheme, the synthetic method of concrete defoamer, characterized by: the manner of dripping the allyl alcohol polyoxyethylene polyoxypropylene ether and the glycosyl acrylate compound in the step 2 is as follows:
controlling the temperature to be 85-95 ℃, and dropwise adding a mixed solution of allyl alcohol polyoxyethylene polyoxypropylene ether and glycosyl acrylate compounds at a constant speed under stirring;
or controlling the temperature to be 85-95 ℃, dropwise adding allyl alcohol polyoxyethylene polyoxypropylene ether at a constant speed under stirring, and dropwise adding a glycosyl acrylate compound at a constant speed;
or controlling the temperature to be 85-95 ℃, dropwise adding the glycosyl acrylate compound at a constant speed under stirring, and then dropwise adding the allyl alcohol polyoxyethylene polyoxypropylene ether at a constant speed.
Further preferred scheme, the synthetic method of concrete defoamer, characterized by: in the step 2, the ratio of the amount of the siloxane or the siloxane derivative with low hydrogen content to the sum of the amounts of the allyl alcohol polyoxyethylene polyoxypropylene ether and the glycosyl acrylate compound is 1: 1.2-1: 1.4.
Further preferred scheme, the synthetic method of concrete defoamer, characterized by: the chloroplatinic acid catalyst is isopropanol solution of chloroplatinic acid, and the platinum content in the catalyst is 10 mu g of the total mass of the reactant system-1～60μg·g-1。
Further preferred scheme, the synthetic method of concrete defoamer, characterized by: in the step 2, the mass ratio of the solvent isopropanol to the total reactants is 30-40%, and the mass ratio of the polymerization inhibitor hydroquinone to the total reactants is 0.15%.
Advantageous effects
The concrete defoamer obtained by the invention is polyether, glycosyl-containing acrylate and low-hydrogen siloxane block polymer, hydrophilic polyether group and glycosyl-containing endow the polymer with water solubility, and hydrophobic polysiloxane and acrylate chain segment endow the polymer with hydrophobicity, and the two are matched in a certain proportion to synthesize the nonionic surfactant, which is easy to dissolve and emulsify, is acid-base resistant, has good compatibility with other concrete admixtures, and has obviously better performance than other defoamers when being applied to the field of concrete.
The invention has the following beneficial effects: (1) the concrete defoamer disclosed by the invention has good solubility, strong acid and alkali resistance and good compatibility with other additives of concrete. (2) The concrete defoamer provided by the invention has the advantages of good wetting and spreading effects, quick defoaming, obvious foam inhibition effect and capability of effectively improving the working performance of concrete.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The concrete defoaming agent provided by the invention takes siloxane or siloxane derivatives with low hydrogen content, glycosyl acrylate compounds and allyl alcohol polyoxyethylene polyoxypropylene ether as raw materials, adopts hydrosilylation reaction, introduces acrylate and polyether on a polysiloxane chain simultaneously, synthesizes a graft type amphiphilic copolymer, has low surface tension provided by lipophilicity of polysiloxane and high surface performance provided by lipophilicity of acrylate, has water solubility provided by hydrophilicity of a polyether chain segment and glycosyl, overcomes the characteristics of specificity and pertinence of the defoaming agent, inhibits or eliminates excessive or harmful bubbles in concrete, can solve the problems of defoaming performance and foam inhibition performance, thereby improving the compactness of concrete and improving the workability of concrete.
The structural formula is as follows:
wherein: a is an integer of 11-15, b is an integer of 11-17, x is an integer of 3-30, y is an integer of 7-30, z is an integer of 1-15, R1 is CH3 or H, and R2 is OH.
