CN112126022A - Formula and preparation method of polycarboxylate superplasticizer - Google Patents
Formula and preparation method of polycarboxylate superplasticizer Download PDFInfo
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- CN112126022A CN112126022A CN202010952764.6A CN202010952764A CN112126022A CN 112126022 A CN112126022 A CN 112126022A CN 202010952764 A CN202010952764 A CN 202010952764A CN 112126022 A CN112126022 A CN 112126022A
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 55
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000009472 formulation Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 68
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 30
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 21
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 20
- 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 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 14
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000008234 soft water Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 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 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- KUDUQBURMYMBIJ-UHFFFAOYSA-N ethylene glycol diacrylate Substances C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 19
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical group OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 18
- -1 isopentenyl Chemical group 0.000 claims description 15
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 14
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 13
- 229930003268 Vitamin C Natural products 0.000 claims description 13
- 239000011718 vitamin C Substances 0.000 claims description 13
- 235000019154 vitamin C Nutrition 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 11
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 11
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 10
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000012856 weighed raw material Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004568 cement Substances 0.000 abstract description 8
- 239000004576 sand Substances 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000010276 construction Methods 0.000 description 7
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000007 visual effect Effects 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
- 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
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a formula of a polycarboxylate superplasticizer, which mainly comprises the following raw material components in parts by weight: 360-370 parts of ether macromonomer, 20-40 parts of acrylic acid, 1-3 parts of diacrylate, 1-3 parts of methylene bisacrylamide, 2-4 parts of oxidant, 0.5-1.5 parts of reducing agent, 1-3 parts of chain transfer agent, 0.025-0.075 part of auxiliary reducing agent, 100-300 parts of cocatalyst, 30-50 parts of 30% sodium hydroxide aqueous solution, 100-300 parts of soft water, 100-300 parts of water, 25-35 parts of styrene, 20-40 parts of unsaturated anhydride, 10-20 parts of butyl acetate, 100-200 parts of absolute ethyl alcohol, 50-90 parts of n-heptane, 2-4 parts of initiator, polyethylene glycol and deionized water. The invention has the technical effects of preventing cement from being quickly adsorbed, having high retentivity and higher slump retaining performance and workability.
Description
Technical Field
The invention relates to the technical field of polycarboxylate superplasticizer processes, and particularly relates to a formula and a preparation method of a polycarboxylate superplasticizer.
Background
In recent years, with the vigorous development of the construction industry, the large-scale use of the machine-made sand leads to the rapid development of the application of the flocculating agent in the water-washing machine-made sand. The flocculating agent is used by sandstone production enterprises because most of machine-made sand is crushed stone sand or mountain sand, which contains mud and powder of different types and quantities, and most of the mud and powder are required to be removed by water washing so as to avoid influencing the use of concrete. The environment-friendly requirement that the water for sand washing needs to be purified and can not be discharged in disorder, and the flocculant can enable solute, colloid or suspended particles in the water solution to generate flocculent precipitate so as to play a role in purifying water quality, so that sand and stone production enterprises at present widely use the flocculant to purify the sand washing water, filter the water quality and recycle the sand and stone. But sandstone production enterprises only consider that the discharge of the sand washing water meets the environmental protection requirement, but cannot consider that a large amount of flocculant contained in the recycled sand washing water can be brought into the machine-made sand, thereby having adverse effect on concrete.
The polyaluminium chloride is one of high-efficiency water treatment agents which develop rapidly in recent decades, and compared with the traditional medicament, the polyaluminium chloride has the characteristics of small dosage, low cost, excellent water purification quality, convenience in use and the like, so that the polyaluminium chloride is widely used in sand washing. According to the feedback of the commodity stirring station: the washed sand treated by polyaluminium chloride is used, so that the loss of the fresh concrete is fast, and the construction cannot be carried out.
Therefore, the formula and the preparation method of the polycarboxylic acid water reducing agent have the advantages of capability of preventing cement from being rapidly adsorbed, high retentivity, high slump loss resistance and high workability, and are very necessary.
Disclosure of Invention
The invention aims to provide a formula and a preparation method of a polycarboxylate superplasticizer, so as to realize the technical effects provided in the background technology.
