CN112708040A - Concrete reinforcing and toughening additive and preparation method thereof - Google Patents
Concrete reinforcing and toughening additive and preparation method thereof Download PDFInfo
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- CN112708040A CN112708040A CN201911115377.0A CN201911115377A CN112708040A CN 112708040 A CN112708040 A CN 112708040A CN 201911115377 A CN201911115377 A CN 201911115377A CN 112708040 A CN112708040 A CN 112708040A
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- 239000004567 concrete Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 230000003014 reinforcing effect Effects 0.000 title claims abstract description 41
- 239000000654 additive Substances 0.000 title claims abstract description 26
- 230000000996 additive effect Effects 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 89
- 239000000178 monomer Substances 0.000 claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 21
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 61
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 claims description 53
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 53
- 235000004279 alanine Nutrition 0.000 claims description 53
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 26
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 26
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 26
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 26
- 239000008096 xylene Substances 0.000 claims description 26
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 241000446313 Lamella Species 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- ZYJWMQAABJXBHW-UHFFFAOYSA-N 1,8-bis(sulfanyl)octane-3,6-dione Chemical compound SCCC(=O)CCC(=O)CCS ZYJWMQAABJXBHW-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 11
- -1 isopentenyl Chemical group 0.000 claims description 11
- 239000001632 sodium acetate Substances 0.000 claims description 11
- 235000017281 sodium acetate Nutrition 0.000 claims description 11
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-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
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 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 2
- 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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 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
- JPTOEYVAAZFYGV-UHFFFAOYSA-M butyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CCCC[N+](C)(C)CCOC(=O)C(C)=C JPTOEYVAAZFYGV-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 31
- 230000036571 hydration Effects 0.000 abstract description 11
- 238000006703 hydration reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004575 stone Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the technical field of concrete additives, in particular to a concrete reinforcing and toughening admixture and a preparation method thereof, wherein the concrete reinforcing and toughening admixture comprises the following preparation raw materials: unsaturated polyoxyethylene ether monomer, esterified monomer, quaternary ammonium salt cationic monomer, methacrylic acid, graphene oxide solution, reducing agent, chain transfer agent and oxidant. The concrete reinforcing and toughening additive provided by the invention has good dispersibility and structural adjustability, can promote the formation of a neat and regular microstructure of cement products in set cement, realizes the orderliness of hydration, and has a remarkable effect of improving the working performance and durability of concrete.
Description
Technical Field
The invention relates to the technical field of concrete additives, in particular to a concrete reinforcing and toughening additive and a preparation method thereof.
Background
In recent years, the requirements of concrete construction engineering structures on the performance of cement-based composite materials are increasingly improved, but the cement hydration process is complex, the microstructure of the product is difficult to regulate and control, and some additives added in the process of mixing the concrete are sensitive and not good in adaptability to the concrete, so that the cement-based composite materials are easy to generate structural defects such as cracks, permeation and the like, and the physical mechanical property and the durability of the cement-based composite materials are further deteriorated. The most important of solving the problems is to improve the strength and toughness of the hardened cement paste in the concrete and reduce the generation of cracks and penetration, thereby achieving the aim of improving the strength, toughness and durability of the concrete.
Graphene Oxide (GO) is used as an intermediate product for preparing graphene by graphite oxidation, a large number of active groups (such as hydroxyl, carboxyl, epoxy and the like) exist on the surface, and the graphene oxide has an ultra-large specific surface area and excellent flexibility. Research reports that GO is used as a template during hydration, original crystal nuclei of cement hydration products are increased through a crystal nucleus effect, the hydration process of cement is promoted, the microstructure of the cement hydration products is regulated, and the cement hydration products have obvious reinforcing and toughening effects on cement stones, so that the GO has a wide application prospect in the technical field of building materials.
However, as GO is used more and more in concrete formulations, problems have been encountered. The existing method is mainly characterized in that GO is compounded with a water reducing agent and then directly applied to the process of mixing concrete, but the problems that GO is difficult to uniformly disperse in cement paste and the fluidity of the cement paste doped with GO is obviously reduced exist.
Disclosure of Invention
In order to solve the problems that GO is difficult to uniformly disperse in cement paste and the fluidity of the cement paste doped with GO is obviously reduced in the background art, the invention provides a concrete reinforcing and toughening additive, which comprises the following preparation raw materials: unsaturated polyoxyethylene ether monomer, esterified monomer, quaternary ammonium salt cationic monomer, methacrylic acid, graphene oxide solution, reducing agent, chain transfer agent and oxidant.
