CN113527587B - Air-entraining type polycarboxylate superplasticizer and preparation method thereof - Google Patents
Air-entraining type polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN113527587B CN113527587B CN202010304767.9A CN202010304767A CN113527587B CN 113527587 B CN113527587 B CN 113527587B CN 202010304767 A CN202010304767 A CN 202010304767A CN 113527587 B CN113527587 B CN 113527587B
- Authority
- CN
- China
- Prior art keywords
- air
- entraining
- polycarboxylate superplasticizer
- solution
- type polycarboxylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 39
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 37
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 24
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 23
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005642 Oleic acid Substances 0.000 claims abstract description 23
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 5
- 239000000243 solution Substances 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 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 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- -1 isopentenyl Chemical group 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 4
- 229930003268 Vitamin C Natural products 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019154 vitamin C Nutrition 0.000 claims description 4
- 239000011718 vitamin C Substances 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-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
- 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 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 31
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000005394 methallyl group Chemical group 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
An air-entraining type polycarboxylate superplasticizer and a preparation method thereof, wherein the raw material proportion for synthesizing the air-entraining type polycarboxylate superplasticizer is polyoxyethylene ether macromonomer 420; 3.5-14% of oleic acid; 44-81 of unsaturated carboxylic acid comonomer; 2.5-5% of an initiator; 0.6-1.2% of a reducing agent; 1.6-2.5% of a chain transfer agent; 1-2 parts of a catalyst; 9-30% of liquid caustic soda; 470-520 parts of water; the PH value of the air-entraining type polycarboxylate superplasticizer is 5-7, and the solid content is about 50%. The air-entraining type polycarboxylate superplasticizer disclosed by the invention is excellent in air-entraining performance, good in air-entraining capacity, adjustable in air-entraining performance and capable of obviously improving the workability of concrete. The water reducing agent has simple preparation process, short preparation time and low energy consumption.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a concrete admixture and a preparation method thereof.
Background
Concrete is used as a building material with huge consumption in more and more fields, which puts higher requirements on various performances of the concrete. For fresh concrete, it is required to have excellent workability and easy construction and pumping. The hardened concrete needs to have good durability, the strength meets the design requirement, the appearance is flat and attractive, and no honeycomb pitted surface exists. The gas content of the concrete is an important factor influencing the performance, and it is very important to introduce a large amount of tiny, uniform and stable bubbles into the concrete. The 'ball' and 'floating' effects of the bubbles can effectively improve the workability of the concrete, and the introduction of the bubbles can improve the pore structure of the hardened concrete and improve the cracking resistance and the freezing resistance.
The concrete air-entraining mode is to use an additive with air-entraining function. The traditional air-entraining admixture is a calcium lignosulfonate water reducing agent, but the water reducing rate of the water reducing agent is low, the mixing amount is large, the air entraining is too high, and the strength of concrete is reduced. At present, the air-entraining admixture is mainly obtained by compounding the air-entraining agent and the polycarboxylic acid water reducing agent, but the problem of incompatibility of the air-entraining agent and the polycarboxylic acid can occur in the compounding process, so that the admixture is layered and the performance is reduced, on the other hand, the problem of poor adaptability of the air-entraining agent and a concrete material can occur, and in some materials, the air-entraining effect is poor. Therefore, more and more researchers have been studying the improvement of air-entraining properties of polycarboxylic acid from its molecular structure.
Chinese patent CN109867758A discloses an air-entraining type polycarboxylate water reducer and a synthesis process thereof, wherein under the condition of 90-130 ℃, fatty alcohol-polyoxyethylene ether and methacrylic acid are subjected to esterification for 5-8 hours to obtain an intermediate product, and then the intermediate product, HPEH, AMPS and methacrylic acid are subjected to polymerization for 3-4 hours to obtain the air-entraining type polycarboxylate water reducer. When the water reducing agent is added into C30 grade concrete, the content of air is 1.4-2.0% when the addition amount is 0.17%, and the 28d strength reaches 37 Mpa.
