CN117819864A - Polycarboxylic acid high-performance water reducer - Google Patents
Polycarboxylic acid high-performance water reducer Download PDFInfo
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- CN117819864A CN117819864A CN202410242967.4A CN202410242967A CN117819864A CN 117819864 A CN117819864 A CN 117819864A CN 202410242967 A CN202410242967 A CN 202410242967A CN 117819864 A CN117819864 A CN 117819864A
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- graphene oxide
- polycarboxylic acid
- polycarboxylate superplasticizer
- performance water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 69
- 239000002253 acid Substances 0.000 title claims abstract description 39
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000008030 superplasticizer Substances 0.000 claims abstract description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012452 mother liquor Substances 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000006260 foam Substances 0.000 claims abstract description 27
- 239000003381 stabilizer Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 12
- -1 isopentenyl Chemical group 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- ITCAUAYQCALGGV-XTICBAGASA-M sodium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Na+].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O ITCAUAYQCALGGV-XTICBAGASA-M 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 39
- 239000002994 raw material Substances 0.000 abstract description 19
- 239000004568 cement Substances 0.000 abstract description 17
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 238000007142 ring opening reaction Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 238000005809 transesterification reaction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 25
- 230000000694 effects Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003973 alkyl amines Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229960004418 trolamine Drugs 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000009456 molecular mechanism Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GVXIVWJIJSNCJO-UHFFFAOYSA-L aluminum;calcium;sulfate Chemical compound [Al+3].[Ca+2].[O-]S([O-])(=O)=O GVXIVWJIJSNCJO-UHFFFAOYSA-L 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- NMGSERJNPJZFFC-UHFFFAOYSA-N carbonic acid;sulfuric acid Chemical compound OC(O)=O.OS(O)(=O)=O NMGSERJNPJZFFC-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229940080117 triethanolamine sulfate Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the technical field of concrete additives, in particular to a polycarboxylic acid high-performance water reducer, which comprises the following preparation raw materials in parts by weight: 40-80 parts of self-made polycarboxylate superplasticizer mother liquor, 19-30 parts of modified graphene oxide, 0.1-0.5 part of foam stabilizer, 0.9-1.7 parts of expanding agent and 220-270 parts of water; according to the invention, the N-N-diethyl-N-hexadecylamine with an early strength function is grafted to the surface of the graphene oxide through the epoxy ring-opening reaction, so that the cement has the early strength function, and the original dispersibility and compatibility of the graphene oxide can be increased; in addition, the self-made polycarboxylate superplasticizer mother liquor is subjected to transesterification reaction of butyl acetate and methanol, so that the compactness and strength of the concrete are improved.
Description
Technical Field
The invention relates to the technical field of concrete additives, in particular to a polycarboxylic acid high-performance water reducer.
Background
The polycarboxylic acid water reducer is a series of water reducers which are formed by copolymerizing unsaturated monomers containing carboxyl and other monomers, so that the concrete has excellent performances in the aspects of water reduction, slump loss protection, plasticization, shrinkage, environmental protection and the like.
At present, research on improving the early strength performance of the polycarboxylate superplasticizer at home and abroad is mainly focused on the following two aspects: (1) the early strength agent is compounded in the polycarboxylate water reducer, so that the water reducer has an early strength function; (2) by designing the molecular structure of the polycarboxylate superplasticizer, the early-strength polycarboxylate superplasticizer with early-strength performance is synthesized.
The compound drought-hardening polycarboxylate water reducer is prepared by adding early-hardening components into a polycarboxylate water reducer, and mixing the early-hardening components and the polycarboxylate water reducer according to a certain proportion, so that the polycarboxylate water reducer has the functions of early-hardening and water reduction. The early strength components can be divided into three types according to chemical components: (1) inorganic salts (including chloride, nitrate, sulfate carbonate, silicate, etc.); (2) organic matters (including triethanolamine, calcium formate, calcium acetate, calcium oxalate, etc.); (3) composite organic matter and inorganic matter, such as triethanolamine and sodium sulfate.
The main mechanism for generating the early strength effect by compounding the traditional inorganic salt (sodium chloride and calcium chloride) and the polycarboxylate water reducer is that the inorganic salt reacts with the chloride salt in cement to generate water-insoluble hydrated chloroaluminate, the solid phase of the hydrated chloroaluminate is separated out, so that the hydration speed is increased, the early strength is improved, but the corrosion rate of steel bars in reinforced concrete is increased by adding the chloride salt, and the application scene is very limited; triethanolamine is the most commonly used early strength component in organic matters, and can accelerate the formation of ettringite in a C-S-H system, so that the early strength of concrete is improved, but the mixing amount of the triethanolamine is very small, and excessive mixing amount can cause phenomena of false setting, strength reduction and the like, so that the mixing amount is difficult to control.