In order to realize the purpose, the invention provides the following technical scheme: the formula of the polycarboxylic acid water reducing agent mainly comprises the following raw materials in parts by weight: 360-370 parts of ether macromonomer, 20-40 parts of acrylic acid, 1-3 parts of diacrylate, 1-3 parts of methylene bisacrylamide, 2-4 parts of oxidant, 0.5-1.5 parts of reducing agent, 1-3 parts of chain transfer agent, 0.025-0.075 part of auxiliary reducing agent, 100-300 parts of cocatalyst, 30-50 parts of 30% sodium hydroxide aqueous solution, 100-300 parts of soft water, 100-300 parts of water, 25-35 parts of styrene, 20-40 parts of unsaturated anhydride, 10-20 parts of butyl acetate, 100-200 parts of absolute ethyl alcohol, 50-90 parts of n-heptane, 2-4 parts of initiator, 100-200 parts of polyethylene glycol and 100-300 parts of deionized water.
Preferably, the ether macromonomer is isopentenyl polyoxyethylene ether 2400.
Preferably, the diacrylate is ethylene glycol diacrylate or 1, 4-butanediol acrylate.
Preferably, the chain transfer agent is mercaptopropionic acid and mercaptoethanol in a mass ratio of 1: 1 in combination.
Preferably, the oxidant is hydrogen peroxide and ammonium persulfate according to a mass ratio of 2: 1 in combination.
Preferably, the reducing agent is vitamin C.
Preferably, the co-reducing agent is ferrous sulfate.
Preferably, the promoter consists of alumina and potassium oxide.
Preferably, the chain transfer agent is one or a mixture of more of thioglycolic acid, mercaptopropionic acid and dodecyl mercaptan.
A preparation method of a polycarboxylate superplasticizer comprises the following steps:
the method comprises the following steps: preparing raw materials: placing a beaker on a high-precision electronic scale, weighing an ether macromonomer, acrylic acid, diacrylate, methylene bisacrylamide, an oxidizing agent, a reducing agent, a chain transfer agent, a co-reducing agent, a cocatalyst, a 30% sodium hydroxide aqueous solution, styrene, unsaturated anhydride, butyl acetate, n-heptane and an initiator according to a proportion by using the beaker, and putting the weighed raw materials into a glass container for later use;
step two: adding the unsaturated anhydride into a four-neck flask with a condensation reflux device, adding the n-heptane and the butyl acetate, placing the mixture into a constant-temperature water bath kettle, introducing nitrogen for protection, keeping the temperature at 40-50 ℃, continuously stirring for 10-20 min, then heating to 70-80 ℃, preheating, and continuously stirring for 20-30 min;
step three: adding the initiator and the chain transfer agent in the step one into the four-neck flask in the step two, stirring for 10-20 min, then beginning to dropwise add styrene, preserving heat after dropwise adding is finished, cooling to room temperature, performing suction filtration, washing with absolute ethyl alcohol, drying, and then adding a ball mill to obtain a reaction intermediate C;
step four: performing copolymerization reaction, namely adding the ether macromonomer in the first step into a flask, heating to 50-70 ℃, stirring to completely melt the ether macromonomer, continuously heating to 80-100 ℃, adding the reaction intermediate C prepared in the third step, uniformly adding and stirring for 20-40 min, heating to 100-120 ℃, keeping the temperature for 2-4 h, and cooling to room temperature to obtain a reaction product D;
step five: mixing acrylic acid, mercaptopropionic acid, mercaptoethanol, ferrous sulfate and soft water to obtain a material A, and mixing vitamin C and water to obtain a material B;
step six: starting stirring in a four-neck flask provided with a thermometer, a speed-regulating stirrer, a reflux condenser and a dropping device, and adding soft water, isopentenyl polyoxyethylene ether 2400, ethylene glycol diacrylate, hydrogen peroxide and ammonium persulfate;
step seven: dripping the material A and the material B into the four-neck flask obtained in the sixth step at the same time, wherein the material A is uniformly dripped for 2-4 h, the material B is uniformly dripped for 3-4 h, after the material B is dripped, curing is carried out for 1-2 h, and then 30% of sodium hydroxide aqueous solution is added;
step eight: and C, adding water into the seventh step until the solid content is 40%, and adding the reaction product D obtained in the fourth step and deionized water for dilution to obtain the polycarboxylic acid water reducer.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the polycarboxylate superplasticizer, a bifunctional monomer diacrylate and methylene bisacrylamide are adopted for copolymerization on the basis of the conventional small monomer acrylic acid, so that a certain amount of network structure is formed by the copolymer, the copolymer is prevented from being quickly adsorbed by cement, and meanwhile, the copolymer is slowly hydrolyzed to release carboxyl, so that the retentivity of fresh concrete is improved, and the preparation method is beneficial to construction.
