CN119192493A - A shrinkage-reducing polycarboxylic acid water-reducing agent and preparation method thereof - Google Patents
A shrinkage-reducing polycarboxylic acid water-reducing agent and preparation method thereof Download PDFInfo
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- CN119192493A CN119192493A CN202411502527.4A CN202411502527A CN119192493A CN 119192493 A CN119192493 A CN 119192493A CN 202411502527 A CN202411502527 A CN 202411502527A CN 119192493 A CN119192493 A CN 119192493A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 51
- 239000002253 acid Substances 0.000 title description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 145
- 229920000570 polyether Polymers 0.000 claims abstract description 145
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 20
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 17
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 47
- 229910052710 silicon Inorganic materials 0.000 claims description 47
- 239000010703 silicon Substances 0.000 claims description 47
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 37
- OBSWSTDGLWZVEI-UHFFFAOYSA-N chloromethyl-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)CCl OBSWSTDGLWZVEI-UHFFFAOYSA-N 0.000 claims description 37
- 239000008030 superplasticizer Substances 0.000 claims description 35
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 18
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical group OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims 3
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims 1
- 239000011372 high-strength concrete Substances 0.000 abstract description 38
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 abstract description 13
- 239000004567 concrete Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 82
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 51
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 41
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- OPRIWFSSXKQMPB-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(C)(C)NC(=O)C=C OPRIWFSSXKQMPB-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous 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
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- 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)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本申请公开了一种减缩型聚羧酸减水剂及其制备方法，涉及混凝土外加剂领域，其中，减缩型聚羧酸减水剂的制备原料包括85‑95重量份硅改性不饱和聚醚大单体、20‑30重量份不饱和磷酸酯单体、4‑6重量份不饱和磺酸或不饱和磺酸盐、30‑40重量份丙烯酸、0.75‑1重量份还原剂、1.5‑2重量份氧化剂、1‑2重量份链转移剂以及500重量份水；硅改性不饱和聚醚单体为氯代硅烷类化合物与端烯丙基端羟基聚醚反应脱除HCl的产物，端烯丙基端羟基聚醚的通式为CH2＝CHCH2O(CH2CH2O)m(CH2CHCH3O)nH,m≥0，n≥0，20≤m+n≤30。该减缩型聚羧酸减水剂在高强混凝土中的分散性与减缩性能好，可有效降低高强混凝土的干燥收缩。The present application discloses a shrinkage-reducing polycarboxylate water-reducing agent and a preparation method thereof, and relates to the field of concrete admixtures. The raw materials for preparing the shrinkage-reducing polycarboxylate water-reducing agent include 85-95 parts by weight of silicon-modified unsaturated polyether macromonomer, 20-30 parts by weight of unsaturated phosphate monomer, 4-6 parts by weight of unsaturated sulfonic acid or unsaturated sulfonate, 30-40 parts by weight of acrylic acid, 0.75-1 parts by weight of reducing agent, 1.5-2 parts by weight of oxidizing agent, 1-2 parts by weight of chain transfer agent and 500 parts by weight of water; the silicon-modified unsaturated polyether monomer is a product of removing HCl by reacting a chlorosilane compound with a terminal allyl-terminated hydroxyl-terminated polyether, and the general formula of the terminal allyl- terminated hydroxyl-terminated polyether is CH2 = CHCH2O ( CH2CH2O ) m ( CH2CHCH3O ) nH , m≥0, n≥0, 20≤m+n≤30. The shrinkage-reducing polycarboxylate water-reducing agent has good dispersibility and shrinkage-reducing performance in high-strength concrete and can effectively reduce the drying shrinkage of high-strength concrete.
Description
Technical Field
The application relates to the field of concrete additives, in particular to a shrinkage-reducing polycarboxylate superplasticizer and a preparation method thereof.
Background
The polycarboxylate water reducer is widely used as one of concrete additives in the construction industry. Its excellent dispersion and low mixing amount make it an indispensable component in modern high-performance concrete.
