CN118027309A - High water-reducing and air-content stable concrete additive and preparation method thereof - Google Patents
High water-reducing and air-content stable concrete additive and preparation method thereof Download PDFInfo
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- CN118027309A CN118027309A CN202410410578.8A CN202410410578A CN118027309A CN 118027309 A CN118027309 A CN 118027309A CN 202410410578 A CN202410410578 A CN 202410410578A CN 118027309 A CN118027309 A CN 118027309A
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- 239000000654 additive Substances 0.000 title claims abstract description 10
- 230000000996 additive effect Effects 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000178 monomer Substances 0.000 claims abstract description 70
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 35
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 35
- VXDHQYLFEYUMFY-UHFFFAOYSA-N 2-methylprop-2-en-1-amine Chemical compound CC(=C)CN VXDHQYLFEYUMFY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 23
- -1 isopentenyl Chemical group 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 10
- 239000011976 maleic acid Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical group OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 6
- 229930003268 Vitamin C Natural products 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 6
- 235000019154 vitamin C Nutrition 0.000 claims description 6
- 239000011718 vitamin C Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 125000005394 methallyl group Chemical group 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 230000003254 anti-foaming effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000013530 defoamer Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- NKTJHWQSYOZAKK-UHFFFAOYSA-N n-(3-amino-4-hydroxyphenyl)methanesulfonamide Chemical compound CS(=O)(=O)NC1=CC=C(O)C(N)=C1 NKTJHWQSYOZAKK-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of high molecular compounds, and particularly relates to a high water-reducing and air-content stable concrete additive and a preparation method thereof. The high water-reducing and air-content stable concrete additive comprises a water-reducing component, a defoaming component and water, wherein the water-reducing component is prepared from unsaturated polyoxyethylene ether monomers, unsaturated acid monomers, functional monomers, modified monomers, an initiator, a reducing agent, a chain transfer agent, a nano titanium dioxide aqueous solution and deionized water, the functional monomers are 2-methylallylamine, and the modified monomers are vinyl triethoxysilane; the defoaming component is a water-insoluble defoaming agent. The invention has high water reducing performance and can stabilize the defoaming component, and the prepared concrete has excellent performance.
Description
Technical Field
The invention belongs to the technical field of high molecular compounds, and particularly relates to a high water-reducing and air-content stable concrete additive and a preparation method thereof.
Background
Concrete admixtures are widely used in concrete to improve its fresh mixing properties, hardening properties and durability properties such as fluidity, strength, freezing resistance, erosion resistance, etc. Concrete admixtures are often used in the form of aqueous solutions. Because the main component polycarboxylic acid water reducer (PCE) in the concrete admixture is a surfactant, the concrete admixture has higher air entraining property, and can cause higher air content of the concrete. The high air content reduces the strength of the hardened concrete to some extent and is liable to cause honeycomb pitting. Therefore, defoamers are often added to concrete admixtures to control the problem of high concrete gas content caused by polycarboxylate water reducers. Most of the defoamers are hydrophobic, mainly organic silicon, mineral oil, phosphate or polypropylene oxide substances, have poor water solubility and are in an unstable state in the concrete admixture. The defoamer is easy to separate in the concrete admixture and enrich on the surface of the admixture, so that the admixture is non-homogeneous. If such an uneven admixture is applied to concrete, it will cause great damage to workability, strength and durability of the concrete.
At present, many researches are made by scientific researchers to solve the problem of poor compatibility of the defoamer in the concrete admixture.
Chinese patent CN112724408a discloses a defoaming functional material, a defoaming polycarboxylate water reducer and a preparation method thereof, wherein the defoaming functional material is prepared by hydrosilation reaction of alkynol and hydrogen-containing silicone oil; the defoaming type polycarboxylate water reducer is prepared by copolymerizing an unsaturated polyoxyethylene ether monomer, the defoaming type functional material and unsaturated carboxylic acid. The preparation process of the defoaming functional material in the patent is complex, and the product yield is low.