On the basis of the scheme, the method further comprises the following preparation raw materials in parts by weight:
on the basis of the scheme, the unsaturated polyoxyethylene ether monomer is isopentene polyoxyethylene ether with the molecular weight of 2000, 2400 or 3000.
On the basis of the scheme, the preparation method of the esterified monomer comprises the following steps:
continuously introducing protective gas, preferably nitrogen, into a container provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at a constant temperature of 100 ℃, preferably for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer.
On the basis of the scheme, n (diethylene glycol monovinyl ether) and n (alanine) are 1.5:1, xylene accounts for 20% of the total mass of the diethylene glycol monovinyl ether and the alanine, and methanesulfonic acid and p-hydroxyanisole respectively account for 1.5% and 1% of the total mass of the diethylene glycol monovinyl ether and the alanine.
On the basis of the scheme, the quaternary ammonium salt cationic monomer is one of acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl dimethyl butyl ammonium bromide, dimethyl diene ammonium chloride, ethyl diene ammonium chloride or 2-acrylamido-2-methylpropanesulfonic acid.
On the basis of the scheme, further, the reducing agent is one of sodium 2-hydroxy-2-sulfinate acetate, sodium bisulfite, ascorbic acid or sodium hypophosphite.
On the basis of the scheme, the chain transfer agent is one of 3, 6-dioxo-1, 8-octanedithiol, mercaptopropionic acid, sodium bisulfite, isopropanol or sodium hypophosphite.
On the basis of the scheme, the oxidant is one of tert-butyl hydroperoxide, ammonium persulfate, hydrogen peroxide or sodium persulfate.
On the basis of the scheme, the neutralizing agent is one of sodium methoxide, sodium hydroxide, sodium tert-butoxide or dimethylethanolamine.
The invention provides a preparation method of a concrete reinforcing and toughening additive, which comprises the following preparation steps:
adding an unsaturated polyoxyethylene ether monomer, an esterified monomer, a quaternary ammonium salt cationic monomer and methacrylic acid into a graphene oxide solution, carrying out ultrasonic treatment, preferably carrying out ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and stirring to form a monomer mixed solution;
step two, mixing a reducing agent, a chain transfer agent and water, and adding the mixture into a first dripping device;
step three, mixing an oxidant and water and adding the mixture into a second dripping device;
respectively dripping the solution in the first dripping device and the solution in the second dripping device into a reaction device, and reacting at a constant temperature of 60 ℃, wherein the constant temperature reaction time is preferably 1 h;
and step five, cooling the reaction temperature to room temperature, adding a neutralizer solution into the reaction device, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
On the basis of the scheme, the invention further provides a preferable scheme of the preparation method of the concrete reinforcing and toughening admixture, which comprises the following preparation steps:
adding 150 parts by weight of unsaturated polyoxyethylene ether monomer, 15-20 parts by weight of esterified monomer, 3-5 parts by weight of quaternary ammonium salt cationic monomer and 10-15 parts by weight of methacrylic acid into 180 parts by weight of graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and stirring to form a monomer mixed solution;
step two, mixing 5 parts by weight of reducing agent, 3 parts by weight of chain transfer agent and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant and 25 parts by weight of water, and adding the mixture into a second dripping device;
respectively dripping the solution in the first dripping device and the solution in the second dripping device into a reaction device, and reacting for 1h at a constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a neutralizer solution into the reaction device, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
On the basis of the above scheme, further, the preparation method of the graphene oxide solution comprises: and (2) placing graphene oxide powder with the lamella diameter of 0.2-10 microns in deionized water, and performing ultrasonic dispersion, wherein the ultrasonic dispersion time is preferably 2 hours, so that the powder lamella is completely peeled and dispersed to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
Compared with the prior art, the concrete reinforcing and toughening admixture and the preparation method thereof provided by the invention have the following technical principles and beneficial effects:
1. according to the invention, the graphene oxide and the polycarboxylic acid water reducing agent are subjected to copolymerization modification, so that a large number of oxygen-containing functional groups can be provided, and cement particles can be better combined together, thereby promoting the uniform dispersion of the nano-phase GO in cement paste without affecting the fluidity of the cement paste, and achieving the purpose of reinforcing and toughening cement concrete.
2. According to the invention, the esterification is carried out by utilizing alanine and diethylene glycol monovinyl ether to synthesize the esterified monomer, and the esterified monomer participates in the next polymerization reaction, so that the prepared reinforcing and toughening additive has an ester group structure, and can continuously release carboxyl in the stirring process to compensate loss and improve the cement dispersibility.