2. The preparation method of the polycarboxylate superplasticizer comprises the steps of reacting an ether macromonomer, acrylic acid, diacrylate and methylene bisacrylamide in an oxidation-reduction initiator, a chain transfer agent and a reducing aid, and neutralizing with a 32% sodium hydroxide aqueous solution to obtain the polycarboxylate superplasticizer suitable for phosphogypsum self-leveling mortar. The polycarboxylate superplasticizer has low energy consumption in the synthesis process and is very suitable for phosphogypsum.
3. According to the preparation method of the polycarboxylate water reducer, the introduced anhydride has a slow release effect, and meanwhile, the long side chain of the polyethylene glycol and the side chain of the benzene ring have good steric hindrance and a micro-bubble introducing effect, so that the polycarboxylate water reducer has good slump retaining performance and workability, and is beneficial to the construction of high-grade concrete.
4. According to the preparation method of the polycarboxylate water reducer, styrene, unsaturated anhydride and isopentenyl polyoxyethylene ether 2400 are used for synthesizing the polycarboxylate water reducer, a benzene ring and anhydride are introduced into a side chain of the polycarboxylate water reducer to adjust the hydrophilic and oleophilic values of the polycarboxylate water reducer, and a long side chain of absolute ethyl alcohol is introduced to increase the infiltration type of the polycarboxylate water reducer on cement particles, so that the polycarboxylate water reducer has better concrete viscosity reduction performance than a common polycarboxylate water reducer.
5. According to the preparation method of the polycarboxylate superplasticizer, the reducing agent is vitamin C, and the alkylene glycol group in the molecular structure of the vitamin C has extremely strong reducibility; the catalyst promoter consists of alumina and potassium oxide, wherein the alumina is a structural catalyst promoter and is used for increasing the specific surface area of the active component or improving the stability of the active structure, and the potassium oxide is a modulation catalyst promoter and can modify the nature of the active component, thereby changing the specific activity of the active component and ensuring the smooth and efficient reaction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example one
The formula of the polycarboxylic acid water reducing agent mainly comprises the following raw materials in parts by weight: 360 parts of ether macromonomer, 20 parts of acrylic acid, 1 part of diacrylate, 1 part of methylene bisacrylamide, 2 parts of oxidant, 0.5 part of reducing agent, 1 part of chain transfer agent, 0.025 part of co-reducing agent, 100 parts of cocatalyst, 30 parts of 30% sodium hydroxide aqueous solution, 100 parts of soft water, 100 parts of water, 25 parts of styrene, 20 parts of unsaturated anhydride, 10 parts of butyl acetate, 100 parts of absolute ethyl alcohol, 50 parts of n-heptane, 2 parts of initiator, 100 parts of polyethylene glycol and 100 parts of deionized water.
In this embodiment, the ether macromonomer is isopentenyl polyoxyethylene ether 2400.
In this embodiment, the diacrylate is ethylene glycol diacrylate or 1, 4-butanediol acrylate.
In this embodiment, the chain transfer agent is mercaptopropionic acid and mercaptoethanol in a mass ratio of 1: 1 in combination.
In this embodiment, the oxidant is hydrogen peroxide and ammonium persulfate, and the mass ratio is 2: 1 in combination.
In this embodiment, the reducing agent is vitamin C.
In this embodiment, the reductant-aid is ferrous sulfate.
In this embodiment, the promoter is composed of alumina and potassium oxide.
In this embodiment, the chain transfer agent is one or a mixture of several of thioglycolic acid, mercaptopropionic acid, and dodecyl mercaptan.
Example two
The formula of the polycarboxylic acid water reducing agent mainly comprises the following raw materials in parts by weight: 370 parts of ether macromonomer, 40 parts of acrylic acid, 3 parts of diacrylate, 3 parts of methylene bisacrylamide, 4 parts of oxidant, 1.5 parts of reducing agent, 3 parts of chain transfer agent, 0.075 part of co-reducing agent, 300 parts of cocatalyst, 50 parts of 30% sodium hydroxide aqueous solution, 300 parts of soft water, 300 parts of water, 35 parts of styrene, 40 parts of unsaturated anhydride, 20 parts of butyl acetate, 200 parts of absolute ethyl alcohol, 90 parts of n-heptane, 4 parts of initiator, 200 parts of polyethylene glycol and 300 parts of deionized water.
In this embodiment, the ether macromonomer is isopentenyl polyoxyethylene ether 2400.
In this embodiment, the diacrylate is ethylene glycol diacrylate or 1, 4-butanediol acrylate.
In this embodiment, the chain transfer agent is mercaptopropionic acid and mercaptoethanol in a mass ratio of 1: 1 in combination.