Chinese patent CN107814886a discloses a defoaming polycarboxylate water reducer and a preparation method thereof, the raw materials of the defoaming polycarboxylate water reducer comprise the following components in parts by weight: 150-180 parts of unsaturated polyoxyethylene ether monomer with molecular weight of 600-3000, 20-50 parts of unsaturated polyoxyethylene polyoxypropylene ether monomer, 15-26 parts of unsaturated acid, 1-10 parts of acetylenic diol polyether, 1.0-3.5 parts of oxidant, 0.1-2.5 parts of reducing agent, 0.5-2.5 parts of chain transfer agent, 320 parts of water and a proper amount of liquid alkali with mass concentration of 30-32%. The patent synthesizes the defoaming type PCE by adopting the alkyne diol polyether with foam inhibition and defoaming functions, but the defoaming type PCE has the problem that the defoaming type functional group quantity in the structure is too small, and the ideal defoaming effect cannot be achieved.
Patent EP1242330A1 discloses a dissolution defoamer for cementitious components, which is prepared by mixing a solubilizer, a hydrophobic defoamer and a dispersant. This patent stabilizes a concrete admixture containing an insoluble defoaming component and a dispersing component by using a solubilizing agent, but the patent has a problem in that the use of the solubilizing agent affects the water reduction rate of the admixture.
Chinese patent CN113003982a discloses a microcrystalline waterproofing agent for concrete and application thereof, and the microcrystalline waterproofing agent comprises the following components in parts by mass: 1-5 parts of a defoaming agent; 2-4 parts of modified silicon dioxide powder; 7-10 parts of a waterproof agent; 0.5-1.5 parts of water reducer. The purpose of stabilizing the defoaming component is achieved by adding the modified silica powder particles into the additive, but the modified silica powder particles are easy to agglomerate, so that the stabilizing effect on the defoaming component in the additive is greatly reduced.
The water-reducing rate of PCE, the main component of the concrete admixture, determines the cost of the concrete admixture. In order to reduce the cost of concrete admixtures, a great deal of research has been conducted in the prior art to increase the water reduction rate of PCE. The molecular structure of the PCE has designability, and the water reduction rate of the PCE can be improved by introducing specific functional groups into the PCE. Chinese patent CN114213597a adopts the acylated esterification product of 2-amino-1-phenol-4-methylsulfonamide and unsaturated acid as functional monomers, chinese patent CN114276499a realizes the introduction of a large number of carboxyl groups in PCE molecular structure by increasing the amount of unsaturated acid, chinese patent CN108558259a uses active monomers containing phosphorous acid functional groups and sulfonic acid functional groups. The method for improving the PCE water reduction rate disclosed in the patent has the problems of complex preparation process of the functional monomer, unobvious improvement of the water reduction effect and difficult industrialization.
Disclosure of Invention
The invention aims to provide the high water-reducing and air-content stable concrete admixture which has high water-reducing performance and can stabilize defoaming components, and the prepared concrete has excellent performance; the invention also provides a preparation method of the high water-reducing and air-content stable concrete admixture.
The high water-reducing and air-content stable concrete admixture comprises a water-reducing component, a defoaming component and water, wherein the water-reducing component is prepared from unsaturated polyoxyethylene ether monomers, unsaturated acid monomers, functional monomers, modified monomers, an initiator, a reducing agent, a chain transfer agent, a nano titanium dioxide aqueous solution and deionized water, the functional monomers are 2-methylallylamine, and the modified monomers are vinyl triethoxysilane; the defoaming component is a water-insoluble defoaming agent.
The unsaturated polyoxyethylene ether monomer is isopentenyl polyoxyethylene ether or methallyl polyoxyethylene ether.
The structural formula of the isopentenyl polyoxyethylene ether is as follows:
wherein n 1 is 25 to 100.
The structural formula of the methallyl polyoxyethylene ether is as follows:
wherein n 1 is 25 to 100.
The unsaturated acid monomer is one or more of acrylic acid, methacrylic acid or maleic acid.
The structural formula of the functional monomer 2-methylallylamine is as follows:
The structural formula of the modified monomer vinyl triethoxysilane is as follows:
The mol ratio of the unsaturated polyoxyethylene ether monomer to the unsaturated acid monomer to the functional monomer to the modified monomer is 1:3.5-4:0.3-0.8:0.25-0.7.
The initiator is one of hydrogen peroxide, ammonium persulfate or sodium peroxide, and the use amount of the initiator is 1.2-1.5% of the total mass of the unsaturated polyoxyethylene ether monomer, the unsaturated acid monomer, the functional monomer and the modified monomer.
The reducing agent is vitamin C or sodium bisulphite, and the mass ratio of the initiator to the reducing agent is 1:0.4-0.7.