The synthesis equation of the main monomer of the defoaming agent is as follows:
the following description of the preparation of the defoaming agent is made with reference to specific examples:
example 1:
step 1: vacuum distilling low hydrogen content siloxane (hydrogen content 0.12%), allyl alcohol polyoxyethylene polyoxypropylene ether, and glucose oxyethyl methacrylate until water content is below 0.1%;
step 2: adding 1mol of siloxane with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor into a three-neck flask provided with a mechanical stirring pipe, a thermometer and a reflux condenser, wherein the mass ratio of the isopropanol as the solvent to the total reactants is 30-40%, and the mass ratio of the hydroquinone as the polymerization inhibitor to the total reactants is 0.15%; heating to 50 deg.C, adding 20 μ g-1Heating the chloroplatinic acid catalyst to 85-95 ℃, dropwise adding 1.20mol of mixed solution of allyl alcohol polyoxyethylene polyoxypropylene ether and glucose oxyethyl methacrylate at a constant speed under stirring for 1 hour, and continuously reacting for 5 hours after dropwise adding; wherein n (allyl alcohol polyoxyethylene polyoxypropylene ether): n (gluconoxyethyl methacrylate) ═ 1: 2;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid serving as a main monomer xp-1 of the defoaming agent;
and 4, step 4: sequentially adding a main monomer xp-1 of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a 100mL beaker, wherein the Span 60 refers to sorbitan monostearate, also called sorbitan monostearate; the Tween60 refers to polyoxyethylene sorbitan stearate, and the mass ratio of the emulsifier Span 60 to the emulsifier Tween60 is 3: 2; stirring the mixture for 5min at the rotation speed of 10000r/min by a high-shear disperser at room temperature to completely disperse the emulsifier uniformly, adding hot water at 70-80 ℃ for 10min along the stirring direction, continuously stirring the mixture for 2min, adding a thickener carboxymethyl cellulose sodium aqueous solution to completely emulsify the defoamer, continuously stirring the mixture for 3min, and adjusting the pH of the emulsion to be 7 by using a NaOH aqueous solution with the mass fraction of 10% to prepare the concrete defoamer xp-1 emulsion.
Example 2:
step 1: vacuum distilling low hydrogen content siloxane (hydrogen content 0.16%), allyl alcohol polyoxyethylene polyoxypropylene ether, and glucose oxyethyl methacrylate until water content is below 0.1%;
step 2: adding 1mol of siloxane with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor into a three-neck flask provided with a mechanical stirring pipe, a thermometer and a reflux condenser, wherein the mass ratio of the isopropanol as the solvent to the total reactants is 30-40%, and the mass ratio of the hydroquinone as the polymerization inhibitor to the total reactants is 0.15%; heating to 50 deg.C, adding 30 μ g-1Heating chloroplatinic acid catalyst to 90 ℃, dropwise adding 1.20mol of mixed solution of allyl alcohol polyoxyethylene polyoxypropylene ether and glucose oxyethyl methacrylate at constant speed while stirring, dropwise adding for 1h, and continuing to react for 5h after dropwise adding; wherein n (allyl alcohol polyoxyethylene polyoxypropylene ether): n (gluconoxyethyl methacrylate) ═ 1: 1;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid serving as a main monomer xp-2 of the defoaming agent;
and 4, step 4: sequentially adding a main monomer xp-2 of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a 100mL beaker, wherein the Span 60 refers to sorbitan monostearate, also called sorbitan monostearate; the Tween60 refers to polyoxyethylene sorbitan stearate, and the mass ratio of the emulsifier Span 60 to the emulsifier Tween60 is 3: 2; stirring the mixture for 5min at the rotation speed of 10000r/min by a high-shear disperser at room temperature to completely disperse the emulsifier uniformly, adding hot water at 70-80 ℃ for 10min along the stirring direction, continuously stirring the mixture for 2min, adding a thickener carboxymethyl cellulose sodium aqueous solution to completely emulsify the defoamer, continuously stirring the mixture for 3min, and adjusting the pH of the emulsion to be 7 by using a NaOH aqueous solution with the mass fraction of 10% to prepare the concrete defoamer xp-2 emulsion.