The patent CN109134783A discloses an air-entraining polycarboxylate superplasticizer and a preparation method thereof, wherein under the condition of 65-70 ℃, unsaturated acid such as acrylic acid and unsaturated ester such as methyl acrylate are subjected to polymerization reaction for 2-3 h to obtain an intermediate product, and then the intermediate product and polyglycol monomethyl ether are subjected to esterification reaction for 5-6 h at 105-115 ℃ to obtain the air-entraining polycarboxylate superplasticizer. When the water reducing agent is added into the dry and hard concrete, the air content is 1.6-5.0% when the addition amount is 0.6%.
Chinese patent CN104744684A discloses a block polyether, an air entraining type polycarboxylate water reducer prepared from the block polyether and a preparation method thereof, wherein under the conditions of high temperature and high pressure, unsaturated monohydric alcohol, ethylene oxide and alkylene oxide of C3-C12 are subjected to polymerization for 6-8 hours to obtain the block polyether, and then the block polyether, common polyether and unsaturated carboxylic acid are subjected to polymerization for 4-6 hours at 50-80 ℃ to obtain the air entraining type polycarboxylate water reducer, wherein the water reducer enables the air content of mixed concrete to be 3-8.
The methods are all two-step methods for preparing the water reducing agent, the preparation process is complex, the reaction time is long, the energy consumption is high, and in esterification reaction and block polyether preparation reaction, concentrated sulfuric acid and other catalysts with strong corrosivity are needed, so that the dangerousness is high. On the other hand, the above method focuses only on the initial gas content of the concrete after using the air-entraining polycarboxylic acid, and does not focus on the change in gas content of the concrete with time. After the fresh concrete is placed, the air bubbles can be broken, and the air content is reduced. If the stability of the bubbles is poor, the loss of air content is too fast, the workability of concrete is rapidly reduced, the working performance is poor, and the construction is influenced.
Therefore, aiming at the defects of the prior art, it is necessary to provide a water reducing agent which has simple and efficient preparation method, is green and environment-friendly and has good gas content.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides the air-entraining type polycarboxylate water reducer which is simple in preparation process, short in preparation time, low in energy consumption, good in air entraining, small in air content loss and adjustable in air entraining capacity, and can obviously improve the air entraining performance of concrete, and the preparation method thereof.
The technical scheme adopted by the invention is as follows:
the air-entraining type polycarboxylate superplasticizer is prepared from the following raw materials in parts by weight:
polyoxyethylene ether macromonomer: 420;
oleic acid: 3.5 to 14;
unsaturated carboxylic acid comonomer: 44-81;
initiator: 2.5 to 5;
reducing agent: 0.6 to 1.2;
chain transfer agent: 1.6-2.5;
catalyst: 1-2;
liquid caustic soda: 9-30 parts of;
water: 470 to 520;
the PH value of the air-entraining type polycarboxylate superplasticizer is 5-7, and the solid content is about 50%.
Further, the reaction molar ratio of the unsaturated carboxylic acid comonomer to the polyoxyethylene ether macromonomer is (3.5-4.0): 1
Further, the polyoxyethylene ether macromonomer is one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether and isopentenyl polyoxyethylene ether, and the molecular weight of the polyoxyethylene ether macromonomer is 2400.
Further, the molecular structural formula of the oleic acid is as follows:
further, the unsaturated carboxylic acid comonomer is one or more of acrylic acid, methacrylic acid and maleic acid.
Further, the initiator is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate with the mass concentration of 27%.
Further, the reducing agent is one or more of vitamin C, sodium sulfite, sodium formaldehyde sulfoxylate and E51.
Further, the chain transfer agent is one or more of mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid and sodium hypophosphite.
Further, the catalyst is ferrous sulfate or ferrous chloride water solution with the mass concentration of 1%.
Further, the liquid alkali is sodium hydroxide or potassium hydroxide aqueous solution.