The existing research on the structure function early-strength polycarboxylate water reducer only aims at one aspect of adjusting the structure molecular parameter of the water reducer or grafting the early-strength functional monomer, and the research is not carried out under the condition of combining the structure function early-strength polycarboxylate water reducer and the grafting early-strength functional monomer; and the production of the composite material increases the requirements on raw materials and process equipment, increases the production cost, and can not be applied to actual engineering.
In the prior art, graphene oxide is used as a modifier to improve the early strength performance of the polycarboxylate superplasticizer, such as the Chinese invention patent with the Chinese patent number of CN103241983A, a natural graphite raw material is firstly prepared into a graphene oxide solution with the oxygen content of more than 30% through an oxidation process, then the graphene oxide solution is used for modifying the polycarboxylate superplasticizer solution, and the modified polycarboxylate superplasticizer can improve the flexural compression resistance of concrete to a certain extent, and the preparation process is reasonable and raw materials are easy to obtain;
however, the invention ignores the problems of poor dispersibility of graphene oxide and poor compatibility with the polycarboxylate water reducer, so that the modified polycarboxylate water reducer has limited effect of improving the early strength performance of concrete and can influence other performances of the concrete.
Therefore, there is a need for a polycarboxylic acid high performance water reducer that combines good early strength properties with dispersing properties without affecting other properties of the cement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the polycarboxylic acid high-performance water reducer which has good early strength performance and dispersion performance and does not influence other performances of cement.
The invention is realized by the following technical scheme: the polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 40-80 parts of self-made polycarboxylate superplasticizer mother liquor, 19-30 parts of modified graphene oxide, 0.1-0.5 part of foam stabilizer, 0.9-1.7 parts of expanding agent and 220-270 parts of water.
Further, according to parts by weight, the self-made polycarboxylate superplasticizer mother liquor comprises: 10-25 parts of conventional polyether macromonomer, 2.5-5 parts of unsaturated acid, 6.4-7.2 parts of mercaptoethanol, 5-10 parts of hydrogen peroxide, 0.2-0.5 part of lithium hydroxide, 1-8 parts of methanol, 10-15 parts of butyl acetate and 18-23 parts of water.
Further, the polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 60 parts of self-made polycarboxylate superplasticizer mother liquor, 24 parts of modified graphene oxide, 0.2 part of foam stabilizer, 1.2 parts of expanding agent and 240 parts of water.
Further, the conventional polyether macromonomer is isopentenyl polyethylene glycol ether; the unsaturated acid is acrylic acid;
further, the preparation steps of the modified graphene oxide are as follows: graphene oxide pretreatment: 10mg of prepared graphene oxide is weighed and added into 20ml of absolute ethyl alcohol to be dispersed to prepare graphene oxide ethanol solution (0.5 mg/ml). Dispersing for 20min by using a water bath ultrasonic instrument, then performing ultrasonic treatment by using a cell grinder for 20min, and finally heating to 50 ℃ and preserving for later use;
graphene oxide modification process: and taking 20ml of the treated raw material liquid, adding the raw material liquid into a tetrafluoroethylene reaction kettle at 50 ℃, simultaneously adding 30 mgN-N-diethyl-N-hexadecylamine, carrying out ultrasonic treatment at 50 ℃ for 20min, placing the raw material liquid into a blast drying box for reacting for 5h at 100 ℃, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and carrying out vacuum drying for 10h to obtain the modified graphene oxide.
The preparation method of the self-made polycarboxylate superplasticizer mother solution comprises the following steps: adding methanol and butyl acetate into a high-temperature reaction kettle, heating to 130-150 ℃, and starting stirring; sequentially adding isopentenyl polyethylene glycol ether, acrylic acid and mercaptoethanol into a reaction kettle, stirring after the temperature is raised to 200 ℃, sequentially adding hydrogen peroxide and lithium hydroxide after the reaction is carried out for 30min, continuously stirring for 10min at 200 ℃, cooling after the reaction temperature is lowered to 60 ℃, continuously stirring for 5min, and obtaining the self-made polycarboxylate superplasticizer mother liquor after the reaction liquid is completely cooled.
The preparation method of the polycarboxylic acid high-performance water reducer comprises the following steps: sequentially adding self-made polycarboxylate superplasticizer mother liquor and modified graphene oxide into a reaction vessel, stirring for 30-45min, adding a foam stabilizer, stirring for 10min, finally adding an expanding agent, and stirring for 5min to obtain the polycarboxylate superplasticizer.