The chain transfer agent is mercaptopropionic acid or mercaptoacetic acid, and the use amount of the chain transfer agent is 0.7-0.9% of the total mass of the unsaturated polyoxyethylene ether monomer, the unsaturated acid monomer, the functional monomer and the modified monomer.
The concentration of the nano titanium dioxide aqueous solution is 15-20 wt%, and the size of the nano titanium dioxide in the nano titanium dioxide aqueous solution is 6-8nm.
The water-insoluble antifoaming agent is tributyl phosphate antifoaming agent or polydimethylsiloxane antifoaming agent.
The consumption of the water reducing component is 68-72% of the mass of the high water reducing and air content stable concrete admixture, and the consumption of the defoaming component is 0.03-0.05% of the mass of the high water reducing and air content stable concrete admixture.
The preparation method of the high water-reducing and air-content stable concrete admixture comprises the following steps:
(1) Stirring and heating an unsaturated polyoxyethylene ether monomer, a modified monomer and deionized water to obtain a base solution;
(2) Mixing an unsaturated acid monomer, a functional monomer, a reducing agent, a chain transfer agent and deionized water to obtain a solution A, and mixing an initiator and deionized water to obtain a solution B;
(3) Adding the solution A and the solution B into the base solution for reaction at the same time, continuing to perform heat preservation reaction after the addition is finished, cooling, adjusting the pH value, and adding deionized water to obtain PCE solution;
(4) Adding the PCE solution obtained in the step (3) into a nano titanium dioxide aqueous solution to react in a nitrogen atmosphere, continuing to react after the addition, cooling, refining and concentrating to obtain a water-reducing component;
(5) The water reducing component, the defoaming component and the water are mixed to obtain the high water reducing and air content stable concrete admixture.
The mass concentration of the base solution in the step (1) is 50-60wt.%.
The heating temperature in the step (1) is 50-60 ℃.
The mass concentration of the solution A in the step (2) is 40-50 wt%, and the mass concentration of the solution B is 3.0-5.0 wt%.
The adding time of the solution A in the step (3) is 2.0-2.5h, and the adding time of the solution B is 2.5-3.5h.
The reaction temperature in the step (3) is 50-60 ℃.
And (3) continuing to keep the temperature of the reaction at 50-60 ℃ for 1.0-1.5h.
And (3) cooling to below 35 ℃.
The pH adjustment in the step (3) is to adjust the pH to 9.0-10 by sodium hydroxide.
The solids content of the PCE solution in step (3) is 28-32wt.%.
The mass ratio of PCE in the PCE solution in the step (4) to the nano titanium dioxide aqueous solution is 29-31:450-600.
And (3) adding the PCE solution in the step (4) for 0.5-1h.
The reaction temperature in the step (4) is 50-60 ℃.
And (3) continuing the reaction in the step (4) for 1.0-1.5h.
And (3) cooling to below 35 ℃ in the step (4).
In the step (4), the refining is performed by adopting a dialysis bag, and the molecular weight cut-off of the dialysis bag is 5000Da.
The solids content of the water-reducing component in step (4) is 22.0-24.0wt.%.
When the high water-reducing and air-containing stable concrete admixture of the invention is applied to concrete, the mixing amount of the high water-reducing and air-containing stable concrete admixture is 1.0 to 2.0wt.% of the dosage of the cementing material.
The invention introduces the functional monomer 2-methylallylamine and the modified monomer vinyl triethoxysilane into the molecular structure of PCE, and then forms a water reducing component with nano titanium dioxide through hydrolytic polycondensation.
The invention introduces an alkoxy silane group (-Si-OR) in modified monomer vinyl triethoxy silane into a PCE molecular structure, and under alkaline condition, the modified monomer is hydrolyzed to obtain-Si-OH with high reaction activity, and the-Si-OH can be combined with nano titanium dioxide with a large number of hydroxyl groups on the surface through polycondensation reaction to obtain a water reducing component. The nanometer titanium dioxide is easy to agglomerate when being singly used, and PCE molecules are connected with the nanometer titanium dioxide through the modified monomer vinyl triethoxysilane, so that the agglomeration phenomenon of the nanometer titanium dioxide can be effectively avoided.