The preparation method of the air-entraining type polycarboxylate superplasticizer comprises the following steps:
(1) adding a polyoxyethylene ether macromonomer and water into a reaction kettle, heating to 60 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved to obtain a macromonomer solution;
(2) adding oleic acid into a reaction kettle, mixing with the macromonomer solution, and uniformly stirring;
(3) mixing unsaturated carboxylic acid comonomer with water, and stirring uniformly to obtain dropping liquid A;
(4) mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to obtain a dropping liquid B;
(5) adding a catalyst and an initiator into a reaction kettle, stirring for 3-5 min, then simultaneously dropwise adding the solution A and the solution B, controlling the dropwise adding time of the solution A to be 120-150 min, controlling the dropwise adding time of the solution B to be 150-180 min, and after dropwise adding is finished, preserving heat for 20-30 min;
(6) and after the reaction is finished, adding liquid caustic soda and water, and adjusting the pH to 5-7 to obtain the air-entraining polycarboxylic acid water reducing agent with the solid content of about 50%.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the oleic acid structure is introduced into the air-entraining polycarboxylate superplasticizer disclosed by the invention, so that the formation of bubbles and the increase of the bubble stability are facilitated. Oleic acid is long-chain fatty acid, has extremely strong hydrophobicity, can reduce the hydrophilicity of polycarboxylic acid by introducing the oleic acid into the molecular structure of the polycarboxylic acid, obviously reduces the surface tension of the polycarboxylic acid, and is beneficial to the formation of bubbles. The introduction of the hydrophobic long straight chain reduces the diffusion rate of gas molecules in the bubbles, and the stability of the bubbles is also increased.
(2) The mole ratio of the unsaturated carboxylic acid comonomer to the polyether macromonomer has an influence on the air entraining performance of the polycarboxylic acid, the air entraining performance is improved along with the increase of the acid-ether ratio, and the air entraining performance is optimal when the acid-ether ratio is (3.5-4.0): 1. The method controls the reaction molar ratio of the unsaturated carboxylic acid comonomer to the polyoxyethylene ether macromonomer to be (3.5-4.0): 1, and further improves the air entraining performance.
(3) The air entraining capacity is related to the addition amount of the oleic acid, and the more the addition amount of the oleic acid is, the stronger the air entraining capacity is. The air entraining capacity of the polycarboxylate superplasticizer can be regulated and controlled by controlling the addition of the oleic acid.
(4) Oleic acid is unsaturated fatty acid, has double bonds in a molecular structure, can be directly polymerized with polyether monomers and unsaturated carboxylic acid small monomers, and omits the preparation process of intermediate products. The method adopts a simple one-step method to prepare the air-entraining type polycarboxylate superplasticizer, greatly shortens the reaction time, only needs about 3 hours in the whole process, and greatly improves the preparation efficiency.
(5) The air-entraining type polycarboxylate superplasticizer prepared by the invention can obviously improve the air-entraining performance of concrete, has good air-entraining performance and small air content loss, and has adjustable air-entraining capacity.
(6) The method has the advantages that the temperature in the whole preparation process is controlled to be 60 ℃, the temperature is lower, the energy consumption is low, and the method does not use harmful substances with strong corrosivity such as concentrated sulfuric acid and the like, and is more environment-friendly.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Adding 420g of isopentenyl polyoxyethylene ether (with the molecular weight of 2400) and 300g of water into a four-mouth bottle reaction kettle, heating to 60 ℃, and stirring until all polyoxyethylene ether macromonomer is dissolved to obtain macromonomer solution; then 14g of oleic acid was added to the reactor, mixed with the macromonomer solution and stirred well. 81g of maleic acid was mixed with 99g of water to obtain solution A, and 1g of vitamin C and 2g of mercaptoethanol were mixed with 67g of water to obtain solution B. The reaction molar ratio of the maleic acid to the isopentenyl polyoxyethylene ether is 4.0: 1. Adding 2g of ferrous sulfate aqueous solution with the mass concentration of 1% into a reaction kettle, stirring for 3min, then adding 2g of hydrogen peroxide with the mass concentration of 27% and 2g of potassium persulfate, stirring for 5min, simultaneously beginning to dropwise add the solution A and the solution B, dropwise adding the solution A for 120min, dropwise adding the solution B for 150min, preserving the temperature for 30min after dropwise adding is finished, then adding 30g of sodium hydroxide solution with the mass concentration of 32% and 54g of water, and stirring to obtain the air-entraining type polycarboxylic acid water reducing agent with the pH of 6 and the solid content of 50%.