Further, the expanding agent is one of sulfoaluminate or calcium sulfoaluminate, preferably calcium sulfoaluminate, and the expanding agent which is applied by the invention and takes calcium aluminum sulfate as an expanding source is purchased from Shandong Gaojuda novel building material technology Co., ltd;
further, the foam stabilizer is one or more of sodium abietate, polyvinyl alcohol and polyacrylamide, and the foam stabilizer which is used by the invention and takes sodium abietate as a raw material is purchased from Henan Qian-Te-way chemical products limited company;
compared with the prior art, the invention has the following advantages and beneficial effects:
1. the graphene oxide modification reaction is based on an epoxy ring-opening reaction of amino groups in N-N-diethyl-N-hexadecylamine and epoxy groups, and after the epoxy ring-opening reaction, the carbon long chain of the N-N-diethyl-N-hexadecylamine grafts the position for replacing the original epoxy groups on the surface of graphene oxide, so that the graphene oxide has larger interlayer spacing, the surface tension of graphene nano sheets is reduced, the agglomeration is reduced, the dispersibility is improved, and meanwhile, the compatibility of the graphene oxide with water reducer and other additives in the water reducer can be improved to a certain extent;
2. the modified graphene oxide surface is grafted with an alkylamine group, the alkylamine group can be decomposed out under the high alkaline condition of the cement paste, and is adsorbed on the surface of cement particles, so that the porosity in the concrete is reduced, the permeability and the water absorption of the concrete are reduced, the early strength of the cement is further improved, and the shrinkage of the cement is reduced;
3. according to the invention, a tetrahedral molecular mechanism generated by transesterification reaction of butyl acetate and methanol in the self-made polycarboxylate superplasticizer mother solution is mixed with modified graphene oxide, and the modified graphene oxide is adsorbed among atoms, so that the compactness and strength of concrete are improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be open ended terms
The words are meant to include, but not be limited to.
The "parts" indicated in the examples below are parts by weight. Examples:
example 1
The polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 40 parts of self-made polycarboxylate water reducer mother liquor, 19 parts of modified graphene oxide, 0.1 part of foam stabilizer, 0.9 part of expanding agent and 220 parts of water.
Wherein, self-made polycarboxylate water reducing agent mother liquor includes: 10 parts of isopentenyl polyethylene glycol ether, 2.5 parts of acrylic acid, 6.4 parts of mercaptoethanol, 5 parts of hydrogen peroxide, 0.2 part of lithium hydroxide, 1 part of methanol, 10 parts of butyl acetate and 18 parts of water.
Wherein the foam stabilizer is sodium abietate; the expanding agent is sulfoaluminate;
wherein, the graphite powder is purchased from Shenzhen vast-pyroxene graphite limited company, and the mesh number is 180 meshes; the concentration of the concentrated sulfuric acid is 98.3 percent; the concentration of the hydrogen peroxide is 30%;
the preparation method of the graphene oxide comprises the following steps: weighing 69ml of concentrated sulfuric acid, adding 4.8g of sodium nitrate for dissolution, magnetically stirring while ice bath, adding 3g of graphite powder, continuously stirring for 45min, slowly adding 9g of potassium permanganate, continuously ice bath and continuously stirring for 60min, then moving a beaker from the ice bath to 40 ℃ oil bath, continuously stirring for 90min, slowly adding 138ml of deionized water, then moving to 100 ℃ oil bath, continuously reacting for 15min, then placing at normal temperature to 60 ℃, adding 270ml of distilled water, slowly adding 45ml of hydrogen peroxide, standing for 12h, centrifuging to obtain a graphene oxide filter cake, washing 5 times with a 5% hydrochloric acid solvent, washing with distilled water until the pH of the solution is=7, filtering, and freeze-drying for later use.
The preparation method of the modified graphene oxide comprises the following steps:
graphene oxide pretreatment: 10mg of prepared graphene oxide is weighed and added into 20ml of absolute ethyl alcohol to be dispersed to prepare graphene oxide ethanol solution (0.5 mg/ml). Dispersing for 20min with a water bath ultrasonic instrument, then performing ultrasonic treatment with a cell pulverizer for 20min, and finally heating to 50 ℃ for storage.
Graphene oxide modification process: and taking 20ml of the treated raw material liquid, adding the raw material liquid into a tetrafluoroethylene reaction kettle at 50 ℃, simultaneously adding 30 mgN-N-diethyl-N-hexadecylamine, carrying out ultrasonic treatment at 50 ℃ for 20min, placing the raw material liquid into a blast drying box for reacting for 5h at 100 ℃, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and carrying out vacuum drying for 10h to obtain the modified graphene oxide.