According to the invention, the functional monomer 2-methylallylamine is introduced into the PCE molecular structure, and the N atom in the 2-methylallylamine contains lone pair electrons, so that the repulsive force between carboxyl groups in the PCE molecules can be effectively increased after the 2-methylallylamine is introduced, the PCE molecules are fully diffused in the solution, the dispersing effect of the PCE molecules on cement particles is increased, and the water reducing rate is further improved. In addition, unlike the acidic nature of the amide group, the-NH 2 in 2-methylallylamine is basic, can provide a basic environment, and can more easily promote the hydrolysis of the alkoxysilane group (-Si-OR) to obtain-Si-OH.
The nano titanium dioxide in the water reducing component can provide a larger surface area, which is beneficial to stabilizing the water-insoluble defoamer in the concrete admixture, so that layering does not occur; in addition, the nano titanium dioxide with a large number of hydroxyl groups on the surface can absorb water to form a water film, so that the dispersing effect among cement particles is enhanced, and the water reduction rate is improved.
The beneficial effects of the invention are as follows:
(1) Introducing modified monomer vinyl triethoxysilane into the molecular structure of PCE, hydrolyzing under alkaline condition to obtain-Si-OH, and continuing to perform polycondensation reaction with hydroxyl on the surface of nano titanium dioxide, so as to increase the binding force between PCE and nano titanium dioxide, form stable water reducing component, and effectively avoid agglomeration phenomenon of nano titanium dioxide.
(2) By introducing a functional monomer 2-methallylamine into the PCE molecules, the diffusion of the PCE molecules in the solution can be promoted, the dispersing effect of the PCE molecules on cement particles is improved, and the water reducing rate is further improved; in addition, the alkaline environment provided by the-NH 2 in the 2-methylallylamine can better promote the hydrolysis of the alkoxysilane groups (-Si-OR) to obtain the-Si-OH.
(3) The larger surface area of the nano titanium dioxide in the water reducing component can stabilize the water-insoluble defoaming component in the concrete admixture, so that the concrete admixture is not layered.
Detailed Description
The invention is further described with reference to the following examples:
Example 1
(1) Stirring and heating 1mol of methyl allyl polyoxyethylene ether with molecular weight 2400, 0.6mol of vinyl triethoxysilane and deionized water to 50 ℃ to obtain a base solution with mass concentration of 60 wt.%;
(2) Mixing acrylic acid, 2-methylallylamine, vitamin C, mercaptopropionic acid and deionized water to obtain a solution A with the mass concentration of 40wt.% and mixing sodium peroxide and deionized water to obtain a solution B with the mass concentration of 3.0 wt.%; wherein the molar ratio of the acrylic acid to the 2-methylallylamine to the methylallyl polyoxyethylene ether is 3.5:0.3:1, the sodium peroxide is 1.5% of the total mass of the methylallyl polyoxyethylene ether, the vinyl triethoxysilane, the acrylic acid and the 2-methylallylamine, the mass ratio of the sodium peroxide to the vitamin C is 1:0.4, and the mercaptopropionic acid is 0.8% of the total mass of the methylallyl polyoxyethylene ether, the vinyl triethoxysilane, the acrylic acid and the 2-methylallylamine;
(3) Simultaneously dropwise adding the solution A and the solution B into a base solution at 50 ℃, keeping the temperature of 50 ℃ for reaction, uniformly dropping the solution A for 2.5h, uniformly dropping the solution B for 3.5h, continuously preserving heat for reaction for 1.2h at 50 ℃ after the solution B is completely dropped, cooling to below 35 ℃, adjusting the pH value to 9.0 by using sodium hydroxide, and adding deionized water to obtain PCE solution with the solid content of 30 wt%;
(4) 450g of 20wt.% nano titanium dioxide aqueous solution (the size of nano titanium dioxide is 6-8 nm) is heated to 30 ℃, and stirred for 30min to be completely dispersed, so as to obtain dispersed nano titanium dioxide aqueous solution; dropwise adding 100g of the PCE solution obtained in the step (3) into the dispersed nano titanium dioxide aqueous solution in a nitrogen atmosphere, keeping the reaction at 50 ℃, keeping the adding time of the PCE solution at 1h, continuing the reaction for 1.0h after the adding is finished, cooling to below 35 ℃, refining by using a dialysis bag with a molecular weight cut-off of 5000Da, and concentrating to obtain a water-reducing component with a solid content of 23.0 wt%; wherein, the nano titanium dioxide in the nano titanium dioxide aqueous solution is provided by Shanghai Yingcheng new material Co., ltd;
(5) The water reducing component, the tributyl phosphate defoamer and water are mixed to obtain the high water reducing and air content stable concrete admixture S1, wherein the water reducing component is 70% of the mass of the high water reducing and air content stable concrete admixture, and the tributyl phosphate defoamer is 0.03% of the mass of the high water reducing and air content stable concrete admixture.