Example 2
Adding 420g of methyl allyl polyoxyethylene ether (with the molecular weight of 2400) and 300g of water into a reaction kettle, heating to 60 ℃, and stirring until polyoxyethylene ether macromonomer is completely dissolved to obtain macromonomer solution; then 3.5g of oleic acid was added to the reaction vessel, mixed with the macromonomer solution, and stirred uniformly. 44g of acrylic acid was mixed with 76g of water to obtain solution A, and 0.6g of sodium sulfite and 1.6g of thioglycolic acid were mixed with 57.8g of water to obtain solution B. The reaction molar ratio of acrylic acid to methallyl polyoxyethylene ether is 3.5: 1. Adding 1g of ferrous chloride aqueous solution with the mass concentration of 1% into a reaction kettle, stirring for 4min, then adding 2.5g of ammonium persulfate, stirring for 5min, simultaneously beginning to dropwise add the solution A and the solution B, dropwise adding the solution A for 150min, dropwise adding the solution B for 160min, keeping the temperature for 25min after dropwise adding is finished, then adding 18g of potassium hydroxide solution with the mass concentration of 32% and 36.2g of water, and stirring to obtain the air-entraining type polycarboxylate superplasticizer with the pH value of 6 and the solid content of 50%.
Example 3
Adding 420g of methyl allyl polyoxyethylene ether (molecular weight of 2400) and 300g of water into a four-mouth bottle reaction kettle, heating to 60 ℃, and stirring until all polyoxyethylene ether macromonomer is dissolved to obtain macromonomer solution; then 10.5g of oleic acid was added to the reaction kettle, mixed with the macromonomer solution, and stirred uniformly. Acrylic acid (30 g), maleic acid (30 g) and water (60 g) were mixed to obtain solution A, and sodium sulfite (0.5 g), E51 (0.2 g) and mercaptopropionic acid (1.6 g) and water (57.7 g) were mixed to obtain solution B. The reaction molar ratio of acrylic acid + maleic acid to methallyl polyoxyethylene ether was 3.9: 1. Adding 2g of ferrous chloride aqueous solution with the mass concentration of 1% into a reaction kettle, stirring for 5min, then adding 5g of ammonium persulfate, stirring for 5min, simultaneously beginning to dropwise add the solution A and the solution B, dropwise adding the solution A for 150min, dropwise adding the solution B for 160min, after dropwise adding, keeping the temperature for 25min, then adding 28g of potassium hydroxide solution with the mass concentration of 32% and 62g of water, and stirring to obtain the air-entraining type polycarboxylate superplasticizer with the pH of 7 and the solid content of 50%.
Example 4
Adding 420g of allyl polyoxyethylene ether (molecular weight of 2400) and 300g of water into a reaction kettle, heating to 60 ℃, and stirring until all polyoxyethylene ether macromonomers are dissolved to obtain a macromonomer solution; then 14g of oleic acid was added to the reactor, mixed with the macromonomer solution and stirred well. 56g of methacrylic acid and 64g of water were mixed to obtain solution A, and 1.2g of sodium formaldehyde sulfoxylate and 2.5g of sodium hypophosphite were mixed with 60g of water to obtain solution B. The reaction molar ratio of methacrylic acid to allyl polyoxyethylene ether was 3.7: 1. Adding 1.5g of ferrous sulfate aqueous solution with the mass concentration of 1% into a reaction kettle, stirring for 3min, then adding 3g of potassium persulfate, stirring for 5min, simultaneously beginning to dropwise add the solution A and the solution B, dropwise adding the solution A for 140min, dropwise adding the solution B for 160min, preserving the temperature for 20min after dropwise adding is finished, then adding 9g of potassium hydroxide solution with the mass concentration of 32% and 55g of water, and stirring to obtain the air-entraining type polycarboxylate superplasticizer with the pH value of 5 and the solid content of 50%.