The method for preparing the polycarboxylate superplasticizer mother liquor comprises the following steps:
adding 1 part of methanol and 10 parts of butyl acetate into a high-temperature reaction kettle, heating to 130-150 ℃, and starting stirring; sequentially adding 10 parts of isopentenyl polyethylene glycol ether, 2.5 parts of acrylic acid and 6.4 parts of mercaptoethanol into a reaction kettle, stirring after the temperature is raised to 200 ℃, sequentially adding 5 parts of hydrogen peroxide and 0.2 part of lithium hydroxide after the reaction is carried out for 30min, continuously stirring for 10min at 200 ℃, cooling, continuously stirring for 5min after the reaction temperature is reduced to 60 ℃, and obtaining the self-made polycarboxylate water reducer mother liquor after the reaction liquid is completely cooled.
The preparation method of the polycarboxylic acid high-performance water reducer comprises the following steps:
18 parts of water, 0.1 part of foam stabilizer and 0.9 part of expanding agent are added into a reaction vessel, after stirring for 10 minutes, 40 parts of polycarboxylate superplasticizer mother liquor is added, stirring is carried out for 30-45 minutes, 19 parts of modified graphene oxide is added, and stirring is carried out for 5 minutes, thus obtaining the polycarboxylate superplasticizer.
And standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
Example 2
The polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 60 parts of self-made polycarboxylate superplasticizer mother liquor, 24 parts of modified graphene oxide, 0.2 part of foam stabilizer, 1.2 parts of expanding agent and 240 parts of water;
wherein, self-made polycarboxylate water reducing agent mother liquor includes: 15 parts of isopentenyl polyethylene glycol ether, 3.5 parts of acrylic acid, 6.7 parts of mercaptoethanol, 7 parts of hydrogen peroxide, 0.4 part of lithium hydroxide, 5 parts of methanol, 13 parts of butyl acetate and 21 parts of water;
wherein the foam stabilizer is polyvinyl alcohol; the expanding agent is sulfoaluminate;
the raw material purchase and preparation methods of the self-made polycarboxylate superplasticizer mother liquor, the modified graphene oxide and the expanding agent in the embodiment 2 are the same as those in the embodiment 1; and standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
Example 3
The polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 40 parts of self-made polycarboxylate water reducer mother liquor, 30 parts of modified graphene oxide, 0.1 part of foam stabilizer, 1.5 parts of expanding agent and 250 parts of water;
wherein, self-made polycarboxylate water reducing agent mother liquor includes: 25 parts of isopentenyl polyethylene glycol ether, 4.5 parts of acrylic acid, 6.4 parts of mercaptoethanol, 10 parts of hydrogen peroxide, 0.3 part of lithium hydroxide, 6 parts of methanol, 12 parts of butyl acetate and 23 parts of water;
wherein the foam stabilizer is polyacrylamide; the expanding agent is calcium sulfoaluminate;
wherein, the raw material purchase and preparation methods of the self-made polycarboxylate superplasticizer mother liquor and the modified graphene oxide in the embodiment 3 are the same as those in the embodiment 1; and standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
Example 4
The polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 80 parts of self-made polycarboxylate water reducer mother liquor, 30 parts of modified graphene oxide, 0.5 part of foam stabilizer, 1.7 parts of expanding agent and 270 parts of water;
wherein, self-made polycarboxylate water reducing agent mother liquor includes: 25 parts of isopentenyl polyethylene glycol ether, 5 parts of acrylic acid, 7.2 parts of mercaptoethanol, 10 parts of hydrogen peroxide, 0.5 part of lithium hydroxide, 8 parts of methanol, 15 parts of butyl acetate and 23 parts of water;
wherein the foam stabilizer is sodium abietate and polyvinyl alcohol; the expanding agent is calcium sulfoaluminate;
wherein, the raw material purchase and preparation methods of the self-made polycarboxylate superplasticizer mother liquor and the modified graphene oxide in the embodiment 4 are the same as those in the embodiment 1; and standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
Example 5
The polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 95 parts of self-made polycarboxylate superplasticizer mother liquor, 45 parts of modified graphene oxide, 0.8 part of foam stabilizer, 1.9 parts of expanding agent and 300 parts of water;
wherein, self-made polycarboxylate water reducing agent mother liquor includes: 15 parts of isopentenyl polyethylene glycol ether, 3.5 parts of acrylic acid, 6.7 parts of mercaptoethanol, 7 parts of hydrogen peroxide, 0.4 part of lithium hydroxide, 5 parts of methanol, 13 parts of butyl acetate and 21 parts of water;
wherein the foam stabilizer is sodium abietate and polyacrylamide; the expanding agent is calcium sulfoaluminate;
wherein, the raw material purchase and preparation methods of the self-made polycarboxylate superplasticizer mother liquor and the modified graphene oxide in the embodiment 5 are the same as those in the embodiment 1; and standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
Comparative example 1
A common commercial polycarboxylate water reducer was selected for comparative example 1.
