CN111592619A - Starch-based polycarboxylate superplasticizer mate, and preparation method and application method thereof - Google Patents
Starch-based polycarboxylate superplasticizer mate, and preparation method and application method thereof Download PDFInfo
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- CN111592619A CN111592619A CN202010558508.9A CN202010558508A CN111592619A CN 111592619 A CN111592619 A CN 111592619A CN 202010558508 A CN202010558508 A CN 202010558508A CN 111592619 A CN111592619 A CN 111592619A
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- polycarboxylate superplasticizer
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- 229920002472 Starch Polymers 0.000 title claims abstract description 73
- 235000019698 starch Nutrition 0.000 title claims abstract description 71
- 239000008107 starch Substances 0.000 title claims abstract description 71
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 63
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920000881 Modified starch Polymers 0.000 claims abstract description 32
- 239000004368 Modified starch Substances 0.000 claims abstract description 32
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 31
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 31
- 235000019426 modified starch Nutrition 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 4
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002261 Corn starch Polymers 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 239000001254 oxidized starch Substances 0.000 claims description 2
- 235000013808 oxidized starch Nutrition 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims 2
- 239000004567 concrete Substances 0.000 abstract description 29
- 230000000740 bleeding effect Effects 0.000 abstract description 6
- 238000005204 segregation Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 230000009044 synergistic interaction Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- 238000002156 mixing Methods 0.000 description 20
- 239000002585 base Substances 0.000 description 16
- 239000004576 sand Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000004568 cement Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 2
- -1 methacrylic acid phosphate ester Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- 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
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a starch-based polycarboxylate superplasticizer mate and a preparation method and a use method thereof, wherein modified starch containing unsaturated double bonds, unsaturated polyoxyethylene ether and deionized water are added into a reaction kettle to obtain a base solution; heating the reaction kettle to 60-90 ℃, and dropwise adding the solution A and the solution B into the base solution within 0.5-3 h respectively, wherein the solution A is an aqueous solution of an acrylic monomer, and the solution B is an aqueous solution of an initiator; and (3) stirring and reacting for 1-5 h after the dropwise adding is finished, cooling to 25-50 ℃ after the reaction is finished, and neutralizing with an alkaline solution until the pH value is 5-8 to obtain the starch-based polycarboxylic acid water reducer mate. The starch-based polycarboxylate superplasticizer mate and the polycarboxylate superplasticizer can be compounded according to the proportion of 5-50: 50-95 for use, have good matching property and synergistic interaction, can reduce the doping amount sensitivity of the polycarboxylate superplasticizer, reduce the segregation, bleeding and bottom grabbing of concrete, and obviously improve the workability of the concrete.
Description
Technical Field
The invention relates to the field of concrete admixtures, in particular to a green and safe starch-based polycarboxylate superplasticizer mate, and a preparation method and a use method thereof.
Background
In large-scale infrastructure construction in China, concrete is widely used as the largest building material, and the performance of the concrete is very important. Concrete admixtures are the core materials for preparing and influencing the performance of modern concrete. The development of the preparation and application technology of the high-performance green additive is beneficial to ensuring the quality of concrete and promoting the development of green buildings and durable buildings.
The concrete high-efficiency water reducing agents such as polycarboxylic acid series, naphthalene series, aliphatic series, sulfamate and the like commonly used in engineering at present are prepared from chemical raw materials obtained in petrochemical industry and coal chemical industry, and have the characteristics of high emission and high energy consumption. Starch is a renewable resource of biomass, is very abundant in reserves in nature, and has the advantages of complete degradability, no pollution to the environment, low price and the like. Under the pressure that petrochemical resources are reduced day by day and the cost of petrochemical raw materials is rapidly increased at present, the concrete admixture prepared by effectively utilizing starch has wide development prospect.