Comparative example 1
To compare the effects of the present invention, the following comparative examples are provided, the preparation methods of which are as follows: adding 420g of isopentenyl polyoxyethylene ether and 300g of water into a four-mouth bottle reaction kettle, heating to 60 ℃, and stirring for dissolving. 81g of maleic acid was mixed with 99g of water to obtain solution A, and 1g of vitamin C and 2g of mercaptoethanol were mixed with 67g of water to obtain solution B. Adding 2g of ferrous sulfate aqueous solution with the mass concentration of 1% into a reaction kettle, stirring for 3min, then adding 4g of hydrogen peroxide with the mass concentration of 27% and 2g of potassium persulfate, stirring for 5min, simultaneously beginning to dropwise add the solution A and the solution B, dropwise adding the solution A for 120min, dropwise adding the solution B for 150min, preserving heat for 30min after dropwise adding is finished, then adding 30g of sodium hydroxide solution with the mass concentration of 32% and 54g of water, and stirring to obtain the polycarboxylic acid water reducer with the solid content of 50%. In this comparative example, compared to example 1, no oleic acid was added.
Comparative example 2
Adding 420g of methyl allyl polyoxyethylene ether and 300g of water into a reaction kettle, heating to 60 ℃, stirring for dissolving, adding 3.5g of oleic acid, and stirring uniformly. Acrylic acid (31.5 g) was mixed with water (88.5 g) to obtain solution A, and sodium sulfite (0.6 g) and thioglycolic acid (1.6 g) were mixed with water (57.8 g) to obtain solution B. Adding 1g of ferrous chloride aqueous solution with the mass concentration of 1% into a reaction kettle, stirring for 4min, then adding 2.5g of ammonium persulfate, stirring for 5min, simultaneously beginning to dropwise add the solution A and the solution B, dropwise adding the solution A for 150min, dropwise adding the solution B for 160min, preserving the temperature for 30min after dropwise adding is finished, then adding 18g of potassium hydroxide solution with the mass concentration of 32% and 36.2g of water, and stirring to obtain the polycarboxylic acid water reducer with the solid content of 50%. In this comparative example, the reaction molar ratio of acrylic acid to methallyl polyoxyethylene ether was 2.5:1, compared to example 2.
Comparative example 3
Adding 420g of methyl allyl polyoxyethylene ether and 300g of water into a four-mouth bottle reaction kettle, heating to 60 ℃, stirring for dissolving, adding 3.5g of oleic acid, and stirring uniformly. 56.7g of acrylic acid was mixed with 63.3g of water to obtain solution A, and 0.6g of sodium sulfite and 1.6g of thioglycolic acid were mixed with 57.8g of water to obtain solution B. Adding 2g of ferrous chloride aqueous solution with the mass concentration of 1% into a reaction kettle, stirring for 4min, then adding 2.5g of ammonium persulfate, stirring for 5min, simultaneously beginning to dropwise add the solution A and the solution B, dropwise adding the solution A for 150min, dropwise adding the solution B for 160min, keeping the temperature for 25min after dropwise adding is finished, then adding 18g of potassium hydroxide solution with the mass concentration of 32% and 36.2g of water, and stirring to obtain the polycarboxylic acid water reducer with the solid content of 50%. In this comparative example, the reaction molar ratio of acrylic acid to methallyl polyoxyethylene ether was 4.5:1, compared to example 2.