The existing polycarboxylate water reducer is generally prepared by reacting an unsaturated polyether macromonomer, unsaturated acid, an unsaturated esterified monomer and an unsaturated phosphate monomer, wherein the unsaturated polyether macromonomer is one or more of isopentenyl alcohol polyoxyethylene ether, methallyl polyoxyethylene ether and allyl polyoxyethylene ether, the unsaturated acid is one or more of acrylic acid and methacrylic acid, the unsaturated esterified monomer is one or more of hydroxyethyl methacrylate and hydroxypropyl methacrylate, and the unsaturated phosphate monomer is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate.
However, the use of such polycarboxylate water reducers in high-strength concrete (C60 or more) is limited because the dispersibility and shrinkage reducing performance of such polycarboxylate water reducers in high-strength concrete are poor, and the shrinkage of the high-strength concrete is easily caused, so that the crack problem of the high-strength concrete is caused.
Disclosure of Invention
In order to solve the problem of poor shrinkage resistance of the polycarboxylate water reducer to high-strength concrete in the related art, the application provides a shrinkage-reducing polycarboxylate water reducer and a preparation method thereof.
The application provides a shrinkage-reducing polycarboxylate superplasticizer, which adopts the following technical scheme:
The preparation raw materials of the shrinkage-reducing type polycarboxylate water reducer comprise 85-95 parts by weight of silicon modified unsaturated polyether macromonomer, 20-30 parts by weight of unsaturated phosphate monomer, 4-6 parts by weight of unsaturated sulfonic acid or unsaturated sulfonate, 30-40 parts by weight of acrylic acid, 0.75-1 part by weight of reducing agent, 1.5-2 parts by weight of oxidant, 1-2 parts by weight of chain transfer agent and 500 parts by weight of water, wherein the silicon modified unsaturated polyether monomer is a product of removing HCl by reacting a chlorosilane compound with allyl-terminated hydroxyl polyether, and the general formula of the allyl-terminated hydroxyl polyether is CH 2＝CHCH2O(CH2CH2O)m(CH2CHCH3O)n H, wherein m is more than or equal to 0, n is more than or equal to 20 and less than or equal to m+n is more than or equal to 30.
The shrinkage-reducing polycarboxylate water reducer disclosed by the application utilizes the dispersibility and slump retaining performance of the silicon-modified unsaturated polyether macromonomer in concrete, and combines the synergistic effect of the unsaturated phosphate monomer, unsaturated sulfonic acid or unsaturated sulfonate and acrylic acid, so that the dispersion effect and shrinkage-reducing performance of the water reducer in high-strength concrete are obviously improved. Specifically, the silicon modified unsaturated polyether macromonomer is a product of removing HCl by reacting a chlorosilane compound with allyl-terminated polyether, the balance of hydrophilicity and hydrophobicity of a polymer can be effectively enhanced, the existence of unsaturated phosphate monomer, unsaturated sulfonic acid or unsaturated sulfonate and acrylic acid further enhances electrostatic repulsion between a water reducing agent and cement paste, so that the water reducing agent is more uniformly dispersed in concrete, on one hand, the effect of the water reducing agent can be improved, the high-strength concrete mixture can maintain excellent fluidity while the water-cement ratio is low, on the other hand, the pore structure of the high-strength concrete can be optimized, the porosity of the high-strength concrete is reduced, and the high-strength concrete with good compactness is obtained, thereby reducing the shrinkage rate of the high-strength concrete. Meanwhile, the shrinkage-reducing polycarboxylate superplasticizer also reduces the surface tension of the high-strength concrete, reduces the shrinkage stress generated when the water of the high-strength concrete evaporates, and is also beneficial to reducing the shrinkage rate of the high-strength concrete.
In some embodiments, the molar ratio of chlorosilane-based compound to allyl-terminated polyether is 1 (1-1.2).
In some specific embodiments, the chlorosilane-based compound is at least one of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxysilane.