Along with the increase of environmental protection force in China, the exploitation of natural resources for concrete is limited, a large amount of materials such as machine-made sand, tailing sand, recycled aggregate, artificial composite admixture and the like are used, and due to the factors such as change of material properties, poor gradation, quality fluctuation and the like and the reason that the monomer polarity of the polycarboxylic acid water reducer is strong, the mixing amount of the polycarboxylic acid water reducer is sensitive, the wrapping property of newly-mixed concrete slurry is poor, the problems of segregation, bleeding, bottom grabbing, pump blockage and the like easily occur, and the workability and the working degree of concrete are poor.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a starch-based polycarboxylate superplasticizer mate, which has simple preparation process, excellent performance, environmental protection and no pollution, so that a product prepared by the method is compatible with the existing polycarboxylate superplasticizers for use, has good synergistic effect, can improve the water reducing rate and the workability. Meanwhile, the sensitivity of the polycarboxylate superplasticizer can be reduced, the cohesiveness of concrete is improved, and the workability problems of segregation, bleeding and the like of the concrete caused by using machine-made sand, tailing sand, recycled aggregate and poor gradation can be solved.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a starch-based polycarboxylate superplasticizer mate comprises the following raw materials in parts by weight: unsaturated double bond-containing modified starch: 5-20 parts of a solvent; unsaturated polyoxyethylene ether: 5-20 parts of a solvent; acrylic monomer: 1-6 parts; initiator: 0.2-3 parts of a stabilizer; deionized water: 50-80 parts; a proper amount of alkaline solution;
the preparation method comprises the following steps:
(1) adding unsaturated double bond-containing modified starch, unsaturated polyoxyethylene ether and part of deionized water into a reaction kettle to obtain a base solution;
(2) heating the reaction kettle to 60-90 ℃, and dropwise adding the solution A and the solution B into the base solution within 0.5-3 h respectively, wherein the solution A is an aqueous solution of an acrylic monomer, and the solution B is an aqueous solution of an initiator;
(3) and (3) stirring and reacting for 1-5 h after the dropwise adding is finished, cooling to 25-50 ℃ after the reaction is finished, and neutralizing with an alkaline solution until the pH value is 5-8 to obtain the starch-based polycarboxylic acid water reducer mate.
Preferably, 8.5-12.5 parts of modified starch containing unsaturated double bonds; unsaturated polyoxyethylene ether: 8.0-13 parts; acrylic monomer: 2-3 parts of a solvent; initiator: 1-2 parts; deionized water: 65-80 parts.
Preferably, in the (2), the reaction kettle temperature: and (3) dripping the liquid A and the liquid B at 75-90 ℃ for the following time: 1-2 h; in the step (3), stirring reaction: neutralizing the pH value for 1-3 h: 5.5 to 7.
Preferably, the unsaturated double bond-containing modified starch is obtained by reacting starch with a double bond-containing modifier after acidification and degradation treatment; the starch is one or more of corn starch, cassava starch, sweet potato starch, wheat starch, oxidized starch, etherified starch or dextrin; the double-bond modifier is one or more of double-bond acid or double-bond ester, silane coupling agent or double-bond epoxy compound.
Preferably, the unsaturated double bond-containing modified starch is phosphate methacrylate modified starch, gamma-methacryloxypropyltrimethoxysilane modified starch, maleic anhydride modified starch or glycidyl methacrylate modified starch.
Preferably, the unsaturated polyoxyethylene ether is one or more of allyl polyoxyethylene ether, methallyl alcohol polyoxyethylene ether and prenyl alcohol polyoxyethylene ether, and the molecular weight is 1000-10000.
Preferably, the acrylic monomer is one or more of acrylic acid, acrylamide, methacrylic acid, sodium acrylate sulfonate, sodium methacrylate sulfonate, acrylonitrile, maleic anhydride, vinyl acetate and methyl methacrylate.
Preferably, the initiator is one or more of ferrous ammonium sulfate, cerium ammonium nitrate, potassium persulfate, ammonium persulfate and hydrogen peroxide.
The invention also provides the starch-based polycarboxylate superplasticizer mate prepared by the preparation method and a use method thereof, and when the starch-based polycarboxylate superplasticizer mate is used in machine-made sand, tailing sand or poor-gradation concrete, the starch-based polycarboxylate superplasticizer mate and the polycarboxylate superplasticizer are compounded according to the proportion of 5-50: 50-95 for use.
The preparation principle of the starch-based polycarboxylate superplasticizer mate disclosed by the invention is as follows: the modified starch containing unsaturated double bonds has higher reaction activity, can perform aqueous solution free radical copolymerization with unsaturated polyoxyethylene ether and acrylic monomers, and has high grafting efficiency, so that a moderately strong polar hydrophilic group is introduced into the molecular structure of the starch, the water solubility of the starch and the adsorption capacity of the starch on the surface of cement particles are improved, and the water reducing effect is achieved. Because the molecular structure of the starch is grafted with the chain segment of the molecular structure of the polycarboxylic acid, the starch is compounded with the polycarboxylic acid water reducing agent for use, has good matching property and synergistic interaction, and can reduce the doping amount sensitivity of the polycarboxylic acid water reducing agent. The starch molecule has a glucose unit chain structure, so that the starch molecule has better steric hindrance and hydrogen bond complexing capacity of water molecules, and is favorable for improving the workability of concrete and reducing segregation and bleeding phenomena.