In this embodiment, the oxidant is hydrogen peroxide and ammonium persulfate, and the mass ratio is 2: 1 in combination.
In this embodiment, the reducing agent is vitamin C.
In this embodiment, the reductant-aid is ferrous sulfate.
In this embodiment, the promoter is composed of alumina and potassium oxide.
In this embodiment, the chain transfer agent is one or a mixture of several of thioglycolic acid, mercaptopropionic acid, and dodecyl mercaptan.
EXAMPLE III
The formula of the polycarboxylic acid water reducing agent mainly comprises the following raw materials in parts by weight: 365 parts of ether macromonomer, 30 parts of acrylic acid, 2 parts of diacrylate, 2 parts of methylene bisacrylamide, 3 parts of oxidizing agent, 1 part of reducing agent, 2 parts of chain transfer agent, 0.05 part of reducing assistant agent, 200 parts of cocatalyst, 40 parts of 30% sodium hydroxide aqueous solution, 200 parts of soft water, 200 parts of water, 30 parts of styrene, 30 parts of unsaturated anhydride, 15 parts of butyl acetate, 150 parts of absolute ethyl alcohol, 70 parts of n-heptane, 3 parts of initiator, 150 parts of polyethylene glycol and 200 parts of deionized water.
In this embodiment, the ether macromonomer is isopentenyl polyoxyethylene ether 2400.
In this embodiment, the diacrylate is ethylene glycol diacrylate or 1, 4-butanediol acrylate.
In this embodiment, the chain transfer agent is mercaptopropionic acid and mercaptoethanol in a mass ratio of 1: 1 in combination.
In this embodiment, the oxidant is hydrogen peroxide and ammonium persulfate, and the mass ratio is 2: 1 in combination.
In this embodiment, the reducing agent is vitamin C.
In this embodiment, the reductant-aid is ferrous sulfate.
In this embodiment, the promoter is composed of alumina and potassium oxide.
In this embodiment, the chain transfer agent is one or a mixture of several of thioglycolic acid, mercaptopropionic acid, and dodecyl mercaptan.
Example four
The formula of the polycarboxylic acid water reducing agent mainly comprises the following raw materials in parts by weight: 360 parts of ether macromonomer, 20 parts of acrylic acid, 1 part of diacrylate, 1 part of methylene bisacrylamide, 2 parts of oxidant, 0.5 part of common reducing agent, 1 part of chain transfer agent, 0.025 part of co-reducing agent, 100 parts of cocatalyst, 30 parts of 30% sodium hydroxide aqueous solution, 100 parts of soft water, 100 parts of water, 25 parts of styrene, 20 parts of unsaturated anhydride, 10 parts of butyl acetate, 100 parts of absolute ethyl alcohol, 50 parts of n-heptane, 2 parts of initiator, 100 parts of polyethylene glycol and 100 parts of deionized water.
In this embodiment, the ether macromonomer is isopentenyl polyoxyethylene ether 2400.
In this embodiment, the diacrylate is ethylene glycol diacrylate or 1, 4-butanediol acrylate.
In this embodiment, the chain transfer agent is mercaptopropionic acid and mercaptoethanol in a mass ratio of 1: 1 in combination.
In this embodiment, the oxidant is hydrogen peroxide and ammonium persulfate, and the mass ratio is 2: 1 in combination.
In this embodiment, the reductant-aid is ferrous sulfate.
In this embodiment, the promoter is composed of alumina and potassium oxide.
In this embodiment, the chain transfer agent is one or a mixture of several of thioglycolic acid, mercaptopropionic acid, and dodecyl mercaptan.
EXAMPLE five
The formula of the polycarboxylic acid water reducing agent mainly comprises the following raw materials in parts by weight: 360 parts of ether macromonomer, 20 parts of acrylic acid, 1 part of diacrylate, 1 part of methylene bisacrylamide, 2 parts of oxidant, 0.5 part of reducing agent, 1 part of chain transfer agent, 0.025 part of co-reducing agent, 30 parts of 30% sodium hydroxide aqueous solution, 100 parts of soft water, 100 parts of water, 25 parts of styrene, 20 parts of unsaturated anhydride, 10 parts of butyl acetate, 100 parts of absolute ethyl alcohol, 50 parts of n-heptane, 2 parts of initiator, 100 parts of polyethylene glycol and 100 parts of deionized water.
In this embodiment, the ether macromonomer is isopentenyl polyoxyethylene ether 2400.
In this embodiment, the diacrylate is ethylene glycol diacrylate or 1, 4-butanediol acrylate.