Example 3:
step 1: vacuum distilling low hydrogen content siloxane (hydrogen content 0.16%), allyl alcohol polyoxyethylene polyoxypropylene ether, and glucose oxyethyl methacrylate until water content is below 0.1%;
step 2: adding 1mol of siloxane with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor into a three-neck flask provided with a mechanical stirring pipe, a thermometer and a reflux condenser, wherein the mass ratio of the isopropanol as the solvent to the total reactants is 30-40%, and the mass ratio of the hydroquinone as the polymerization inhibitor to the total reactants is 0.15%; heating to 50 deg.C, adding 30 μ g-1Heating chloroplatinic acid catalyst to 90 ℃, firstly dripping 0.6mol of allyl alcohol polyoxyethylene polyoxypropylene ether at a constant speed under stirring, then dripping 0.6mol of glucose oxyethyl methacrylate at a constant speed, and continuing to react for 5 hours after dripping;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid which is a main monomer xp-3 of the defoaming agent;
and 4, step 4: sequentially adding a main monomer xp-3 of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a 100mL beaker, wherein the Span 60 refers to sorbitan monostearate, also called sorbitan monostearate; the Tween60 refers to polyoxyethylene sorbitan stearate, and the mass ratio of the emulsifier Span 60 to the emulsifier Tween60 is 3: 2; stirring the mixture for 5min at the rotation speed of 10000r/min by a high-shear disperser at room temperature to completely disperse the emulsifier uniformly, adding hot water at 70-80 ℃ for 10min along the stirring direction, continuously stirring the mixture for 2min, adding a thickener carboxymethyl cellulose sodium aqueous solution to completely emulsify the defoamer, continuously stirring the mixture for 3min, and adjusting the pH of the emulsion to be 7 by using a NaOH aqueous solution with the mass fraction of 10% to prepare the concrete defoamer xp-3 emulsion.
Example 4:
step 1: vacuum distilling low hydrogen content siloxane (hydrogen content 0.16%), allyl alcohol polyoxyethylene polyoxypropylene ether, and glucose oxyethyl acrylate to water content below 0.1%;
step 2: adding 1mol of siloxane with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor into a three-neck flask provided with a mechanical stirring pipe, a thermometer and a reflux condenser, wherein the mass ratio of the isopropanol as the solvent to the total reactants is 30-40%, and the mass ratio of the hydroquinone as the polymerization inhibitor to the total reactants is 0.15%; heating to 50 deg.C, adding 40 μ g-1Heating chloroplatinic acid catalyst to 85 ℃, firstly dripping 0.7mol of glucose oxyethyl acrylate at a constant speed under stirring, then dripping 0.5mol of allyl alcohol polyoxyethylene polyoxypropylene ether at a constant speed, and continuing to react for 5 hours after dripping;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid which is a main monomer xp-4 of the defoaming agent;
and 4, step 4: sequentially adding a main monomer xp-4 of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a 100mL beaker, wherein the Span 60 refers to sorbitan monostearate and is also called sorbitan monostearate; the Tween60 refers to polyoxyethylene sorbitan stearate, and the mass ratio of the emulsifier Span 60 to the emulsifier Tween60 is 3: 2; stirring the mixture for 5min at the rotation speed of 10000r/min by a high-shear disperser at room temperature to completely disperse the emulsifier uniformly, adding hot water at 70-80 ℃ for 10min along the stirring direction, continuously stirring the mixture for 2min, adding a thickener carboxymethyl cellulose sodium aqueous solution to completely emulsify the defoamer, continuously stirring the mixture for 3min, and adjusting the pH of the emulsion to be 7 by using a NaOH aqueous solution with the mass fraction of 10% to prepare the concrete defoamer xp-4 emulsion.
Example 5:
step 1: vacuum distilling low hydrogen content siloxane (hydrogen content 0.18%), allyl alcohol polyoxyethylene polyoxypropylene ether, and glucose oxyethyl methacrylate until water content is below 0.1%;
step 2: 1mol of siloxane with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor are added into a three-mouth bottle provided with a mechanical stirring device, a thermometer and a reflux condenser, wherein the mass ratio of the isopropanol as the solvent to the total reactants is 30-40%,the mass ratio of the polymerization inhibitor hydroquinone to the total reactant is 0.15%; heating to 50 deg.C, adding 50 μ g-1Heating chloroplatinic acid catalyst to 95 ℃, firstly dripping 0.6mol of allyl alcohol polyoxyethylene polyoxypropylene ether at a constant speed under stirring, then dripping 0.6mol of glucose oxyethyl methacrylate at a constant speed, and continuing to react for 5 hours after dripping;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid which is taken as a main monomer xp-5 of the defoaming agent;
and 4, step 4: sequentially adding a main monomer xp-5 of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a 100mL beaker, wherein the Span 60 refers to sorbitan monostearate, also called sorbitan monostearate; the Tween60 refers to polyoxyethylene sorbitan stearate, and the mass ratio of the emulsifier Span 60 to the emulsifier Tween60 is 3: 2; stirring for 5min at the rotating speed of 10000r/min by a high-shear disperser at room temperature to completely disperse the emulsifier uniformly, adding hot water at 70-80 ℃ for 10min along the stirring direction, continuously stirring for 2min, adding a thickener carboxymethyl cellulose sodium aqueous solution to completely emulsify the defoamer, continuously stirring for 3min, adjusting the pH of the emulsion to be 7 by using a NaOH aqueous solution with the mass fraction of 10%, and preparing the concrete defoamer xp-5 emulsion.