By adopting the technical scheme, the invention at least has the following beneficial effects:
1. the starch-based polycarboxylate superplasticizer mate prepared by the preparation method is a concrete functional auxiliary agent, has higher water reducing rate and concrete workability improving function, is compounded with a polycarboxylate superplasticizer for use according to a certain proportion, has a synergistic interaction effect, and can obviously solve the problems of poor wrapping property, easy segregation, bleeding, bottom grabbing, pump blockage and the like in the application process of the polycarboxylate superplasticizer; meanwhile, the problems of sensitivity and adaptability of the polycarboxylate superplasticizer in the mixing amount are solved, the working states of concrete workability, cohesiveness and the like are improved, the concrete pouring working efficiency and the hardened concrete quality are favorably improved, and the polycarboxylate superplasticizer has excellent adaptability to different cements, admixtures, artificial sand, environmental temperatures and concrete mixing ratio fluctuation.
2. The preparation method of the invention selects cheap and renewable starch as the main raw material, and adopts a green and safe aqueous solution free radical polymerization process, and the prepared product belongs to a low-cost green concrete admixture.
3. The invention has no toxicity, no smell and no three wastes discharge in the production and use processes.
Detailed Description
The above is only an outline of the technical solution of the present invention, and in order to make the technical means of the present invention more clear, the present invention is described in further detail in example 1 below
A starch-based polycarboxylate superplasticizer partner comprises: methacrylic acid phosphate ester modified starch: 8.5 wt%; allyl polyoxyethylene ether: 8.2 wt%; acrylic acid: 2.1 wt%; ammonium persulfate: 1.3 wt%; deionized water: 77.4 wt%; 30% strength liquid caustic soda: 2.5 wt%.
The preparation method of the starch-based polycarboxylate superplasticizer mate comprises the following specific steps:
1. weighing 8.5g of methacrylic acid phosphate modified starch, 8.2g of unsaturated polyoxyethylene ether and 50.0g of water, and adding the materials into a reaction kettle to obtain a base solution;
2. weighing 2.1g of acrylic acid and 13.4g of deionized water, adding into a No. 1 dripping tank, and fully and uniformly mixing to obtain a solution A; weighing 1.3g of ammonium persulfate and 14.0g of deionized water, adding into a No. 2 dripping tank, and fully and uniformly mixing to obtain a solution B;
3. the temperature of the reaction kettle is raised to 82 ℃, and the solution A and the solution B are respectively dripped into the base solution within 1.5 h. Stirring and reacting for 3.0h after the dropwise addition is finished, cooling to 50 ℃ after the reaction is finished, adding 2.5g of liquid alkali (with the concentration of 30%) for neutralization, and adjusting the pH value to 6.5 to obtain the starch-based polycarboxylate superplasticizer mate.
Example 2
A starch-based polycarboxylate superplasticizer partner comprises: gamma-methacryloxypropyltrimethoxysilane modified starch: 11.5 wt%; prenol polyoxyethylene ether: 12.2 wt%; methacrylic acid: 2.6 wt%; hydrogen peroxide: 1.5 wt%; deionized water: 68.7 wt%; 30% strength liquid caustic soda: 3.5 wt%.
The preparation method of the starch-based polycarboxylate superplasticizer mate comprises the following specific steps:
1. weighing 11.5g of gamma-methacryloxypropyltrimethoxysilane modified starch, 12.2g of isopentenol polyoxyethylene ether and 45.0g of water, and adding the starch, the isopentenol polyoxyethylene ether and the water into a reaction kettle to obtain a base solution;
2. weighing 2.6g of methacrylic acid and 11.7g of deionized water, adding into a No. 1 dripping tank, and fully and uniformly mixing to obtain a solution A; weighing 1.5g of hydrogen peroxide and 12.0g of deionized water, adding into a No. 2 dripping tank, and fully and uniformly mixing to obtain a solution B;
3. and (3) heating the reaction kettle to 75 ℃, and dropwise adding the solution A and the solution B into the base solution within 2.0 h. Stirring and reacting for 2.0h after the dropwise addition is finished, cooling to 45 ℃ after the reaction is finished, adding 3.5g of liquid alkali (with the concentration of 30%) for neutralization, and adjusting the pH value to 6.0 to obtain the starch-based polycarboxylate superplasticizer mate.