In some specific embodiments, the chlorosilane-based compound is a combination of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxysilane, wherein the molar ratio of chloromethyl pentamethyl disiloxane to chloropropyl trimethoxysilane is 1 (3-4).
The chlorosilane compound adopts a composition of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxy silane, so that the shrinkage reducing performance of the polycarboxylate water reducer on high-strength concrete can be further improved. Specifically, when the chlorosilane compound adopts a composition with specific molar ratio of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxyl silane, the silicon modified unsaturated polyether macromonomer comprises a product of removing HCl by reacting chloromethyl pentamethyl disiloxane with allyl hydroxyl-terminated polyether and a product of removing HCl by reacting chloropropyl trimethoxyl silane with allyl hydroxyl-terminated polyether, the composite silicon modified unsaturated polyether macromonomer has more excellent dispersibility, can further improve the compactness of high-strength concrete, reduce the shrinkage rate of the high-strength concrete, is beneficial to the high-strength concrete to form a more stable molecular structure, and improves the splitting strength of the high-strength concrete.
In some embodiments, m is in the range of 15 to 20 and n is in the range of 5 to 10.
In the application, the dispersibility of the polycarboxylate water reducer can be further improved by controlling the values of m and n in the allyl hydroxyl-terminated polyether, so that the doping amount of the polycarboxylate water reducer is further improved on the premise of ensuring the low shrinkage rate of the high-strength concrete, and the production cost of the high-strength concrete is further reduced.
In some specific embodiments, the method of preparing the silicon-modified unsaturated polyether monomer comprises the steps of:
Adding a chlorosilane compound and a catalyst into a first solvent, and uniformly dissolving to obtain a solution A;
Adding allyl hydroxyl-terminated polyether into a second solvent, and uniformly dissolving to obtain a solution B;
Adding the solution B into the solution A, stirring for 2.5-3.5h at room temperature, filtering, concentrating, filtering, and removing residual reactants in the filtrate by reduced pressure distillation to obtain the silicon modified unsaturated polyether monomer.
The catalyst adopts amine catalyst such as triethylamine, ethylenediamine, etc., wherein the dosage of the catalyst is 0.01-0.02% of the weight of the chlorosilane compound.
The first solvent and the second solvent can be prepared from raw materials capable of dissolving chlorosilane compounds and allyl-terminated hydroxyl-terminated polyether, such as tetrahydrofuran. Wherein, the dosage of the first solvent is 40-50% of the weight of the chlorosilane compound, and the dosage of the second solvent is 35-45% of the weight of the allyl-terminated hydroxyl polyether.
In the application, after nucleophilic substitution reaction is carried out on the chlorosilane compound and the allyl hydroxyl-terminated polyether under the action of the catalyst to remove HCl, the silicon modified unsaturated polyether monomer is obtained through impurity removal, and can play a synergistic effect with the unsaturated phosphate monomer and the unsaturated sulfonic acid or the unsaturated sulfonate, so that the dispersion effect and the shrinkage reduction performance of the water reducer in high-strength concrete are obviously improved.
In some embodiments, the unsaturated phosphate monomer is a phosphate methacrylate.
In some specific embodiments, the unsaturated sulfonic acid or unsaturated sulfonate is selected from at least one of sodium 2-acrylamido-2-methylpropanesulfonic acid, sodium 2-acrylamido-2-methylpropanesulfonic acid.
In some specific embodiments, the oxidizing agent is at least one of sodium persulfate, ammonium persulfate, and potassium persulfate, the reducing agent is at least one of ascorbic acid, sodium sulfite, and sodium bisulfite, and the chain transfer agent is at least one of thioglycolic acid, mercaptoethanol, and mercaptopropionic acid.