Example 6:
step 1: vacuum distilling low hydrogen content siloxane (hydrogen content 0.18%), allyl alcohol polyoxyethylene polyoxypropylene ether, and glucose oxyethyl methacrylate until water content is below 0.1%;
step 2: adding 1mol of siloxane with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor into a three-neck flask provided with a mechanical stirring pipe, a thermometer and a reflux condenser, wherein the mass ratio of the isopropanol as the solvent to the total reactants is 30-40%, and the mass ratio of the hydroquinone as the polymerization inhibitor to the total reactants is 0.15%; heating to 50 deg.C, adding 50 μ g-1Heating chloroplatinic acid catalyst to 95 ℃, dropwise adding 1.20mol of mixed solution of allyl alcohol polyoxyethylene polyoxypropylene ether and glucose oxyethyl methacrylate at constant speed while stirring, dropwise adding for 1h, and continuing to react for 5h after dropwise adding; it is composed ofMedium n (allyl alcohol polyoxyethylene polyoxypropylene ether): n (gluconoxyethyl methacrylate) ═ 1: 1;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid which is taken as a main monomer xp-6 of the defoaming agent;
and 4, step 4: sequentially adding a main monomer xp-6 of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a 100mL beaker, wherein the Span 60 refers to sorbitan monostearate, also called sorbitan monostearate; the Tween60 refers to polyoxyethylene sorbitan stearate, and the mass ratio of the emulsifier Span 60 to the emulsifier Tween60 is 3: 2; stirring the mixture for 5min at the rotation speed of 10000r/min by a high-shear disperser at room temperature to completely disperse the emulsifier uniformly, adding hot water at 70-80 ℃ for 10min along the stirring direction, continuously stirring the mixture for 2min, adding a thickener carboxymethyl cellulose sodium aqueous solution to completely emulsify the defoamer, continuously stirring the mixture for 3min, and adjusting the pH of the emulsion to be 7 by using a NaOH aqueous solution with the mass fraction of 10% to prepare the concrete defoamer xp-6 emulsion.
Comparative tests were carried out on the concrete defoaming agents synthesized in examples 1 to 6 of the present invention and commercially available concrete defoaming agent products:
the performance of the concrete defoamer prepared in the embodiment of the invention is verified by taking the defoaming time, the re-foaming height (the re-foaming height is based on the foam height after 5 min), the gas content of concrete and the compressive strength of concrete as indexes, and the concrete defoamer is compared with a certain commercially available organosilicon defoamer XGZ321, and the test results are shown in Table 1. In the test, the cement used is Jidong P.O 42.5.5 ordinary portland cement, the mineral powder is produced by Shaanxi Li forest building materials Co., Ltd, the fly ash is Huaneng II-grade fly ash, the sand used is river sand, the stone is continuous graded broken stone, the admixture is an aqueous solution of a polycarboxylic acid water reducing agent compounded with an antifoaming agent and other additives (wherein the antifoaming agent accounts for 5 ten-thousandths of the mass of the admixture), and the mixing proportion of the concrete is shown in Table 2. The defoaming performance of the defoaming agent is measured according to a related measuring method in GB/T26527-; the compression strength test of the fresh concrete is detected by referring to GB/T50081-2002 'test method for mechanical properties of ordinary concrete'.