In this embodiment, the chain transfer agent is mercaptopropionic acid and mercaptoethanol in a mass ratio of 1: 1 in combination.
In this embodiment, the oxidant is hydrogen peroxide and ammonium persulfate, and the mass ratio is 2: 1 in combination.
In this embodiment, the reducing agent is vitamin C.
In this embodiment, the reductant-aid is ferrous sulfate.
In this embodiment, the chain transfer agent is one or a mixture of several of thioglycolic acid, mercaptopropionic acid, and dodecyl mercaptan.
A preparation method of a polycarboxylate superplasticizer comprises the following steps:
the method comprises the following steps: preparing raw materials: placing a beaker on a high-precision electronic scale, weighing an ether macromonomer, acrylic acid, diacrylate, methylene bisacrylamide, an oxidizing agent, a reducing agent, a chain transfer agent, a co-reducing agent, a cocatalyst, a 30% sodium hydroxide aqueous solution, styrene, unsaturated anhydride, butyl acetate, n-heptane and an initiator according to a proportion by using the beaker, and putting the weighed raw materials into a glass container for later use;
step two: adding the unsaturated anhydride into a four-neck flask with a condensation reflux device, adding the n-heptane and the butyl acetate, placing the mixture into a constant-temperature water bath kettle, introducing nitrogen for protection, keeping the temperature at 40-50 ℃, continuously stirring for 10-20 min, then heating to 70-80 ℃, preheating, and continuously stirring for 20-30 min;
step three: adding the initiator and the chain transfer agent in the step one into the four-neck flask in the step two, stirring for 10-20 min, then beginning to dropwise add styrene, preserving heat after dropwise adding is finished, cooling to room temperature, performing suction filtration, washing with absolute ethyl alcohol, drying, and then adding a ball mill to obtain a reaction intermediate C;
step four: performing copolymerization reaction, namely adding the ether macromonomer in the first step into a flask, heating to 50-70 ℃, stirring to completely melt the ether macromonomer, continuously heating to 80-100 ℃, adding the reaction intermediate C prepared in the third step, uniformly adding and stirring for 20-40 min, heating to 100-120 ℃, keeping the temperature for 2-4 h, and cooling to room temperature to obtain a reaction product D;
step five: mixing acrylic acid, mercaptopropionic acid, mercaptoethanol, ferrous sulfate and soft water to obtain a material A, and mixing vitamin C and water to obtain a material B;
step six: starting stirring in a four-neck flask provided with a thermometer, a speed-regulating stirrer, a reflux condenser and a dropping device, and adding soft water, isopentenyl polyoxyethylene ether 2400, ethylene glycol diacrylate, hydrogen peroxide and ammonium persulfate;
step seven: dripping the material A and the material B into the four-neck flask obtained in the sixth step at the same time, wherein the material A is uniformly dripped for 2-4 h, the material B is uniformly dripped for 3-4 h, after the material B is dripped, curing is carried out for 1-2 h, and then 30% of sodium hydroxide aqueous solution is added;
step eight: and C, adding water into the seventh step until the solid content is 40%, and adding the reaction product D obtained in the fourth step and deionized water for dilution to obtain the polycarboxylic acid water reducer.
Experiment one: the polycarboxylate superplasticizers prepared in the first, second, third, fourth and fifth examples and the polycarboxylate superplasticizers prepared in the prior art are respectively subjected to initial slump/initial expansion and 1.5h slump/1 h expansion detection experiments, wherein the smaller the difference between the initial slump/initial expansion and 1.5h slump/1 h expansion is, the better the cement is prevented from being rapidly adsorbed, the higher the retention property is and the higher the slump retaining property is, and the experimental results are shown in the following table:
the experimental results are as follows: the effect, the retentivity and the slump retention performance of the polycarboxylate water reducing agents prepared in the first embodiment, the second embodiment and the third embodiment are slightly higher than those of the polycarboxylate water reducing agents prepared in the fourth embodiment and the fifth embodiment, and the effect, the retentivity and the slump retention performance of the polycarboxylate water reducing agents prepared in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment and the fifth embodiment are obviously higher than those of the polycarboxylate water reducing agents in the prior art.