Example 3
A starch-based polycarboxylate superplasticizer partner comprises: maleic anhydride-modified starch: 12.4 wt%; methallyl alcohol polyoxyethylene ether: 9.6 wt%; acrylic acid: 1.7 wt%; 0.8 wt% of sodium methallyl sulfonate; potassium persulfate: 1.4 wt%; deionized water: 71.3 wt%; 30% strength liquid caustic soda: 2.8 wt%.
The preparation method of the starch-based polycarboxylate superplasticizer mate comprises the following specific steps:
1. weighing 12.4g of maleic anhydride modified starch, 9.6g of methallyl alcohol polyoxyethylene ether and 46.0g of water, and adding the materials into a reaction kettle to obtain a base solution;
2. weighing 1.7g of acrylic acid, 0.8g of sodium methallyl sulfonate and 12.0g of deionized water, adding into a No. 1 dripping tank, and fully and uniformly mixing to obtain a solution A; weighing 1.4g of potassium persulfate and 13.3g of deionized water, adding into a No. 2 dripping tank, and fully and uniformly mixing to obtain a solution B;
3. and (3) heating the reaction kettle to 85 ℃, and dropwise adding the solution A and the solution B into the base solution within 1.0 hour. Stirring and reacting for 3.0h after the dropwise addition is finished, cooling to 48 ℃ after the reaction is finished, adding 2.8g of liquid alkali (with the concentration of 30%) for neutralization, and adjusting the pH value to 6.2 to obtain the starch-based polycarboxylate superplasticizer mate.
Example 4
A starch-based polycarboxylate superplasticizer partner comprises: glycidyl methacrylate modified starch: 9.3 wt%; allyl polyoxyethylene ether: 12.8 wt%; acrylic acid: 2.9 wt%; hydrogen peroxide: 1.6 wt%; deionized water: 70.0 wt%; 30% strength liquid caustic soda: 3.4 wt%.
The preparation method of the starch-based polycarboxylate superplasticizer mate comprises the following specific steps:
1. weighing 9.3g of glycidyl methacrylate modified starch, 12.8g of allyl polyoxyethylene ether and 45.0g of water, and adding the materials into a reaction kettle to obtain a base solution;
2. weighing 2.9g of acrylic acid and 12.0g of deionized water, adding into a No. 1 dripping tank, and fully and uniformly mixing to obtain a solution A; weighing 1.6g of hydrogen peroxide and 13.0g of deionized water, adding into a No. 2 dripping tank, and fully and uniformly mixing to obtain a solution B;
3. the temperature of the reaction kettle is raised to 88 ℃, and the solution A and the solution B are respectively dripped into the base solution within 2.0 h. Stirring and reacting for 3.0h after the dropwise addition is finished, cooling to 50 ℃ after the reaction is finished, adding 3.4g of liquid alkali (with the concentration of 30%) for neutralization, and adjusting the pH value to 5.8 to obtain the starch-based polycarboxylate superplasticizer mate.
Example 5
A starch-based polycarboxylate superplasticizer partner comprises: maleic anhydride-modified starch: 5.0 wt%; allyl polyoxyethylene ether: 20.0 wt%; methacrylic acid: 5.1 wt%; ammonium persulfate: 1.9 wt%; deionized water: 64.0 wt%; 30% strength liquid caustic soda: 4.0 wt%.
The preparation method of the starch-based polycarboxylate superplasticizer mate comprises the following specific steps:
1. weighing 5.0g of maleic anhydride modified starch, 20.0g of allyl polyoxyethylene ether and 40.0g of water, and adding the materials into a reaction kettle to obtain a base solution;
2. weighing 5.1g of methacrylic acid and 10.0g of deionized water, adding into a No. 1 dripping tank, and fully and uniformly mixing to obtain a solution A; weighing 1.9g of ammonium persulfate and 14.0g of deionized water, adding into a No. 2 dripping tank, and fully and uniformly mixing to obtain a solution B;
3. the temperature of the reaction kettle is raised to 82 ℃, and the solution A and the solution B are respectively dripped into the base solution within 2.5 h. Stirring and reacting for 2.0h after the dropwise addition is finished, cooling to 40 ℃ after the reaction is finished, adding 4.0g of liquid alkali (with the concentration of 30%) for neutralization, and adjusting the pH value to 6.5 to obtain the starch-based polycarboxylate superplasticizer mate.