In a second aspect, the preparation method of the shrinkage-reducing type polycarboxylate superplasticizer provided by the application adopts the following technical scheme that the preparation method of the shrinkage-reducing type polycarboxylate superplasticizer comprises the following steps:
Adding silicon modified unsaturated polyether macromonomer, unsaturated phosphate monomer, unsaturated sulfonic acid or unsaturated sulfonate and acrylic acid into water accounting for 20-30% of the total weight of the water formula to obtain solution A;
adding an oxidant into water accounting for 30-40% of the total weight of the water formula to obtain a solution B;
adding a reducing agent and a chain transfer agent into the balance of water to obtain a solution C;
and (3) simultaneously dripping the solution B and the solution C into the solution A for 80-100min to obtain the shrinkage-reducing polycarboxylate superplasticizer.
The preparation method of the reduced polycarboxylate superplasticizer can improve the reaction sufficiency of the reduced polycarboxylate superplasticizer, and is favorable for obtaining the reduced polycarboxylate superplasticizer with good dispersion effect and good reduction performance in high-strength concrete.
In summary, the application at least comprises the following beneficial technical effects:
(1) The shrinkage-reducing type polycarboxylate water reducer provided by the application is prepared by utilizing a silicon modified unsaturated polyether macromonomer obtained by removing HCl through the reaction of a chlorosilane compound and allyl hydroxyl-terminated polyether, and simultaneously combining the synergistic effect of an unsaturated phosphate monomer, unsaturated sulfonic acid or unsaturated sulfonate and acrylic acid, so that the dispersion effect and shrinkage-reducing performance of the water reducer in high-strength concrete are obviously improved.
(2) The chlorosilane compound adopts a composition of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxy silane, so that the shrinkage reducing performance of the polycarboxylate water reducer on high-strength concrete can be further improved.
(3) In the application, the dispersibility of the polycarboxylate water reducer can be further improved by controlling the values of m and n in the allyl hydroxyl-terminated polyether, so that the doping amount of the polycarboxylate water reducer is further improved on the premise of ensuring the low shrinkage rate of the high-strength concrete, and the production cost of the high-strength concrete is further reduced.
Detailed Description
The application is further described below in connection with specific experiments.
Preparation example
[ PREPARATION EXAMPLE 1]
A silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloromethyl pentamethyl disiloxane with allyl-terminated hydroxyl-terminated polyether, wherein the structural formula of the allyl-terminated hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)10(CH2CHCH3O)10 H, and the molar ratio of the chloromethyl pentamethyl disiloxane to the allyl-terminated hydroxyl-terminated polyether is 1:1.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
s1, adding chloromethyl pentamethyl disiloxane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloromethyl pentamethyl disiloxane is 196.82g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the S1 step is 88.57g;
S2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1078g, and the dosage of the tetrahydrofuran in the S2 step is 380g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
[ PREPARATION EXAMPLE 2]
The silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloropropyl trimethoxyl silane with allyl hydroxyl-terminated polyether, the structural formula of the allyl hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)10(CH2CHCH3O)10 H, and the molar usage ratio of the chloropropyl trimethoxyl silane to the allyl hydroxyl-terminated polyether is 1:1.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
s1, adding chloropropyl trimethoxyl silane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloropropyl trimethoxyl silane is 198.72g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the S1 step is 89.42g;
S2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1078g, and the dosage of the tetrahydrofuran in the S2 step is 380g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
[ PREPARATION EXAMPLE 3]
The silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloromethyl pentamethyl disiloxane, chloropropyl trimethoxyl silane and allyl hydroxyl-terminated polyether, the structural formula of the allyl hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)10(CH2CHCH3O)10 H, and the ratio of the sum of the molar dosages of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxyl silane to the molar amount of the allyl hydroxyl-terminated polyether is 1:1.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
S1, adding chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloromethyl pentamethyl disiloxane is 49.21g, the dosage of the chloropropyl trimethoxysilane is 149.04g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the step S1 is 89.42g, namely the molar dosage ratio of the chloromethyl pentamethyl disiloxane to the chloropropyl trimethoxysilane is 1:3;
S2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1078g, and the dosage of the tetrahydrofuran in the S2 step is 380g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
[ PREPARATION EXAMPLE 4]
The difference between the silicon modified unsaturated polyether monomer and the preparation example 3 is that the values of m and n in the allyl terminal hydroxyl-terminated polyether are different.