Experiment two: the polycarboxylate water reducing agents prepared in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment and the fifth embodiment and the polycarboxylate water reducing agents in the prior art are subjected to workability test experiments, and the workability refers to that the freshly mixed cement concrete is easy to construct and operate in various working procedures (stirring, transporting, pouring, tamping and the like) and can obtain uniform-quality and densely-formed performances, and the meanings of the workability include flowability, cohesiveness and water-retaining property. Also known as workability of concrete; the workability of the concrete mixture is a comprehensive concept, and is difficult to be comprehensively and properly expressed by a simple evaluation method, usually, the slump test is adopted to measure the fluidity of the concrete mixture, and visual experience is used for evaluating the cohesiveness and the water-retaining property to comprehensively evaluate; the fluidity of concrete is generally expressed according to the concrete slump measured on site, an instrument for measuring the concrete slump is a slump cone, the measuring method is that a horn-shaped slump cone with an upper opening of 100mm, a lower opening of 200mm and a height of 300mm is used for filling concrete for three times, a rammer is used for uniformly ramming the concrete along the wall of the cone from outside to inside for 25 times after each filling, and the concrete is leveled after ramming. And then pulling up the barrel, wherein the concrete generates a collapse phenomenon due to self weight, and the height of the highest point of the collapsed concrete is subtracted from the barrel height (300mm), so that the measured value of the collapse degree is obtained. The larger the slump value, the larger the fluidity, and vice versa. The water retention refers to the property that fresh concrete has certain water retention capacity and does not cause serious bleeding phenomenon in the construction process. The water retention reflects the stability of the concrete mixture. A water permeable channel is easily formed in the concrete with poor water retention, the compactness of the concrete is influenced, and the strength and the durability of the concrete are reduced. The workability, cohesiveness and water retentivity of the concrete can be expressed by the time taken for observing the appearance of the concrete in a solidified state when the slump of the concrete is tested, and the emptying time taken for water to be contained when the appearance is solidified. The results of the experiments are shown in the following table:
the experimental results are as follows: the workability of the polycarboxylate water reducers prepared in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment and the fifth embodiment is obviously higher than that of the polycarboxylate water reducers in the prior art.
The technical effects are as follows: according to the preparation method of the polycarboxylate superplasticizer, a bifunctional monomer diacrylate and methylene bisacrylamide are adopted for copolymerization on the basis of the conventional small monomer acrylic acid, so that a certain amount of network structure is formed by the copolymer, the copolymer is prevented from being quickly adsorbed by cement, and meanwhile, the copolymer is slowly hydrolyzed to release carboxyl, so that the retentivity of fresh concrete is improved, and the preparation method is beneficial to construction. The preparation method of the polycarboxylate superplasticizer comprises the steps of reacting an ether macromonomer, acrylic acid, diacrylate and methylene bisacrylamide in an oxidation-reduction initiator, a chain transfer agent and a reducing aid, and neutralizing with a 32% sodium hydroxide aqueous solution to obtain the polycarboxylate superplasticizer suitable for phosphogypsum self-leveling mortar. The polycarboxylate superplasticizer has low energy consumption in the synthesis process and is very suitable for phosphogypsum. According to the preparation method of the polycarboxylate water reducer, the introduced anhydride has a slow release effect, and meanwhile, the long side chain of the polyethylene glycol and the side chain of the benzene ring have good steric hindrance and a micro-bubble introducing effect, so that the polycarboxylate water reducer has good slump retaining performance and workability, and is beneficial to the construction of high-grade concrete. According to the preparation method of the polycarboxylate water reducer, styrene, unsaturated anhydride and isopentenyl polyoxyethylene ether 2400 are used for synthesizing the polycarboxylate water reducer, a benzene ring and anhydride are introduced into a side chain of the polycarboxylate water reducer to adjust the hydrophilic and oleophilic values of the polycarboxylate water reducer, and a long side chain of absolute ethyl alcohol is introduced to increase the infiltration type of the polycarboxylate water reducer on cement particles, so that the polycarboxylate water reducer has better concrete viscosity reduction performance than a common polycarboxylate water reducer.
According to the preparation method of the polycarboxylate superplasticizer, the reducing agent is vitamin C, and the alkylene glycol group in the molecular structure of the vitamin C has extremely strong reducibility; the catalyst promoter consists of alumina and potassium oxide, wherein the alumina is a structural catalyst promoter and is used for increasing the specific surface area of the active component or improving the stability of the active structure, and the potassium oxide is a modulation catalyst promoter and can modify the nature of the active component, thereby changing the specific activity of the active component and ensuring the smooth and efficient reaction.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The formula of the polycarboxylic acid water reducing agent is characterized in that: the raw material components mainly comprise the following components in parts by weight: 360-370 parts of ether macromonomer, 20-40 parts of acrylic acid, 1-3 parts of diacrylate, 1-3 parts of methylene bisacrylamide, 2-4 parts of oxidant, 0.5-1.5 parts of reducing agent, 1-3 parts of chain transfer agent, 0.025-0.075 part of auxiliary reducing agent, 100-300 parts of cocatalyst, 30-50 parts of 30% sodium hydroxide aqueous solution, 100-300 parts of soft water, 100-300 parts of water, 25-35 parts of styrene, 20-40 parts of unsaturated anhydride, 10-20 parts of butyl acetate, 100-200 parts of absolute ethyl alcohol, 50-90 parts of n-heptane, 2-4 parts of initiator, 100-200 parts of polyethylene glycol and 100-300 parts of deionized water.
2. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the ether macromonomer is isopentenyl polyoxyethylene ether 2400.
3. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the diacrylate ester is ethylene glycol diacrylate ester or 1, 4-butanediol acrylate ester.
4. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the chain transfer agent is mercaptopropionic acid and mercaptoethanol, and the mass ratio of the mercaptopropionic acid to the mercaptoethanol is 1: 1 in combination.
5. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the oxidant is hydrogen peroxide and ammonium persulfate, and the mass ratio of the hydrogen peroxide to the ammonium persulfate is 2: 1 in combination.
6. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the reducing agent is vitamin C.
7. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the auxiliary reducing agent is ferrous sulfate.
8. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the catalyst promoter consists of aluminum oxide and potassium oxide.
9. The polycarboxylate superplasticizer formulation as claimed in claim 1, wherein: the chain transfer agent is one or a mixture of more of thioglycolic acid, mercaptopropionic acid and dodecyl mercaptan.
10. A preparation method of a polycarboxylate superplasticizer is characterized by comprising the following steps: the method specifically comprises the following steps:
the method comprises the following steps: preparing raw materials: placing a beaker on a high-precision electronic scale, weighing an ether macromonomer, acrylic acid, diacrylate, methylene bisacrylamide, an oxidizing agent, a reducing agent, a chain transfer agent, a co-reducing agent, a cocatalyst, a 30% sodium hydroxide aqueous solution, styrene, unsaturated anhydride, butyl acetate, n-heptane and an initiator according to a proportion by using the beaker, and putting the weighed raw materials into a glass container for later use;
step two: adding the unsaturated anhydride into a four-neck flask with a condensation reflux device, adding the n-heptane and the butyl acetate, placing the mixture into a constant-temperature water bath kettle, introducing nitrogen for protection, keeping the temperature at 40-50 ℃, continuously stirring for 10-20 min, then heating to 70-80 ℃, preheating, and continuously stirring for 20-30 min;
step three: adding the initiator and the chain transfer agent in the step one into the four-neck flask in the step two, stirring for 10-20 min, then beginning to dropwise add styrene, preserving heat after dropwise adding is finished, cooling to room temperature, performing suction filtration, washing with absolute ethyl alcohol, drying, and then adding a ball mill to obtain a reaction intermediate C;
step four: performing copolymerization reaction, namely adding the ether macromonomer in the first step into a flask, heating to 50-70 ℃, stirring to completely melt the ether macromonomer, continuously heating to 80-100 ℃, adding the reaction intermediate C prepared in the third step, uniformly adding and stirring for 20-40 min, heating to 100-120 ℃, keeping the temperature for 2-4 h, and cooling to room temperature to obtain a reaction product D;
step five: mixing acrylic acid, mercaptopropionic acid, mercaptoethanol, ferrous sulfate and soft water to obtain a material A, and mixing vitamin C and water to obtain a material B;
step six: starting stirring in a four-neck flask provided with a thermometer, a speed-regulating stirrer, a reflux condenser and a dropping device, and adding soft water, isopentenyl polyoxyethylene ether 2400, ethylene glycol diacrylate, hydrogen peroxide and ammonium persulfate;
step seven: dripping the material A and the material B into the four-neck flask obtained in the sixth step at the same time, wherein the material A is uniformly dripped for 2-4 h, the material B is uniformly dripped for 3-4 h, after the material B is dripped, curing is carried out for 1-2 h, and then 30% of sodium hydroxide aqueous solution is added;