Comparative example 1
A starch-based polycarboxylate superplasticizer partner comprises: corn starch: 8.5 wt%; allyl polyoxyethylene ether: 8.2 wt%; acrylic acid: 2.1 wt%; ammonium persulfate: 1.3 wt%; deionized water: 77.4 wt%; 30% strength liquid caustic soda: 2.5 wt%.
The preparation method of the starch-based polycarboxylate superplasticizer mate comprises the following specific steps:
1. weighing 8.5g of corn starch, 8.2g of unsaturated polyoxyethylene ether and 50.0g of water, and adding the materials into a reaction kettle to obtain a base solution;
2. weighing 2.1g of acrylic acid and 13.4g of deionized water, adding into a No. 1 dripping tank, and fully and uniformly mixing to obtain a solution A; weighing 1.3g of ammonium persulfate and 14.0g of deionized water, adding into a No. 2 dripping tank, and fully and uniformly mixing to obtain a solution B;
3. the temperature of the reaction kettle is raised to 82 ℃, and the solution A and the solution B are respectively dripped into the base solution within 1.5 h. Stirring and reacting for 3.0h after the dropwise addition is finished, cooling to 50 ℃ after the reaction is finished, adding 2.5g of liquid alkali (with the concentration of 30%) for neutralization, and adjusting the pH value to 6.5 to obtain the starch-based polycarboxylate superplasticizer mate.
Comparative example 2
A starch-based polycarboxylate superplasticizer partner comprises: methacrylic acid phosphate ester modified starch: 8.5 wt%; allyl polyoxyethylene ether: 8.2 wt%; acrylic acid: 2.1 wt%; ammonium persulfate: 1.3 wt%; deionized water: 77.4 wt%; 30% strength liquid caustic soda: 2.5 wt%.
The preparation method of the starch-based polycarboxylate superplasticizer mate comprises the following specific steps:
1. weighing 8.5g of methacrylic acid phosphate modified starch, 8.2g of unsaturated polyoxyethylene ether and 50.0g of water, and adding the materials into a reaction kettle to obtain a base solution;
2. weighing 2.1g of acrylic acid and 13.4g of deionized water, adding into a No. 1 dripping tank, and fully and uniformly mixing to obtain a solution A; weighing 1.3g of ammonium persulfate and 14.0g of deionized water, adding into a No. 2 dripping tank, and fully and uniformly mixing to obtain a solution B;
3. the temperature of the reaction kettle is raised to 55 ℃, and the solution A and the solution B are respectively dripped into the base solution within 1.5 h. Stirring and reacting for 3.0h after the dropwise adding is finished, cooling to 20 ℃ after the reaction is finished, adding 2.5g of liquid alkali (with the concentration of 30%) for neutralization, and adjusting the pH value to 6.5 to obtain the starch-based polycarboxylate superplasticizer mate.
Application example 1
The starch-based polycarboxylate water reducer mate obtained in examples 1, 2, 3, 4 and 5 and comparative examples 1 and 2 is compounded with a polycarboxylate water reducer in a compounding ratio of 20:80, and the working performance indexes of C30 concrete (the mixing ratio is cement, fly ash, mineral powder, sand, gravel and water is 210: 76: 76: 865:1059:164) under the action of different water reducers are respectively tested. The type of the polycarboxylic acid water reducer sold in the market is PCE, and the test standard is GB/T8076-.