In the preparation example, the silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and allyl-terminated hydroxyl-terminated polyether, and the structural formula of the allyl-terminated hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)15(CH2CHCH3O)5 H.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
S1, adding chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloromethyl pentamethyl disiloxane is 49.21g, the dosage of the chloropropyl trimethoxysilane is 149.04g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the step S1 is 89.42g;
S2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1008g, and the dosage of the tetrahydrofuran in the S2 step is 353g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
[ PREPARATION EXAMPLE 5]
The difference between the silicon modified unsaturated polyether monomer and the preparation example 3 is that the values of m and n in the allyl terminal hydroxyl-terminated polyether are different.
In the preparation example, the silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and allyl-terminated hydroxyl-terminated polyether, and the structural formula of the allyl-terminated hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)20(CH2CHCH3O)5 H.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
S1, adding chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloromethyl pentamethyl disiloxane is 49.21g, the dosage of the chloropropyl trimethoxysilane is 149.04g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the step S1 is 89.42g;
s2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1228g, and the dosage of the tetrahydrofuran in the S2 step is 430g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
[ PREPARATION EXAMPLE 6]
The difference between the silicon modified unsaturated polyether monomer and the preparation example 3 is that the values of m and n in the allyl terminal hydroxyl-terminated polyether are different.
In the preparation example, the silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and allyl-terminated hydroxyl-terminated polyether, and the structural formula of the allyl-terminated hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)20(CH2CHCH3O)10 H.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
S1, adding chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloromethyl pentamethyl disiloxane is 49.21g, the dosage of the chloropropyl trimethoxysilane is 149.04g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the step S1 is 89.42g;
S2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1518g, and the dosage of the tetrahydrofuran in the S2 step is 530g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
[ PREPARATION EXAMPLE 7]
The difference between the silicon modified unsaturated polyether monomer and the preparation example 3 is that the values of m and n in the allyl terminal hydroxyl-terminated polyether are different.
In the preparation example, the silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and allyl-terminated hydroxyl-terminated polyether, and the structural formula of the allyl-terminated hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)5(CH2CHCH3O)15 H.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
S1, adding chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloromethyl pentamethyl disiloxane is 49.21g, the dosage of the chloropropyl trimethoxysilane is 149.04g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the step S1 is 89.42g;
S2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1148g, and the dosage of the tetrahydrofuran in the S2 step is 402g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
[ PREPARATION EXAMPLE 8]
The difference between the silicon modified unsaturated polyether monomer and the preparation example 3 is that the values of m and n in the allyl terminal hydroxyl-terminated polyether are different.
In the preparation example, the silicon modified unsaturated polyether monomer is a product of removing HCl by reacting chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and allyl-terminated hydroxyl-terminated polyether, and the structural formula of the allyl-terminated hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)10(CH2CHCH3O)20 H.
In the preparation example, the preparation method of the silicon modified unsaturated polyether monomer comprises the following steps:
S1, adding chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane and triethylamine into tetrahydrofuran, and dissolving uniformly to obtain a solution A, wherein the dosage of the chloromethyl pentamethyl disiloxane is 49.21g, the dosage of the chloropropyl trimethoxysilane is 149.04g, the dosage of the triethylamine is 2g, and the dosage of the tetrahydrofuran in the step S1 is 89.42g;
S2, adding allyl-terminated polyether into tetrahydrofuran, and dissolving uniformly to obtain a solution B, wherein the dosage of the allyl-terminated polyether is 1438g, and the dosage of the tetrahydrofuran in the S2 step is 503g;
and S3, adding the solution B into the solution A, stirring for 3 hours at room temperature, filtering, concentrating, filtering, taking filtrate, and distilling under reduced pressure to remove residual reactants and tetrahydrofuran in the filtrate, thereby obtaining the silicon modified unsaturated polyether monomer.