Example 2
(1) Stirring and heating 1mol of isopentenyl polyoxyethylene ether with molecular weight of 3000, 0.7mol of vinyl triethoxysilane and deionized water to 60 ℃ to obtain a base solution with mass concentration of 50 wt.%;
(2) Mixing acrylic acid, maleic acid, 2-methylallylamine, sodium bisulphite, thioglycollic acid and deionized water to obtain a solution A with the mass concentration of 50 wt%, and mixing ammonium persulfate and deionized water to obtain a solution B with the mass concentration of 3.0 wt%; wherein the mol ratio of the acrylic acid to the maleic acid to the 2-methylallylamine to the isopentenyl polyoxyethylene ether is 3:1:0.4:1, the ammonium persulfate is 1.2% of the total mass of the isopentenyl polyoxyethylene ether, the vinyl triethoxysilane, the acrylic acid, the maleic acid and the 2-methylallylamine, the mass ratio of the ammonium persulfate to the sodium bisulfate is 1:0.7, and the mercaptoacetic acid is 0.9% of the total mass of the isopentenyl polyoxyethylene ether, the vinyl triethoxysilane, the acrylic acid, the maleic acid and the 2-methylallylamine;
(3) Simultaneously dropwise adding the solution A and the solution B into a base solution at 60 ℃, keeping the temperature of 60 ℃ for reaction, uniformly dropping the solution A for 2.5h, uniformly dropping the solution B for 3.0h, continuously preserving heat for reaction at 60 ℃ for 1.0h after the solution B is completely dropped, cooling to below 35 ℃, adjusting the pH value to 10 by using sodium hydroxide, and adding deionized water to obtain PCE solution with the solid content of 28 wt%;
(4) Heating 500g of 18wt.% nano titanium dioxide aqueous solution (the size of nano titanium dioxide is 6-8 nm) to 25 ℃, and stirring for 45min to completely disperse to obtain dispersed nano titanium dioxide aqueous solution; dropwise adding 107g of PCE solution obtained in the step (3) into the dispersed nano titanium dioxide aqueous solution in a nitrogen atmosphere, keeping the reaction at 60 ℃, keeping the adding time of the PCE solution at 0.5h, continuing the reaction for 1.5h after the adding is finished, cooling to below 35 ℃, refining by using a dialysis bag with a molecular weight cutoff of 5000Da, and concentrating to obtain a water-reducing component with a solid content of 22.4 wt%;
(5) The water reducing component, the polydimethylsiloxane defoamer and water are mixed to obtain the high water reducing and air content stable concrete admixture S2, wherein the water reducing component is 72% of the mass of the high water reducing and air content stable concrete admixture, and the polydimethylsiloxane defoamer is 0.05% of the mass of the high water reducing and air content stable concrete admixture.