The air-entraining type polycarboxylate superplasticizer synthesized in the embodiment is compared with the polycarboxylate superplasticizer synthesized in the comparative example for concrete application performance, tests are carried out according to national standards GB 8076-2018 concrete admixture and GB/T50080-2016 common concrete mixture performance test method, and the initial slump, the expansion degree and the gas content of concrete, the gas content of 1h and the compressive strength of 28d are detected. The test materials are shown in table 1 as follows: P.O 42.5.5 g of jade bead cement; machine-made sand, Mx 2.6, MB 1.0; river sand, Mx ═ 2.9; crushing stone, wherein the particle size is 5-20 mm, and continuously grading; mineral powder, grade S75; fly ash, grade II.
TABLE 1C30 concrete mixing ratio
From the results of table 2 it can be seen that: the air-entraining type polycarboxylic acid water reducing agent synthesized in the examples 1-4 has high initial air content and low loss of air content for 1h, and the polycarboxylic acid prepared in the examples has excellent air-entraining performance and low loss of air content; comparing the relationship between the gas content and the oleic acid consumption of the 4 embodiments, it can be seen that the more the oleic acid consumption, the larger the gas content, the better the gas-entraining performance, and the gas-entraining capacity can be controlled by the oleic acid consumption; comparing the example 1 with the comparative example 1, it is obvious that the polycarboxylic acid prepared by adding oleic acid obviously improves the air entraining performance; comparing the acid ether ratio with 3.5-4.5, and the air entraining performance of the polycarboxylate superplasticizer is better; and fourthly, the polycarboxylate superplasticizer prepared in the embodiment has obvious improvement on the workability of the concrete, and does not influence the strength of the concrete. Therefore, the air-entraining type polycarboxylate superplasticizer prepared in the embodiment has excellent air-entraining performance, small air content loss and adjustable air-entraining capacity, obviously improves the workability of concrete, and achieves the technical aim of the invention.
Table 2 concrete test data sheet
Claims (10)
1. The air entraining type polycarboxylate superplasticizer is characterized by comprising the following raw materials in parts by weight:
polyoxyethylene ether macromonomer: 420;
oleic acid: 3.5 to 14;
unsaturated carboxylic acid comonomer: 44-81;
initiator: 2.5-5;
reducing agent: 0.6 to 1.2;
chain transfer agent: 1.6-2.5;
catalyst: 1-2;
liquid caustic soda: 9-30;
water: 470 to 520;
the PH value of the air-entraining type polycarboxylate superplasticizer is 5-7, and the solid content is about 50%.
2. The air-entraining type polycarboxylate superplasticizer according to claim 1, characterized in that the reaction molar ratio of the unsaturated carboxylic acid comonomer to the polyoxyethylene ether macromonomer is (3.5-4.0): 1.
3. The air-entraining type polycarboxylate superplasticizer according to claim 1, characterized in that the polyoxyethylene ether macromonomer is one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether and isopentenyl polyoxyethylene ether, and has a molecular weight of 2400.
4. The air-entraining type polycarboxylate superplasticizer according to claim 1, characterized in that the unsaturated carboxylic acid comonomer is one or more of acrylic acid, methacrylic acid and maleic acid.
5. The air entraining type polycarboxylate superplasticizer according to claim 1, wherein the initiator is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate.
6. The air-entraining type polycarboxylate superplasticizer according to claim 1, characterized in that the reducing agent is one or more of vitamin C, sodium sulfite, sodium formaldehyde sulfoxylate and E51.
7. The air-entraining polycarboxylate superplasticizer according to claim 1, wherein the chain transfer agent is one or more of mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid and sodium hypophosphite.
8. The air entraining type polycarboxylate superplasticizer according to claim 1, wherein the catalyst is 1% by mass concentration of ferrous sulfate or ferrous chloride aqueous solution.
9. The air-entraining type polycarboxylate superplasticizer according to claim 1, characterized in that the liquid alkali is an aqueous solution of sodium hydroxide or potassium hydroxide.