3. The quaternary ammonium salt cationic monomer is added, in the cement hydration process, the coagulation of cement paste is prevented through electrostatic interaction and steric hindrance effect, the dispersing performance of the cement paste is improved, and because the environment is in an alkaline condition, the amide group is hydrolyzed to release carboxyl, so that the further hydration of cement products is promoted, and the performances such as the compactness of a concrete structure, the strength of concrete and the like are improved.
4. According to the invention, by utilizing the template effect and the regulation and control effect of the graphene oxide, the formation of a neat and regular microstructure of a cement hydration product in the set cement is promoted, and the ordering of hydration is realized, so that the working performance and the durability of the cement concrete are improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention also provides the following embodiments:
example 1:
adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Example 2
Adding 150 parts by weight of isopentenyl polyoxyethylene ether with molecular weight of 2000, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Example 3
Adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 2400, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Example 4
Adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Example 5:
adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent sodium bisulfite, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant ammonium persulfate and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Example 6:
adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent mercaptopropionic acid and 25 parts by weight of water, and adding the mixture into a first addition device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
It should be noted that the specific parameters or some reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
The invention provides the following comparative examples:
comparative example 1:
adding 150 parts by weight of isopentenyl polyoxyethylene ether with molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 180 parts by weight of distilled water, carrying out ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Comparative example 2:
adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 40 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 40 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Comparative example 3:
adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 80 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 80 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Comparative example 4:
adding 150 parts by weight of isopentenyl polyoxyethylene ether with the molecular weight of 3000, 15 parts by weight of distilled water, 3 parts by weight of acryloyloxyethyl trimethyl ammonium chloride and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution, performing ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
Comparative example 5:
adding 150 parts by weight of isopentene group polyoxyethylene ether with molecular weight of 3000, 15 parts by weight of esterified monomer, 3 parts by weight of distilled water and 10 parts by weight of methacrylic acid into 160 parts by weight of prepared graphene oxide solution in advance, carrying out ultrasonic treatment for 30min, adding into a reaction device, heating to 60 ℃, and maintaining stirring to form a monomer mixed solution;
the preparation method of the graphene oxide solution comprises the following steps: and (3) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion for 2 hours to completely strip and disperse the powder lamellae to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
The preparation of the esterified monomer comprises the following steps: continuously introducing nitrogen into a four-neck flask provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃ for 4 hours, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer. Wherein n (diethylene glycol monovinyl ether) n (alanine) is 1.5:1, xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
Step two, uniformly mixing 5 parts by weight of reducing agent 2-hydroxy-2-sulfinic acid sodium acetate, 3 parts by weight of chain transfer agent 3, 6-dioxo-1, 8-octanedithiol and 25 parts by weight of water, and adding the mixture into a first dripping device;
step three, mixing 5 parts by weight of oxidant tert-butyl hydroperoxide and 25 parts by weight of water, and adding the mixture into a second dripping device;
step four, respectively dripping the solution in the first dripping device and the solution in the second dripping device into the reaction device, finishing dripping for about 2 hours, and then reacting for 1 hour at the constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a proper amount of sodium methoxide solution, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
In order to further illustrate the performance effect of the concrete reinforcing and toughening admixture provided by the invention, the performance and durability of the concrete are tested according to GB 8076-. Experimental raw materials: P.O 42.5.5 Minfu cement; river sand (fineness modulus 2.6); small stones (10-20 mm continuous gradation); large stones (16-31.5 mm continuous gradation); mineral powder (S95); fly ash (grade II). The concrete mix ratio is shown in table 1.
Table 1 concrete mix proportion units: kg/m3
| Cement | Sand | Small stone | Large stone | Fly ash | Mineral powder | Water (W) |
| 430 | 700 | 368 | 682 | 90 | 30 | 167 |
In concrete experiments, the water-cement ratio is 0.3, and the mixing amount of the water reducing agent prepared in each example and the comparative example is 0.35%. However, comparative example 1 was prepared by externally adding the graphene oxide solution in an amount of 0.08%. The concrete workability tests are shown in table 2. The concrete carbonation resistance test is shown in table 3.
Table 2 concrete working performance test
TABLE 3 evaluation of concrete anti-carbonation Properties
As can be seen from the table, too low reaction temperature can affect the dissolution and dispersion of raw materials, and too high reaction temperature can damage the monomer structure and cause partial aggregation; according to the concrete reinforcing and toughening additive, specific preparation conditions are adopted, so that the dissolving and dispersing of raw materials in the synthesis and preparation process can be promoted, the reaction can be faster, the effect between the GO solution and the water reducer monomer can be improved, the compression strength and the breaking strength of concrete are greatly improved by skillfully matching various preparation raw materials and combining a specific preparation method, and the carbonization resistance of the concrete is obviously improved in the aspect of durability.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (12)
1. The concrete reinforcing and toughening additive is characterized by comprising the following preparation raw materials: unsaturated polyoxyethylene ether monomer, esterified monomer, quaternary ammonium salt cationic monomer, methacrylic acid, graphene oxide solution, reducing agent, chain transfer agent and oxidant.
2. The concrete reinforcing and toughening admixture according to claim 1, which comprises the following preparation raw materials in parts by weight:
3. the concrete reinforcing and toughening admixture according to claim 1, wherein: the unsaturated polyoxyethylene ether monomer is isopentenyl polyoxyethylene ether with molecular weight of 2000, 2400 or 3000.
4. The concrete reinforcing and toughening admixture according to claim 1, wherein the preparation method of the esterified monomer is as follows:
continuously introducing protective gas into a container provided with a condensing device, sequentially adding diethylene glycol monovinyl ether, alanine, xylene, methanesulfonic acid and p-hydroxyanisole, reacting at constant temperature of 100 ℃, and cooling to 40 ℃ after the reaction is finished to obtain the esterified monomer.
5. The concrete reinforcing and toughening admixture according to claim 4, wherein: n (diethylene glycol monovinyl ether) ((alanine)) (-1.5: 1), xylene accounts for 20% of the total mass of diethylene glycol monovinyl ether and alanine, and methanesulfonic acid and p-hydroxyanisole account for 1.5% and 1% of the total mass of diethylene glycol monovinyl ether and alanine, respectively.
6. The concrete reinforcing and toughening admixture according to claim 1, wherein: the quaternary ammonium salt cationic monomer is one of acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl dimethyl butyl ammonium bromide, dimethyl diene ammonium chloride, ethyl diene ammonium chloride or 2-acrylamido-2-methylpropanesulfonic acid.
7. The concrete reinforcing and toughening admixture according to claim 1, wherein: the reducing agent is one of 2-hydroxy-2-sulfinic acid sodium acetate, sodium bisulfite, ascorbic acid or sodium hypophosphite.
8. The concrete reinforcing and toughening admixture according to claim 1, wherein: the chain transfer agent is one of 3, 6-dioxo-1, 8-octanedithiol, mercaptopropionic acid, sodium bisulfite, isopropanol or sodium hypophosphite.
9. The concrete reinforcing and toughening admixture according to claim 1, wherein: the oxidant is one of tert-butyl hydroperoxide, ammonium persulfate, hydrogen peroxide or sodium persulfate.
10. The concrete reinforcing and toughening admixture according to claim 1, wherein: the neutralizing agent is one of sodium methoxide, sodium hydroxide, sodium tert-butoxide or dimethylethanolamine.
11. A method for preparing a concrete reinforcing and toughening admixture according to any one of claims 1 to 10, comprising the following preparation steps:
adding an unsaturated polyoxyethylene ether monomer, an esterified monomer, a quaternary ammonium salt cationic monomer and methacrylic acid into a graphene oxide solution, carrying out ultrasonic treatment, adding into a reaction device, heating to 60 ℃, and stirring to form a monomer mixed solution;
step two, mixing a reducing agent, a chain transfer agent and water, and adding the mixture into a first dripping device;
step three, mixing an oxidant and water and adding the mixture into a second dripping device;
respectively dripping the solution in the first dripping device and the solution in the second dripping device into a reaction device, and reacting at a constant temperature of 60 ℃;
and step five, cooling the reaction temperature to room temperature, adding a neutralizer solution into the reaction device, and adjusting the pH value of the mixed solution to 7-8 to obtain the concrete reinforcing and toughening additive.
12. The preparation method of the concrete reinforcing and toughening admixture according to claim 11, wherein the preparation method of the graphene oxide solution comprises the following steps: and (2) placing the graphene oxide powder with the lamella diameter of 0.2-10 mu m into deionized water, performing ultrasonic dispersion to ensure that the powder lamella is completely peeled and dispersed to obtain a graphene oxide solution, and controlling the mass fraction of the graphene oxide to be 2%.
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| CN114524909B (en) * | 2022-04-21 | 2022-07-29 | 石家庄市长安育才建材有限公司 | Ultra-high-strength concrete additive, preparation method thereof and ultra-high-strength concrete |
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