step eight: and C, adding water into the seventh step until the solid content is 40%, and adding the reaction product D obtained in the fourth step and deionized water for dilution to obtain the polycarboxylic acid water reducer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402679A (en) * | 2021-06-16 | 2021-09-17 | 西南科技大学 | Method for synthesizing polycarboxylic acid water reducing agent by catalyzing magnesium oxide, aluminum oxide or copper oxide |
| CN114478942A (en) * | 2022-01-26 | 2022-05-13 | 四川同舟化工科技有限公司 | Polycarboxylate superplasticizer capable of effectively resisting influence of flocculating agent and preparation method thereof |
| CN116119974A (en) * | 2023-04-14 | 2023-05-16 | 石家庄市长安育才建材有限公司 | Polycarboxylate superplasticizer applicable to plateau areas and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275280A (en) * | 2013-06-17 | 2013-09-04 | 武汉东彭科技发展有限公司 | Synthetic method for polycarboxylate type high slump-retaining water reducing agent at normal temperature |
| CN104150807A (en) * | 2014-07-29 | 2014-11-19 | 太仓新亚逊生物科技有限公司 | Polycarboxylic acid water reducer for pre-stressed high-strength concrete pipe pile and application of polycarboxylic acid water reducer |
| CN104446093A (en) * | 2014-12-04 | 2015-03-25 | 河北铁园科技发展有限公司 | Polycarboxylate-based water reducing agent with integrated functions of water reduction and slump retaining |
| WO2018086610A1 (en) * | 2016-11-14 | 2018-05-17 | 清华大学 | Polymer and preparation method and application thereof |
| CN108484839A (en) * | 2018-03-23 | 2018-09-04 | 刘翠芬 | A kind of amphipathic carboxylic dispersants and preparation method thereof |
| CN108911561A (en) * | 2018-05-25 | 2018-11-30 | 湖北工业大学 | 2200 molecular weight polyether polycarboxylic acid slump retaining agents of one kind and preparation method |
| CN109824836A (en) * | 2019-01-29 | 2019-05-31 | 广东瑞安科技实业有限公司 | Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN110041468A (en) * | 2019-04-26 | 2019-07-23 | 四川同舟化工科技有限公司 | Viscosity reduction type polycarboxylate water-reducer |
-
2020
- 2020-09-11 CN CN202010952764.6A patent/CN112126022A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275280A (en) * | 2013-06-17 | 2013-09-04 | 武汉东彭科技发展有限公司 | Synthetic method for polycarboxylate type high slump-retaining water reducing agent at normal temperature |
| CN104150807A (en) * | 2014-07-29 | 2014-11-19 | 太仓新亚逊生物科技有限公司 | Polycarboxylic acid water reducer for pre-stressed high-strength concrete pipe pile and application of polycarboxylic acid water reducer |
| CN104446093A (en) * | 2014-12-04 | 2015-03-25 | 河北铁园科技发展有限公司 | Polycarboxylate-based water reducing agent with integrated functions of water reduction and slump retaining |
| WO2018086610A1 (en) * | 2016-11-14 | 2018-05-17 | 清华大学 | Polymer and preparation method and application thereof |
| CN108484839A (en) * | 2018-03-23 | 2018-09-04 | 刘翠芬 | A kind of amphipathic carboxylic dispersants and preparation method thereof |
| CN108911561A (en) * | 2018-05-25 | 2018-11-30 | 湖北工业大学 | 2200 molecular weight polyether polycarboxylic acid slump retaining agents of one kind and preparation method |
| CN109824836A (en) * | 2019-01-29 | 2019-05-31 | 广东瑞安科技实业有限公司 | Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN110041468A (en) * | 2019-04-26 | 2019-07-23 | 四川同舟化工科技有限公司 | Viscosity reduction type polycarboxylate water-reducer |
Non-Patent Citations (1)
| Title |
|---|
| 蔡正华，等: "基于HPEG 大单体常温合成高保坍型聚羧酸减水剂的研究", 《新型建筑材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402679A (en) * | 2021-06-16 | 2021-09-17 | 西南科技大学 | Method for synthesizing polycarboxylic acid water reducing agent by catalyzing magnesium oxide, aluminum oxide or copper oxide |
| CN114478942A (en) * | 2022-01-26 | 2022-05-13 | 四川同舟化工科技有限公司 | Polycarboxylate superplasticizer capable of effectively resisting influence of flocculating agent and preparation method thereof |
| CN114478942B (en) * | 2022-01-26 | 2023-08-08 | 四川同舟化工科技有限公司 | Polycarboxylate superplasticizer capable of effectively resisting influence of flocculant and preparation method thereof |
| CN116119974A (en) * | 2023-04-14 | 2023-05-16 | 石家庄市长安育才建材有限公司 | Polycarboxylate superplasticizer applicable to plateau areas and preparation method thereof |
| CN116119974B (en) * | 2023-04-14 | 2023-09-05 | 石家庄市长安育才建材有限公司 | Polycarboxylate superplasticizer applicable to plateau areas and preparation method thereof |
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