The specific test results are as follows:
the starch-based polycarboxylate superplasticizer mate prepared by the invention can be used as a concrete admixture and can be compounded with a polycarboxylate superplasticizer for use, and has stable performance and good compatibility with other additives; the starch-based polycarboxylate superplasticizer mate and the polycarboxylate superplasticizer are compounded according to the proportion of 1-50: 50-99, so that the mixing amount sensitivity of the polycarboxylate superplasticizer can be reduced, the workability of concrete can be improved, segregation and bleeding can be reduced, and the performance of the concrete can be integrally improved. The starch machine polycarboxylate superplasticizer mate also can be independently used as a superplasticizer, and has excellent adaptability to different cement, admixture, artificial sand, environment temperature and concrete mixing ratio fluctuation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention in any way, and it will be apparent to those skilled in the art that the above description of the present invention can be applied to various modifications, equivalent variations or modifications without departing from the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the starch-based polycarboxylate superplasticizer mate is characterized by comprising the following raw materials in parts by weight: unsaturated double bond-containing modified starch: 5-20 parts of a solvent; unsaturated polyoxyethylene ether: 5-20 parts of a solvent; acrylic monomer: 1-6 parts; initiator: 0.2-3 parts of a stabilizer; deionized water: 50-80 parts; a proper amount of alkaline solution;
the preparation method comprises the following steps:
(1) adding unsaturated double bond-containing modified starch, unsaturated polyoxyethylene ether and part of deionized water into a reaction kettle to obtain a base solution;
(2) heating the reaction kettle to 60-90 ℃, and dropwise adding the solution A and the solution B into the base solution within 0.5-3 h respectively, wherein the solution A is an aqueous solution of an acrylic monomer, and the solution B is an aqueous solution of an initiator;
(3) and (3) stirring and reacting for 1-5 h after the dropwise adding is finished, cooling to 25-50 ℃ after the reaction is finished, and neutralizing with an alkaline solution until the pH value is 5-8 to obtain the starch-based polycarboxylic acid water reducer mate.
2. The preparation method of the starch-based polycarboxylate superplasticizer mate according to claim 1, wherein 8.5-12.5 parts of modified starch containing unsaturated double bonds; unsaturated polyoxyethylene ether: 8.0-13 parts; acrylic monomer: 2-3 parts of a solvent; initiator: 1-2 parts; deionized water: 65-80 parts.
3. The preparation method of the starch-based polycarboxylate superplasticizer mate according to claim 1 or 2, wherein in the step (2), the reaction kettle temperature: and (3) dripping the liquid A and the liquid B at 75-90 ℃ for the following time: 1-2 h; in the step (3), stirring reaction: neutralizing the pH value for 1-3 h: 5.5 to 7.
4. The preparation method of the starch-based polycarboxylate superplasticizer mate according to claim 1 or 2, wherein the unsaturated double bond-containing modified starch is obtained by reacting starch with a double bond-containing modifier after acidification and degradation treatment;
the starch is one or more of corn starch, cassava starch, sweet potato starch, wheat starch, oxidized starch, etherified starch or dextrin;
the double-bond modifier is one or more of double-bond acid or double-bond ester, silane coupling agent or double-bond epoxy compound.
5. The preparation method of the starch-based polycarboxylate superplasticizer mate according to claim 4, wherein the unsaturated double bond-containing modified starch is phosphate methacrylate modified starch, gamma-methacryloxypropyltrimethoxysilane modified starch, maleic anhydride modified starch or glycidyl methacrylate modified starch.
6. The preparation method of the starch-based polycarboxylate superplasticizer mate according to claim 1 or 2, wherein the unsaturated polyoxyethylene ether is one or more of allyl polyoxyethylene ether, methallyl alcohol polyoxyethylene ether and isoamyl alcohol polyoxyethylene ether, and the molecular weight is 1000-10000.
7. The preparation method of the starch-based polycarboxylate superplasticizer mate according to claim 1 or 2, wherein the acrylic monomer is one or more of acrylic acid, acrylamide, methacrylic acid, sodium acrylate sulfonate, sodium methacrylate sulfonate, acrylonitrile, maleic anhydride, vinyl acetate and methyl methacrylate.
8. The preparation method of the starch-based polycarboxylate superplasticizer mate according to claim 1 or 2, wherein the initiator is one or more of ferrous ammonium sulfate, cerium ammonium nitrate, potassium persulfate, ammonium persulfate and hydrogen peroxide.
9. A starch-based polycarboxylate superplasticizer mate, which is characterized by being prepared according to the preparation method of the starch-based polycarboxylate superplasticizer mate of any one of claims 1-8.
10. The use method of the starch-based polycarboxylate superplasticizer mate of claim 9 is characterized in that the starch-based polycarboxylate superplasticizer mate and the polycarboxylate superplasticizer are compounded according to the proportion of 5-50: 50-95 for use.
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