Example 3
(1) Stirring and heating 1mol of isopentenyl polyoxyethylene ether with molecular weight of 1200, 0.25mol of vinyl triethoxysilane and deionized water to 55 ℃ to obtain a base solution with mass concentration of 55 wt.%;
(2) Mixing maleic acid 3.5mol, 2-methylallylamine, vitamin C, mercaptopropionic acid and deionized water to obtain a solution A with a mass concentration of 40 wt%, and mixing hydrogen peroxide and deionized water to obtain a solution B with a mass concentration of 5.0 wt%; wherein the mol ratio of maleic acid, 2-methylallylamine and isopentenyl polyoxyethylene ether is 3.5:0.8:1, the hydrogen peroxide is 1.3% of the total mass of isopentenyl polyoxyethylene ether, vinyl triethoxysilane, maleic acid and 2-methylallylamine, the mass ratio of hydrogen peroxide to vitamin C is 1:0.6, and the mercaptopropionic acid is 0.7% of the total mass of isopentenyl polyoxyethylene ether, vinyl triethoxysilane, maleic acid and 2-methylallylamine;
(3) Simultaneously dropwise adding the solution A and the solution B into a base solution at 55 ℃, keeping the temperature of 55 ℃ for reaction, uniformly dropping the solution A for 2.0h, uniformly dropping the solution B for 2.5h, continuously preserving heat for reaction for 1.5h at 55 ℃ after the solution B is completely dropped, cooling to below 35 ℃, adjusting the pH value to 9.5 by using sodium hydroxide, and adding deionized water to obtain PCE solution with the solid content of 32 wt%;
(4) Heating 600g of 15wt.% nano titanium dioxide aqueous solution (the size of nano titanium dioxide is 6-8 nm) to 20 ℃, and stirring for 60min to completely disperse to obtain dispersed nano titanium dioxide aqueous solution; dropwise adding 94g of the PCE solution obtained in the step (3) into the dispersed nano titanium dioxide aqueous solution in a nitrogen atmosphere, keeping the temperature of 55 ℃ for reaction, keeping the adding time of the PCE solution at 0.8h, continuing to react for 1.2h after the adding is finished, cooling to below 35 ℃, refining by using a dialysis bag with a molecular weight cutoff of 5000Da, and concentrating to obtain a water-reducing component with a solid content of 23.6 wt%;
(5) The water reducing component, the tributyl phosphate defoamer and water are mixed to obtain the high water reducing and air content stable concrete admixture S3, wherein the water reducing component is 68% of the mass of the high water reducing and air content stable concrete admixture, and the tributyl phosphate defoamer is 0.04% of the mass of the high water reducing and air content stable concrete admixture.
Comparative example 1
The procedure of example 1 was otherwise repeated except that 2-methylallylamine was not added to obtain a concrete admixture C1.
Comparative example 2
The procedure of example 1 was repeated except that vinyltriethoxysilane was not added to obtain a concrete admixture C2.
Comparative example 3
The procedure of example 1 was otherwise repeated without adding an aqueous solution of nano titanium dioxide to obtain a concrete admixture C3.
The concrete admixture of examples 1 to 3 and comparative examples 1 to 3 was subjected to stability test, and the test results are shown in Table 1.
As can be seen from table 1, after the different concrete admixtures were left at 25 ℃ and 40 ℃ for 7 days, the concrete admixture C1 appeared to be slightly layered, the concrete admixture C2 appeared to be slightly layered, and the concrete admixture C3 appeared to be significantly layered; the concrete additives S1, S2 and S3 are stable, and the solution is uniform and does not delaminate. From the above, it was found that, compared with example 1, comparative examples 1 to 3 were not able to obtain a uniform, non-layered solution without any of the raw materials of 2-methylallylamine, vinyltriethoxysilane and nano titania aqueous solutions.
Detecting concrete according to GB8076-2008, wherein reference cement is selected, sand is sand in a zone II, the fineness modulus is 2.8, and the mud content is 1.3%; the stone adopts crushed stone with nominal grain diameter of 5-20mm, adopts secondary grading, wherein 5-10mm accounts for 40% and 10-20mm accounts for 60%, and meets the requirement of continuous grading. The reference concrete mixing ratio is cement: sand: stone: water = 360:855:965:230, the mixing amount of the concrete admixture is 1.0wt.% of the cement. The water reduction rate and the air content of the tested concrete doped with different concrete additives are detected, and the results are shown in Table 2.
As can be seen from Table 2, the concrete admixture S1 has a higher water reduction rate and a smaller change value of the air content after 60 minutes as compared with the concrete admixtures C1, C2 and C3, indicating that the concrete admixture S1 has better water reduction and air content stability.
Claims (10)
1. The high water-reducing and air-content stable concrete additive comprises a water-reducing component, a defoaming component and water, and is characterized in that the water-reducing component is prepared from unsaturated polyoxyethylene ether monomers, unsaturated acid monomers, functional monomers, modified monomers, an initiator, a reducing agent, a chain transfer agent, a nano titanium dioxide aqueous solution and deionized water, wherein the functional monomers are 2-methylallylamine, and the modified monomers are vinyltriethoxysilane; the defoaming component is a water-insoluble defoaming agent.
2. The high water-reducing and air-containing stable concrete admixture according to claim 1, wherein the unsaturated polyoxyethylene ether monomer is isopentenyl polyoxyethylene ether or methallyl polyoxyethylene ether.