Examples
[ Example 1]
The shrinkage-reducing polycarboxylate superplasticizer is prepared from the following raw materials:
85g of unsaturated polyether macromonomer, in this example, the unsaturated polyether macromonomer prepared by [ preparation example 1] is specifically used;
30g of unsaturated phosphate monomer, in this example, methacrylic acid phosphate is specifically used as the unsaturated phosphate monomer;
4g of unsaturated sulfonic acid or unsaturated sulfonate, in this example, 2-acrylamido-2-methylpropanesulfonic acid is specifically used;
30g of acrylic acid;
0.75g of reducing agent, in the embodiment, sodium sulfite is specifically adopted as the reducing agent;
1.5g of oxidant, in the embodiment, sodium persulfate is specifically adopted as the oxidant;
1g of chain transfer agent, in this example, thioglycollic acid is specifically used as the chain transfer agent;
500g of water.
In this embodiment, the preparation method of the shrinkage-reducing polycarboxylate superplasticizer comprises the following steps:
Adding silicon modified unsaturated polyether macromonomer, unsaturated phosphate monomer, unsaturated sulfonic acid or unsaturated sulfonate and acrylic acid into 125g of water to obtain solution A;
Adding an oxidant into 175g of water to obtain a solution B;
adding a reducing agent and a chain transfer agent into the balance of water to obtain a solution C;
And (3) simultaneously dripping the solution B and the solution C into the solution A, wherein the dripping time is controlled to be 100 minutes, and thus the shrinkage-reducing polycarboxylate superplasticizer is obtained.
[ Example 2]
The shrinkage-reducing polycarboxylate superplasticizer is prepared from the following raw materials:
95g of unsaturated polyether macromonomer, in this example, the unsaturated polyether macromonomer prepared by [ preparation example 1] is specifically used;
20g of unsaturated phosphate monomer, in this example, methacrylic acid phosphate is specifically used as the unsaturated phosphate monomer;
6g of unsaturated sulfonic acid or unsaturated sulfonate, in the embodiment, the unsaturated sulfonic acid or unsaturated sulfonate specifically adopts 2-acrylamide-2-methylpropanesulfonic acid sodium salt;
40g of acrylic acid;
1g of reducing agent, in the embodiment, sodium sulfite is specifically adopted as the reducing agent;
2g of oxidant, in the embodiment, sodium persulfate is specifically adopted as the oxidant;
2g of chain transfer agent, in this example, mercaptopropionic acid is specifically used as the chain transfer agent;
500g of water.
In this embodiment, the preparation method of the shrinkage-reducing polycarboxylate superplasticizer comprises the following steps:
Adding silicon modified unsaturated polyether macromonomer, unsaturated phosphate monomer, unsaturated sulfonic acid or unsaturated sulfonate and acrylic acid into 125g of water to obtain solution A;
Adding an oxidant into 175g of water to obtain a solution B;
adding a reducing agent and a chain transfer agent into the balance of water to obtain a solution C;
And (3) simultaneously dripping the solution B and the solution C into the solution A, wherein the dripping time is controlled to be 100 minutes, and thus the shrinkage-reducing polycarboxylate superplasticizer is obtained.
[ Example 3]
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different. In this example, the unsaturated polyether macromonomer obtained in [ preparation example 2 ] was used.
[ Example 4]
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different. In this example, the unsaturated polyether macromonomer obtained in [ preparation example 3 ] was used.
[ Example 5]
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different. In this example, the unsaturated polyether macromonomer obtained in [ preparation example 4] was used.
[ Example 6]
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different. In this example, the unsaturated polyether macromonomer obtained in [ preparation example 5] was used.
[ Example 7]
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different. In this example, the unsaturated polyether macromonomer obtained in [ preparation example 6 ] was used.
[ Example 8]
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different. In this example, the unsaturated polyether macromonomer obtained in [ preparation example 7 ] was used.
[ Example 9]
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different. In this example, the unsaturated polyether macromonomer obtained in [ preparation example 8 ] was used.
Comparative example
Comparative example 1
A shrinkage-reducing polycarboxylate superplasticizer is distinguished from example 1 in that the unsaturated polyether macromonomer is different.