10. The preparation method of the air-entraining type polycarboxylate superplasticizer according to any one of claims 1 to 9, characterized by comprising the following steps:
(1) adding a polyoxyethylene ether macromonomer and water into a reaction kettle, heating to 60 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved to obtain a macromonomer solution;
(2) adding oleic acid into a reaction kettle, mixing with the macromonomer solution, and uniformly stirring;
(3) mixing unsaturated carboxylic acid comonomer with water, and stirring uniformly to obtain dropping liquid A;
(4) mixing a reducing agent, a chain transfer agent and water, and uniformly stirring to obtain a dropping liquid B;
(5) adding a catalyst and an initiator into a reaction kettle, stirring for 3-5 min, then simultaneously dropwise adding the solution A and the solution B, controlling the dropwise adding time of the solution A to be 120-150 min, controlling the dropwise adding time of the solution B to be 150-180 min, and after dropwise adding is finished, preserving heat for 20-30 min;
(6) and after the reaction is finished, adding liquid caustic soda and water, and adjusting the pH to 5-7 to obtain the air-entraining polycarboxylic acid water reducing agent with the solid content of about 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010304767.9A CN113527587B (en) | 2020-04-17 | 2020-04-17 | Air-entraining type polycarboxylate superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010304767.9A CN113527587B (en) | 2020-04-17 | 2020-04-17 | Air-entraining type polycarboxylate superplasticizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113527587A CN113527587A (en) | 2021-10-22 |
| CN113527587B true CN113527587B (en) | 2022-08-19 |
Family
ID=78123342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010304767.9A Active CN113527587B (en) | 2020-04-17 | 2020-04-17 | Air-entraining type polycarboxylate superplasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113527587B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805701B (en) * | 2022-04-13 | 2024-06-25 | 厦门路桥翔通建材科技有限公司 | Mortar concrete reinforced composition and preparation method thereof |
| CN115010933B (en) * | 2022-06-14 | 2023-09-12 | 武汉三源特种建材有限责任公司 | Six-carbon foam-stabilizing type water reducer and preparation method thereof |
| CN115073045A (en) * | 2022-06-29 | 2022-09-20 | 贵州中兴南友建材有限公司 | Low-sensitivity anti-freezing polycarboxylate superplasticizer and preparation method thereof |
| CN115433326A (en) * | 2022-09-16 | 2022-12-06 | 新疆大学 | Oleic acid modified polycarboxylic acid water reducing agent, and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948267A (en) * | 2010-09-01 | 2011-01-19 | 科之杰新材料(漳州)有限公司 | Concrete air entraining agent and preparation method thereof |
| CN102951865A (en) * | 2012-11-01 | 2013-03-06 | 重庆健杰科技有限公司 | Air entraining type poly carboxylic acid high performance water reducing agent and preparation method thereof |
| CN103864340A (en) * | 2014-03-24 | 2014-06-18 | 成都理工大学 | Water-repellent admixture for mortar and concrete |
| CN108249866A (en) * | 2018-03-27 | 2018-07-06 | 刘群 | Freeze proof pervious concrete of high intensity and preparation method thereof |
| CN109134783A (en) * | 2018-07-27 | 2019-01-04 | 刘翠芬 | A kind of research work of air entrained type polycarboxylate water-reducer and preparation method thereof |
| CN109516715A (en) * | 2018-05-25 | 2019-03-26 | 湖北工业大学 | A kind of polycarboxylate water-reducer work liquid and preparation method thereof suitable for clear-water concrete |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN113248381A (en) * | 2021-07-02 | 2021-08-13 | 北京金隅水泥节能科技有限公司 | Modified fatty acid, polycarboxylate superplasticizer and preparation method of polycarboxylate superplasticizer |
| CN114315214A (en) * | 2022-01-12 | 2022-04-12 | 临沂大学 | Anti-crack concrete additive and preparation method thereof |
-
2020
- 2020-04-17 CN CN202010304767.9A patent/CN113527587B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948267A (en) * | 2010-09-01 | 2011-01-19 | 科之杰新材料(漳州)有限公司 | Concrete air entraining agent and preparation method thereof |
| CN102951865A (en) * | 2012-11-01 | 2013-03-06 | 重庆健杰科技有限公司 | Air entraining type poly carboxylic acid high performance water reducing agent and preparation method thereof |