3. The high water-reducing and air-containing stable concrete admixture according to claim 2, characterized in that the isopentenyl polyoxyethylene ether has the following structural formula:
Wherein n 1 is 25 to 100;
the structural formula of the methallyl polyoxyethylene ether is as follows:
wherein n 1 is 25 to 100.
4. The high water-reducing and air-containing stable concrete admixture according to claim 1, wherein the unsaturated acid monomer is one or more of acrylic acid, methacrylic acid or maleic acid, and the molar ratio of unsaturated polyoxyethylene ether monomer, unsaturated acid monomer, functional monomer and modified monomer is 1:3.5-4:0.3-0.8:0.25-0.7; the initiator is one of hydrogen peroxide, ammonium persulfate or sodium peroxide, and the use amount of the initiator is 1.2-1.5% of the total mass of the unsaturated polyoxyethylene ether monomer, the unsaturated acid monomer, the functional monomer and the modified monomer; the reducing agent is vitamin C or sodium bisulphite, and the mass ratio of the initiator to the reducing agent is 1:0.4-0.7; the chain transfer agent is mercaptopropionic acid or mercaptoacetic acid, and the use amount of the chain transfer agent is 0.7-0.9% of the total mass of the unsaturated polyoxyethylene ether monomer, the unsaturated acid monomer, the functional monomer and the modified monomer; the concentration of the nano titanium dioxide aqueous solution is 15-20 wt%, and the size of the nano titanium dioxide in the nano titanium dioxide aqueous solution is 6-8nm.
5. The high water-reducing and air-containing stable concrete admixture according to claim 1, wherein the non-water-soluble antifoaming agent is tributyl phosphate antifoaming agent or polydimethylsiloxane antifoaming agent, the water-reducing component is used in an amount of 68-72% by mass of the high water-reducing and air-containing stable concrete admixture, and the antifoaming component is used in an amount of 0.03-0.05% by mass of the high water-reducing and air-containing stable concrete admixture.
6. A method for preparing the high water-reducing and air-content stable concrete admixture according to any one of claims 1 to 5, comprising the steps of:
(1) Stirring and heating an unsaturated polyoxyethylene ether monomer, a modified monomer and deionized water to obtain a base solution;
(2) Mixing an unsaturated acid monomer, a functional monomer, a reducing agent, a chain transfer agent and deionized water to obtain a solution A, and mixing an initiator and deionized water to obtain a solution B;
(3) Adding the solution A and the solution B into the base solution for reaction at the same time, continuing to perform heat preservation reaction after the addition is finished, cooling, adjusting the pH value, and adding deionized water to obtain PCE solution;
(4) Adding the PCE solution obtained in the step (3) into a nano titanium dioxide aqueous solution to react in a nitrogen atmosphere, continuing to react after the addition, cooling, refining and concentrating to obtain a water-reducing component;
(5) The water reducing component, the defoaming component and the water are mixed to obtain the high water reducing and air content stable concrete admixture.
7. The method for preparing a stable concrete admixture with high water and air content according to claim 6, wherein the mass concentration of the base liquid in the step (1) is 50-60wt.% and the heating temperature is 50-60 ℃.
8. The method for preparing a high water-reducing and air-containing stable concrete admixture according to claim 6, wherein the mass concentration of the solution a in the step (2) is 40 to 50wt.%, and the mass concentration of the solution B is 3.0 to 5.0wt.%.
9. The method for preparing the high water-reducing and air-content stable concrete admixture according to claim 6, wherein the adding time of the solution A in the step (3) is 2.0-2.5h, the adding time of the solution B is 2.5-3.5h, the reaction temperature is 50-60 ℃, the heat-preserving reaction time is 1.0-1.5h, the temperature is reduced to below 35 ℃, the pH is adjusted to 9.0-10 by sodium hydroxide, and the solid content of the PCE solution is 28-32wt.%.
10. The method for preparing the high water-reducing and air-content stable concrete admixture according to claim 6, wherein in the step (4), the mass ratio of PCE to nano titanium dioxide aqueous solution in the PCE solution is 29-31:450-600, the addition time of the PCE solution is 0.5-1h, the reaction temperature is 50-60 ℃, the continuous reaction time is 1.0-1.5h, the temperature is reduced to below 35 ℃, the refining is performed by adopting a dialysis bag, and the solid content of the water-reducing component is 22.0-24.0wt.%.
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