In the comparative example, the unsaturated polyether macromonomer specifically adopts an allyl-terminated hydroxyl-terminated polyether, and the structural formula of the allyl-terminated hydroxyl-terminated polyether is CH 2＝CHCH2O(CH2CH2O)10(CH2CHCH3O)10 H.
Performance test
In this test, the mixing ratio of the reference concrete C60 is shown in table 1 below:
TABLE 1
1. The shrinkage ratio is tested by referring to section 6.6.2 in GB/T8076-2008, the test period is 28d, and the mixing amount (folding and fixing) of the shrinkage-reducing type polycarboxylate superplasticizer is 0.5% and 1.5% respectively.
2. The splitting strength is detected by referring to section 9 in GB/T50081-2019, and the doping amount (folding and fixing) of the shrinkage-reducing type polycarboxylate superplasticizer is respectively 0.5% and 1.5%.
TABLE 2
Comparative example 1 is different from example 1 in that the unsaturated polyether macromonomer in comparative example 1 uses the allyl-terminated hydroxyl-terminated polyether which has not been modified with the chlorosilane-based compound, and it is seen from the data in Table 2 that the shrinkage reducing performance of the polycarboxylic acid water reducer to high-strength concrete in comparative example 1 is lowered, and particularly when the blending amount (folding-over) of the polycarboxylic acid water reducer is 0.5%, the shrinkage reducing performance of the polycarboxylic acid water reducer to high-strength concrete is significantly lowered. In addition, the effect of the polycarboxylic acid water reducer on the cleavage strength of the high-strength concrete in comparative example 1 was also reduced, and particularly when the blending amount (folding fixation) of the polycarboxylic acid water reducer was 0.5%, the effect of the polycarboxylic acid water reducer on the cleavage strength of the high-strength concrete was significantly reduced.
Examples 3-4 differ from example 1 in that the unsaturated silicon modified polyether monomer of example 4 used chloromethyl pentamethyl disiloxane, chloropropyl trimethoxysilane reacted with allyl hydroxyl terminated polyether to remove HCl product, whereas the silicon modified unsaturated polyether monomer of example 3 used chloropropyl trimethoxysilane reacted with allyl hydroxyl terminated polyether to remove HCl product, and the silicon modified unsaturated polyether monomer of example 1 used chloromethyl pentamethyl disiloxane reacted with allyl hydroxyl terminated polyether to remove HCl product. As can be seen from the data in Table 2, compared with the examples 1 and 3, the polycarboxylic acid water reducer in the example 4 has improved shrinkage reducing performance on the high-strength concrete and improved enhancement effect on the splitting strength of the high-strength concrete, and the fact that the unsaturated silicon modified polyether monomer in the shrinkage reducing polycarboxylic acid water reducer adopts chloromethyl pentamethyl disiloxane, chloropropyl trimethoxyl silane and allyl-terminated hydroxyl polyether with a specific molar ratio to react to remove HCl products is more beneficial to improving the shrinkage reducing performance and splitting resistance of the high-strength concrete.
Examples 8-9 differ from example 4 in that the silicon modified unsaturated polyether macromer employed has a different value for m and n in the allyl-terminated hydroxyl-terminated polyether. The data in the table 2 shows that the general formula of the allyl-terminated hydroxyl polyether is CH 2＝CHCH2O(CH2CH2O)m(CH2CHCH3O)n H, wherein the value range of m is 15-20, the value range of n is 5-10, and the dispersibility of the polycarboxylate water reducer can be further improved, so that the doping amount of the polycarboxylate water reducer is further improved on the premise of ensuring the low shrinkage rate of the high-strength concrete, and the production cost of the high-strength concrete is further reduced.
The present embodiment is merely illustrative of the present application and not limiting, and one skilled in the art, after having read the present specification, may make modifications to the embodiment without creative contribution as required, but is protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A shrinkage-reducing type polycarboxylate water reducer is characterized in that the preparation raw materials of the shrinkage-reducing type polycarboxylate water reducer comprise 85-95 parts by weight of silicon modified unsaturated polyether macromonomer, 20-30 parts by weight of unsaturated phosphate monomer, 4-6 parts by weight of unsaturated sulfonic acid or unsaturated sulfonate, 30-40 parts by weight of acrylic acid, 0.75-1 part by weight of reducing agent, 1.5-2 parts by weight of oxidant, 1-2 parts by weight of chain transfer agent and 500 parts by weight of water, wherein the silicon modified unsaturated polyether monomer is a product of removing HCl by reacting a chlorosilane compound with allyl-terminated hydroxyl polyether, and the general formula of the allyl-terminated hydroxyl polyether is CH 2＝CHCH2O(CH2CH2O)m(CH2CHCH3O)n H, wherein m is more than or equal to 0, n is more than or equal to 0, and m+n is more than or equal to 20 and less than or equal to 30.
2. The shrinkage-reducing polycarboxylate superplasticizer as set forth in claim 1, wherein the molar ratio of the chlorosilane compound to the allyl-terminated hydroxyl-terminated polyether is 1 (1-1.2).
3. The shrinkage-reducing polycarboxylate superplasticizer as set forth in claim 1, wherein said chlorosilane compound is at least one of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxysilane.
4. A shrinkage-reducing polycarboxylate water reducer according to claim 3, wherein the chlorosilane compound is a combination of chloromethyl pentamethyl disiloxane and chloropropyl trimethoxysilane, and the molar ratio of the chloromethyl pentamethyl disiloxane to the chloropropyl trimethoxysilane is 1 (3-4).
5. The shrinkage-reducing polycarboxylate superplasticizer as set forth in claim 4, wherein m is 15-20 and n is 5-10.
6. The shrinkage-reducing polycarboxylate superplasticizer as defined in any one of claims 1-5, wherein the preparation method of the silicon-modified unsaturated polyether monomer comprises the following steps:
Adding a chlorosilane compound and a catalyst into a first solvent, and uniformly dissolving to obtain a solution A;
Adding allyl hydroxyl-terminated polyether into a second solvent, and uniformly dissolving to obtain a solution B;
Adding the solution B into the solution A, stirring for 2.5-3.5h at room temperature, filtering, concentrating, filtering, and removing residual reactants in the filtrate by reduced pressure distillation to obtain the silicon modified unsaturated polyether monomer.
7. A shrinkage-reducing polycarboxylate superplasticizer as defined in any one of claims 1-5, wherein the unsaturated phosphate monomer is methacrylic acid phosphate.
8. A shrinkage-reducing polycarboxylate superplasticizer as defined in any one of claims 1-5, wherein the unsaturated sulfonic acid or unsaturated sulfonate is at least one selected from 2-acrylamido-2-methylpropanesulfonic acid and sodium 2-acrylamido-2-methylpropanesulfonate.
9. A shrinkage-reducing polycarboxylate superplasticizer as defined in any one of claims 1-5, wherein the oxidant is at least one of sodium persulfate, ammonium persulfate and potassium persulfate, the reducing agent is at least one of ascorbic acid, sodium sulfite and sodium bisulfite, and the chain transfer agent is at least one of thioglycollic acid, mercaptoethanol and mercaptopropionic acid.
10. A method for preparing a shrinkage-reducing polycarboxylate superplasticizer as defined in any one of claims 1-9, comprising the steps of:
Adding silicon modified unsaturated polyether macromonomer, unsaturated phosphate monomer, unsaturated sulfonic acid or unsaturated sulfonate and acrylic acid into water accounting for 20-30% of the total weight of the water formula to obtain solution A;
adding an oxidant into water accounting for 30-40% of the total weight of the water formula to obtain a solution B;
adding a reducing agent and a chain transfer agent into the balance of water to obtain a solution C;
and (3) simultaneously dripping the solution B and the solution C into the solution A for 80-100min to obtain the shrinkage-reducing polycarboxylate superplasticizer.
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