TABLE 1 antifoam Properties
TABLE 2C 60 concrete mixing ratio (kg/m)3)
The comparison in Table 1 shows that the defoaming agent prepared by the invention has good defoaming performance, wherein the performances of the embodiment 2 and the embodiment 6 are superior to those of the XGZ321 defoaming agent on the market; in the comparison of the foam inhibition performance, the foam inhibition performance of the examples 1 to 6 is better than that of XGZ 321; as can be seen from concrete tests, after the defoamer prepared in the embodiment is added, the gas content of the concrete is lower than that of the concrete prepared by the commercial XGZ321 defoamer, and the compressive strength of the concrete meets the relevant regulation of the strength value of the C60 self-compacting concrete in GB/T50107-2010 concrete strength detection and evaluation Standard, so that the comprehensive performance of the defoamer prepared in the invention is obviously better than that of the commercial XGZ321 defoamer.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (6)
1. A method for synthesizing a concrete defoamer is characterized by comprising the following steps: the concrete defoamer has a structural formula as follows:
wherein: a is an integer of 11 to 15, b is an integer of 11 to 17, x is an integer of 3 to 30, y is an integer of 7 to 30, z is an integer of 1 to 15, R1Is CH3Or H, R2Is OH;
the concrete defoamer is prepared by taking siloxane with low hydrogen content, glycosyl acrylate compounds and allyl alcohol polyoxyethylene polyoxypropylene ether as raw materials and adopting hydrosilylation reaction; the glycosyl acrylate compound is glucose oxygen ethyl acrylate or glucose oxygen ethyl methacrylate;
the method comprises the following specific steps:
step 1: vacuum distilling low hydrogen content siloxane, allyl alcohol polyoxyethylene polyoxypropylene ether, and glycosyl acrylate compound;
step 2: adding siloxane with low hydrogen content, isopropanol as a solvent and hydroquinone as a polymerization inhibitor into a three-necked bottle provided with a stirring pipe, a thermometer and a reflux condenser, heating to 50 ℃, adding a chloroplatinic acid catalyst, heating to 85-95 ℃, dropwise adding mixed solution of allyl alcohol polyoxyethylene polyoxypropylene ether and glycosyl acrylate compound at constant speed under stirring, dropwise adding for 1h, and continuing to react for 5h after dropwise adding;
and step 3: after the reaction is finished, carrying out reduced pressure distillation to remove isopropanol and other low-boiling-point impurities to obtain a light yellow transparent viscous liquid as a main monomer of the defoaming agent;
and 4, step 4: sequentially adding a main monomer of a defoaming agent, an emulsifier Span 60 and an emulsifier Tween60 into a container, stirring for 5min at room temperature by using a high-shear disperser at a rotating speed of not less than 10000r/min to completely disperse the emulsifier uniformly, then adding hot water at 70-80 ℃ for 10min along the stirring direction, continuing stirring for 2min, then adding a thickening agent sodium carboxymethyl cellulose aqueous solution to completely emulsify the defoaming agent, continuing stirring for 3min, and adjusting the pH value of the emulsion to be 7 by using a NaOH aqueous solution to obtain the concrete defoaming agent emulsion.
2. The method of claim 1, wherein the concrete defoamer is prepared by: the low-hydrogen siloxane contains 0.1-0.2% of hydrogen.
3. The method of claim 1, wherein the concrete defoamer is prepared by: the mol ratio of the allyl alcohol polyoxyethylene polyoxypropylene ether dropwise added in the step 2 to the glycosyl acrylate compound is 1: 1-2.
4. The method of claim 1, wherein the concrete defoamer is prepared by: in the step 2, the ratio of the amount of the low-hydrogen siloxane to the sum of the amounts of the allyl alcohol polyoxyethylene polyoxypropylene ether and the glycosyl acrylate compound is 1: 1.2-1: 1.4.
5. The method of claim 1, wherein the concrete defoamer is prepared by: the chloroplatinic acid catalyst is isopropanol solution of chloroplatinic acid, and the platinum content in the catalyst is 10 mu g of the total mass of the reactant system-1～60μg·g-1。
6. The method of claim 1, wherein the concrete defoamer is prepared by: in the step 2, the mass ratio of the solvent isopropanol to the total reactants is 30-40%, and the mass ratio of the polymerization inhibitor hydroquinone to the total reactants is 0.15%.
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