| CN103864340A (en) * | 2014-03-24 | 2014-06-18 | 成都理工大学 | Water-repellent admixture for mortar and concrete |
| CN108249866A (en) * | 2018-03-27 | 2018-07-06 | 刘群 | Freeze proof pervious concrete of high intensity and preparation method thereof |
| CN109516715A (en) * | 2018-05-25 | 2019-03-26 | 湖北工业大学 | A kind of polycarboxylate water-reducer work liquid and preparation method thereof suitable for clear-water concrete |
| CN109134783A (en) * | 2018-07-27 | 2019-01-04 | 刘翠芬 | A kind of research work of air entrained type polycarboxylate water-reducer and preparation method thereof |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN113248381A (en) * | 2021-07-02 | 2021-08-13 | 北京金隅水泥节能科技有限公司 | Modified fatty acid, polycarboxylate superplasticizer and preparation method of polycarboxylate superplasticizer |
| CN114315214A (en) * | 2022-01-12 | 2022-04-12 | 临沂大学 | Anti-crack concrete additive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113527587A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113527587B (en) | Air-entraining type polycarboxylate superplasticizer and preparation method thereof | |
| CN109400821B (en) | Concrete bleeding-resistant inhibitor with water reducing function and preparation method thereof | |
| CN109575198B (en) | Enhanced polycarboxylate superplasticizer and preparation method thereof | |
| CN111607039A (en) | Slow-release high slump loss resistant polycarboxylic acid concrete water reducer and preparation method thereof | |
| CN114195421A (en) | Preparation method of polycarboxylic acid admixture for machine-made sand concrete | |
| CN108948288B (en) | Preparation method of crosslinking type polycarboxylate superplasticizer by adopting carboxyl functional monomer | |
| CN109337024B (en) | Preparation method of retarding polycarboxylate superplasticizer | |
| CN108751774B (en) | Preparation method of polycarboxylate superplasticizer for concrete prefabricated part | |
| CN110606922B (en) | Preparation method of polycarboxylate superplasticizer with hydration heat regulation and control function | |
| CN111116844B (en) | Air-entraining type polycarboxylate superplasticizer and preparation method thereof | |
| CN105218757B (en) | Early-strength polycarboxylate superplasticizer with slump retaining function and preparation method thereof | |
| CN109485323B (en) | Application of early-strength viscosity-reduction type polycarboxylate superplasticizer in preparation of precast concrete | |
| CN116622034A (en) | Slow-release viscosity-reduction type polycarboxylate superplasticizer for high-strength concrete and preparation method thereof | |
| CN112250807B (en) | Copolymer water reducing agent for fabricated building components and preparation method thereof | |
| CN114031728A (en) | High-water-reduction-type EPEG polycarboxylic acid water reducer and preparation method thereof | |
| CN112608424B (en) | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof | |
| CN113072666B (en) | Preparation method and application of high-water-reduction type polycarboxylic acid superplasticizer | |
| CN109721271B (en) | Polycarboxylate water reducing agent composition for self-compacting high-workability concrete | |
| CN115873182A (en) | Mud-resistant slump-retaining ester type polycarboxylate superplasticizer and preparation method thereof | |
| CN113354782B (en) | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN114702683A (en) | Hyperbranched polycarboxylic acid water reducer and preparation method thereof | |
| CN114163578A (en) | Viscosity-controlled polycarboxylate superplasticizer and preparation method thereof | |
| CN109721722B (en) | Viscosity-reducing type polycarboxylate superplasticizer containing double viscosity-reducing functional groups, and preparation method and application thereof | |
| CN109776034B (en) | Application of viscosity-reducing water reducer containing alkyl in preparation of C100 concrete | |
| CN109749020B (en) | Alkyl-containing early-strength viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: An air entrained polycarboxylate water reducer and its preparation method Granted publication date: 20220819 Pledgee: Bank of China Limited Kunming Panlong Sub branch Pledgor: YUNNAN JIANTOU POLYMER MATERIALS Co.,Ltd. Registration number: Y2024980016040 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |