CN117024669B - Mud-resistant polycarboxylate superplasticizer and preparation method thereof - Google Patents
Mud-resistant polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000008030 superplasticizer Substances 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013067 intermediate product Substances 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 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- WNAXDEIPNWZUPQ-UHFFFAOYSA-N 2-[chloro-(2,6-dimethylphenyl)phosphoryl]-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1P(Cl)(=O)C1=C(C)C=CC=C1C WNAXDEIPNWZUPQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 3
- 239000004568 cement Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 7
- 239000004576 sand Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 unsaturated alcohol amine compounds Chemical class 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WPJGWJITSIEFRP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrate Chemical compound O.NC1=NC(N)=NC(N)=N1 WPJGWJITSIEFRP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent 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
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an anti-mud type modified polycarboxylate water reducer which is characterized in that EPEG3000, maleic anhydride and a modified monomer are used as monomers, and the anti-mud type modified polycarboxylate water reducer is prepared through polymerization under the action of an initiator and a chain transfer agent; the preparation method of the modified monomer comprises the following steps: adding acrylic acid, ferrocenyl glycidyl ether, p-toluenesulfonic acid and hydroquinone into a reaction vessel, and continuously introducing N 2 Stirring for reaction, and washing to remove unreacted substances to obtain an intermediate product; adding the intermediate product and triethylamine into N-octane, continuously introducing N 2 Dropwise adding bis (2, 6-xylyl) phosphoryl chloride under stirring, continuing stirring for reaction after the dropwise adding, removing the solvent by rotary evaporation, washing and drying the product to obtain a modified monomer; the prepared modified polycarboxylate water reducer can effectively improve the mechanical strength, slump and water reducing rate of concrete, and can meet the construction requirements of concrete engineering.
Description
Technical Field
The invention relates to the technical field of water reducers, in particular to an anti-mud polycarboxylate water reducer and a preparation method thereof.
Background
The essence of the water reducer is a surfactant which has strong adsorption and dispersion effects on cement particles, and is also called superplasticizer. After the cement is mixed into cement, the flocculation structure of cement particles is destroyed, so that the water wrapped in cement floccules is released, the fluidity of concrete is improved, the workability of the concrete is improved, the concrete structure becomes compact, and the strength is increased. After the water reducer is doped into cement, lipophilic groups in molecules of the water reducer are adsorbed on the surfaces of cement particles, and the hydrophilic groups are adsorbed in a water phase, so that the cement particles are charged with the same charge, and meanwhile, a hydration film is formed on the surfaces of the cement particles after polar groups are adsorbed in the liquid phase. The mutual repulsion between the same charges causes the cement particles to be dispersed, and the hydration film plays a role in lubrication, so that the water reducer has the function of dispersing the cement particles.
The water reducer can be divided into lignin sulfonic acid water reducer, melamine water reducer, naphthalene water reducer, sulfamate water reducer and polycarboxylate high-efficiency water reducer according to chemical components.
The polycarboxylate water reducer is a new generation of high-efficiency water reducer. The molecular side chain contains a plurality of hydrophilic groups such as hydroxyl, ether group, carboxyl and the like, and the molecular main chain also has a plurality of active groups. Two main groups can be distinguished according to the differences in the backbone structure: the main chain of the polymer is composed of (methyl) acrylic acid as a monomer, and the side chain is composed of polyether macromonomers with different molecular weights; the other is to polymerize maleic anhydride as monomer to form main chain and graft polyether macromonomer with different polymerization degree to the main chain to form side chain. The polycarboxylate water reducer is called as a new generation of green environment-friendly water reducer, has a special comb-shaped structure, and represents the development direction of the concrete water reducer in the future.
With the rapid development of large-scale infrastructure construction and the enhancement of environmental protection, coarse and fine aggregate resources such as natural sand, cobble and the like are increasingly deficient, sand aggregate with stable quality, good grain grading and low mud content tends to be reduced, especially in industrial and civil construction, a large amount of machine-made sand with high mud content and high stone powder content is directly used for concrete mixing, the consumption of water reducing agent by the concrete can be greatly increased by clay, and the water reducing rate and slump retaining performance of the concrete are reduced.
Chinese patent document CN202111354036.6 discloses a high water-reducing EPEG type polycarboxylate superplasticizer and a preparation method thereof. Wherein, the high water-reducing type EPEG type polycarboxylate water reducer comprises ethylene glycol monovinyl polyethylene glycol ether (EPEG), unsaturated acid monomers, amide polymers, unsaturated carboxylic acid/anhydride, unsaturated sulfonate and a function regulator; wherein the function regulator is a polymer of unsaturated alcohol amine compounds, unsaturated ester monomers and unsaturated phosphoric acid monomers; the polycarboxylate water reducer has poor mud resistance, and the water reducing rate is obviously reduced when the polycarboxylate water reducer is applied to sandstone concrete with high mud content and high stone powder content.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the anti-mud polycarboxylic acid water reducer and the preparation method thereof, wherein the water reducer has high water reducing rate, stable performance and excellent mud resisting effect, can solve the problem of reduced fluidity of the concrete with high mud sand Dan Yuban content, and effectively improves the mechanical strength, slump and water reducing rate of the concrete.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the anti-mud modified polycarboxylate water reducer is prepared by using EPEG3000, maleic anhydride and modified monomers as monomers through free radical polymerization under the action of an initiator and a chain transfer agent.
Preferably, the preparation method of the modified monomer comprises the following steps:
(1) Adding acrylic acid, ferrocenyl glycidyl ether, p-toluenesulfonic acid and hydroquinone into a reaction vessel, and continuously introducing N 2 Stirring for reaction, and washing to remove unreacted substances to obtain an intermediate product;
(2) Adding the intermediate product and triethylamine into N-octane, continuously introducing N 2 And (3) dropwise adding bis (2, 6-xylyl) phosphoryl chloride under stirring, continuing stirring for reaction after the dropwise adding is finished, removing the solvent by rotary evaporation, washing and drying the product, and thus obtaining the modified monomer.
Preferably, in the step (1), the molar ratio of acrylic acid, ferrocenyl glycidyl ether, p-toluenesulfonic acid and hydroquinone is 1:1 to 1.5:0.01 to 0.05: 0.002-0.02.
Preferably, in the step (1), the stirring reaction condition is 70-100 ℃ for 4-8 hours.
Preferably, in the step (2), the weight ratio of the intermediate product to the triethylamine to the bis (2, 6-xylyl) phosphoryl chloride is 30-50: 2 to 5:5 to 10.
Preferably, in the step (2), the dropping of the bis (2, 6-xylyl) phosphoryl chloride is completed for 1-2 hours.
Preferably, in the step (2), the stirring reaction condition is 50-80 ℃ for 4-8 hours.
The invention also claims a preparation method of the water reducer, which comprises the following steps: adding EPEG3000, modified monomer and thioglycollic acid into deionized water, continuously introducing N 2 Heating to 30-50 ℃, uniformly mixing reactants, heating to 60-90 ℃, then dropwise adding maleic anhydride and potassium persulfate, stirring and reacting for 1-3 h, and regulating the pH of the product by alkali liquor to obtain the mud-resistant modified polycarboxylate water reducer.
Preferably, the weight ratio of EPEG3000, modified monomer, maleic anhydride, thioglycollic acid and potassium persulfate is 80-100: 5-10: 20-40: 1.5 to 5:0.5 to 3.
Preferably, the alkali liquor is 30wt% NaOH solution, and the pH of the solution is adjusted to 6-7.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention adopts the reaction of epoxy group of ferrocenyl glycidyl ether and carboxylic acid group of acrylic acid, and grafts the ferrocenyl glycidyl ether onto the acrylic acid to obtain hydroxyl ester; and then, the nucleophilic reaction of the phosphorus-chlorine bond of the bis (2, 6-xylyl) phosphoryl chloride and the hydroxyl group of the hydroxyl ester is utilized to obtain the anti-mud modified polycarboxylate water reducer, which has the advantages of low cost, high water reducing rate, stable performance and excellent mud resistance, can solve the problem of the decline of the fluidity of the concrete with high mud sand Dan Yuban content, effectively improves the mechanical strength, slump and water reducing rate of the concrete on the premise of not increasing the doping amount of the water reducer, and can meet the construction requirements of concrete engineering.
2) The invention provides an anti-mud type modified polycarboxylate water reducer, which introduces ferrocene groups into carboxylic acid groups of acrylic acid monomers, and inhibits the surface adsorption and intercalation adsorption of clay on the water reducer by utilizing the steric hindrance effect of the ferrocene groups, so that the anti-adsorption capacity of the water reducer on clay is effectively improved; and then, a phosphoric acid group containing a methyl benzene ring is introduced into the molecular structure of the water reducer, so that the physical size of a side chain of the polycarboxylate water reducer is greatly increased, the steric hindrance is increased, and clay minerals are not easy to adsorb and penetrate into the water reducer molecules; the introduction of the phosphoric acid groups enables clay in the aggregate to be preferentially adsorbed on the phosphoric acid groups through competitive adsorption, so that the sensitivity of the polycarboxylate water reducer to the mud content of sand and stone can be reduced, and the phenomena of large mixing amount of the water reducer and too fast slump loss of concrete when the mud content is high are effectively solved; and the modification is obtained by bonding acrylic acid monomers, ferrocenyl glycidyl ether and bis (2, 6-xylyl) phosphoryl chloride through chemical bonds, so that the prepared modified water reducer has stable performance and is not influenced by concrete system temperature and pH when in use.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the molecular structural formula of the modified monomer prepared by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
The invention will be further illustrated by the following examples.
Example 1
The preparation method of the anti-mud modified polycarboxylate superplasticizer comprises the following steps of:
(1) 1mol of acrylic acid, 1.5mol of ferrocenyl glycidyl ether, 0.03mol of p-toluenesulfonic acid and 0.01mol of hydroquinone are added into a reaction vessel, and N is continuously introduced 2 Stirring and reacting for 8 hours at 100 ℃, and washing to remove unreacted substances to obtain an intermediate product;
(2) 50g of intermediate product and 5g of triethylamine are added into 80g of N-octane, and N is continuously introduced 2 Adding 10g of bis (2, 6-xylyl) phosphoryl chloride dropwise under stirring, reacting for 8 hours under stirring at 80 ℃ after the completion of the dropwise addition, removing the solvent by rotary evaporation, washing and drying the product to obtain a modified monomer;
(3) 100g of EPEG3000, 10g of modified monomer and 3g of thioglycollic acid are added into deionized water, and N is continuously introduced 2 Heating to 40 ℃ to uniformly mix reactants, heating to 80 ℃, then dropwise adding 30g of maleic anhydride and 2g of potassium persulfate, stirring and reacting for 2 hours, and regulating the pH of the product to 7 by using 30wt% NaOH solution to obtain the anti-mud modified polycarboxylate water reducer.
Example 2
The preparation method of the anti-mud modified polycarboxylate superplasticizer comprises the following steps of:
(1) 1mol of acrylic acid, 1mol of ferrocenyl glycidyl ether, 0.03mol of p-toluenesulfonic acid and 0.01mol of hydroquinone are added into a reaction vessel, and N is continuously introduced 2 Stirring at 70 ℃ for reaction for 4 hours, and washing to remove unreacted substances to obtain an intermediate product;
(2) 30g of intermediate product and 2g of triethylamine are added into 80g of N-octane, and N is continuously introduced 2 Dropwise adding 5g of bis (2, 6-xylyl) phosphoryl chloride under stirring, stirring at 50 ℃ for 4 hours after the completion of the dropwise adding, removing the solvent by rotary evaporation, washing and drying the product to obtain a modified monomer;
(3) 100g of EPEG3000, 10g of modified monomer,3g of thioglycollic acid is added into deionized water, and N is continuously introduced 2 Heating to 40 ℃ to uniformly mix reactants, heating to 80 ℃, then dropwise adding 30g of maleic anhydride and 2g of potassium persulfate, stirring and reacting for 2 hours, and regulating the pH of the product to 7 by using 30wt% NaOH solution to obtain the anti-mud modified polycarboxylate water reducer.
Example 3
The preparation method of the anti-mud modified polycarboxylate superplasticizer comprises the following steps of:
(1) 1mol of acrylic acid, 1.2mol of ferrocenyl glycidyl ether, 0.03mol of p-toluenesulfonic acid and 0.01mol of hydroquinone are added into a reaction vessel, and N is continuously introduced 2 Stirring and reacting for 6 hours at 90 ℃, and washing to remove unreacted substances to obtain an intermediate product;
(2) 40g of intermediate product and 4g of triethylamine are added into 80g of N-octane, and N is continuously introduced 2 8g of bis (2, 6-xylyl) phosphoryl chloride is dropwise added under stirring, after the completion of the dropwise addition, stirring is carried out at 70 ℃ for 6 hours, the solvent is removed by rotary evaporation, and the product is washed and dried to obtain a modified monomer;
(3) 100g of EPEG3000, 10g of modified monomer and 3g of thioglycollic acid are added into deionized water, and N is continuously introduced 2 Heating to 40 ℃ to uniformly mix reactants, heating to 80 ℃, then dropwise adding 30g of maleic anhydride and 2g of potassium persulfate, stirring and reacting for 2 hours, and regulating the pH of the product to 7 by using 30wt% NaOH solution to obtain the anti-mud modified polycarboxylate water reducer.
Comparative example 1
A preparation method of a polycarboxylate superplasticizer comprises the following steps:
(1) 1mol of acrylic acid, 1.5mol of ferrocenyl glycidyl ether, 0.03mol of p-toluenesulfonic acid and 0.01mol of hydroquinone are added into a reaction vessel, and N is continuously introduced 2 Stirring and reacting for 8 hours at 100 ℃, and washing to remove unreacted substances to obtain an intermediate product;
(2) 100g of EPEG3000, 10g of intermediate product and 3g of thioglycollic acid are added into deionized water, and N is continuously introduced 2 Heating to 40 ℃ to uniformly mix reactants, heating to 80 ℃, then dripping 30g of maleic anhydride and 2g of potassium persulfate, stirring and reacting for 2 hours, regulating the pH of the product to 7 by using 30wt% NaOH solution,and obtaining the polycarboxylate water reducer.
Comparative example 2
A preparation method of a polycarboxylate superplasticizer comprises the following steps:
100g of EPEG3000, 10g of acrylic acid and 3g of thioglycollic acid are added into deionized water, and N is continuously introduced 2 Heating to 40 ℃ to uniformly mix reactants, heating to 80 ℃, then dropwise adding 30g of maleic anhydride and 2g of potassium persulfate, stirring and reacting for 2 hours, and regulating the pH of the product to 7 by using 30wt% NaOH solution to obtain the polycarboxylate water reducer.
The water reducers prepared in examples 1 to 3 and comparative examples 1 to 2 are mixed into concrete, the fluidity of cement paste is measured according to GB/T8077-2012 "concrete admixture homogeneity test method", standard test blocks are manufactured according to GB/T50081-2019 "common concrete mechanical property test method Standard", and the compressive strength and flexural strength of the standard test blocks for curing 7d and 28d are measured; slump was measured with reference to GB 8076-2008 concrete admixture.
Bentonite (produced in mineral product processing factories of Ming run county) is used for replacing cement with corresponding quality according to an internal mixing method, the mixing amount of bentonite is 4%, the cement is selected as reference cement, the mixing amount of water reducing agent is 0.18% (folding fixation), the water cement ratio of cement paste is 0.29, and the test result is shown in table 1.
Table 1 results of concrete performance test
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The anti-mud modified polycarboxylate water reducer is characterized in that EPEG3000, maleic anhydride and modified monomers are used as monomers, and the anti-mud modified polycarboxylate water reducer is prepared through polymerization under the action of an initiator and a chain transfer agent;
the preparation method of the modified monomer comprises the following steps:
(1) Adding acrylic acid, ferrocenyl glycidyl ether, p-toluenesulfonic acid and hydroquinone into a reaction vessel, and continuously introducing N 2 Stirring for reaction, and washing to remove unreacted substances to obtain an intermediate product;
(2) Adding the intermediate product and triethylamine into N-octane, continuously introducing N 2 And (3) dropwise adding bis (2, 6-xylyl) phosphoryl chloride under stirring, continuing stirring for reaction after the dropwise adding is finished, removing the solvent by rotary evaporation, washing and drying the product, and thus obtaining the modified monomer.
2. The water reducing agent according to claim 1, wherein in the step (1), the molar ratio of acrylic acid, ferrocenyl glycidyl ether, p-toluene sulfonic acid, hydroquinone is 1:1 to 1.5:0.01 to 0.05: 0.002-0.02.
3. The water reducing agent according to claim 1, wherein in the step (1), the reaction is carried out at 70 to 100 ℃ for 4 to 8 hours under stirring.
4. The water reducing agent according to claim 1, wherein in the step (2), the weight ratio of the intermediate product, triethylamine, bis (2, 6-xylyl) phosphoryl chloride is 30 to 50:2 to 5:5 to 10.
5. The water reducing agent according to claim 1, wherein in the step (2), the dropping of the bis (2, 6-xylyl) phosphoryl chloride is completed for 1 to 2 hours.
6. The water reducing agent according to claim 1, wherein in the step (2), the reaction is carried out at 50 to 80 ℃ for 4 to 8 hours under stirring.
7. A method for preparing a water reducing agent as claimed in any one of claims 1 to 6, characterized by the steps of: EPEG3000, modified monomer and sulfhydryl group BAdding acid into deionized water, continuously introducing N 2 Heating to 30-50 ℃, uniformly mixing reactants, heating to 60-90 ℃, then dropwise adding maleic anhydride and potassium persulfate, stirring and reacting for 1-3 h, and regulating the pH of the product by alkali liquor to obtain the mud-resistant modified polycarboxylate water reducer.
8. The preparation method according to claim 7, wherein the weight ratio of EPEG3000, modified monomer, maleic anhydride, thioglycollic acid and potassium persulfate is 80-100: 5-10: 20-40: 1.5 to 5:0.5 to 3.
9. The process according to claim 7, wherein the lye is 30wt% naoh solution and the pH of the solution is adjusted to 6-7.
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