Comparative example 2
The polycarboxylate water reducer comprises the following components in parts by weight: 60 parts of self-made polycarboxylate superplasticizer mother liquor, 0.2 part of foam stabilizer, 1.2 parts of expanding agent and 240 parts of water;
wherein, self-made polycarboxylate water reducing agent mother liquor includes: 15 parts of isopentenyl polyethylene glycol ether, 3.5 parts of acrylic acid, 6.7 parts of mercaptoethanol, 7 parts of hydrogen peroxide, 0.4 part of lithium hydroxide, 5 parts of methanol, 13 parts of butyl acetate and 21 parts of water;
wherein, the raw material purchase and preparation methods of the self-made polycarboxylate superplasticizer mother liquor, foam stabilizer and expanding agent in comparative example 2 are the same as those of example 1; and standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
Comparative example 3
The polycarboxylate water reducer comprises the following components in parts by weight: 40 parts of a commercially available polycarboxylate superplasticizer, 30 parts of modified graphene oxide, 0.1 part of a foam stabilizer, 1.5 parts of an expanding agent and 250 parts of water;
wherein the modified graphene oxide comprises: 20 parts of N-N-diethyl-N-hexadecylamine, 13 parts of graphene oxide and 13 parts of absolute ethyl alcohol;
wherein, the raw material purchase and preparation methods of the modified graphene oxide, the foam stabilizer and the expanding agent in the comparative example 3 are the same as those of the example 1; and standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
Comparative example 4
The polycarboxylate water reducer comprises the following components in parts by weight: 80 parts of self-made polycarboxylate superplasticizer mother liquor, 30 parts of graphene oxide, 0.5 part of foam stabilizer, 1.7 parts of expanding agent and 270 parts of water;
wherein, self-made polycarboxylate water reducing agent mother liquor includes: 25 parts of isopentenyl polyethylene glycol ether, 5 parts of acrylic acid, 7.2 parts of mercaptoethanol, 10 parts of hydrogen peroxide, 0.5 part of lithium hydroxide, 8 parts of methanol, 15 parts of butyl acetate and 23 parts of water;
wherein, the raw material purchase and preparation methods of the self-made polycarboxylate superplasticizer mother liquor, foam stabilizer and expanding agent in comparative example 4 are the same as those of example 1; and standing the prepared polycarboxylate superplasticizer for 24 hours, and then using the polycarboxylate superplasticizer for testing C50 concrete.
The polycarboxylic acid high-performance water reducer prepared in the above examples 1-5 and the polycarboxylic acid water reducer prepared in the comparative examples 1-4 were used for C50 concrete testing.
The polycarboxylic acid high-performance water reducer is used for optimizing the performance of concrete, wherein, the design of the concrete mixing proportion needs to consider a plurality of factors including working performance, strength development, durability and the like. Cement as cementing material, sand and stone as aggregate, polycarboxylic acid high performance water reducer as concrete performance modifier, water (with or without admixture and admixture) in certain proportion, and stirring to obtain concrete with certain performance.
In the experimental example, the mixing ratio of cement, sand and crushed stone is 1:1.15:2.45, the sand content is 32%, the water cement ratio is about 0.4, the cement adopts 52.5R.P.II cement in the field, and the dosage of the polycarboxylate water reducer is 0.2% (folding and solid mixing amount).
Application test example 1
Concrete slump test: slump test and slump loss test with time are carried out by referring to the relevant regulations of GB50080-2016 "common concrete mixture Performance test method Standard"; compressive strength test: the concrete compressive strength is tested by referring to the relevant regulations of GB/T50081-2016 "ordinary concrete mechanical property test method Standard"; the experimental results are shown in Table 1.
Table 1 concrete strength test
Analysis of test results: wherein, the compressive strength is measured as the early strength of the concrete; the slump is measured by the flow dispersibility of concrete, wherein the early strength performance and the flow dispersibility of the polycarboxylic acid high-performance water reducer prepared in the optimal proportion example 2 in the examples are better than those of the polycarboxylic acid high-performance water reducer prepared in other proportions, even the compressive strength of 1d in the example 2 is 88% higher than that of 1d in the comparative example 1, and the compressive strengths of 3d, 7d and 28d are also respectively increased by 88%, 70% and 67%, so that the polycarboxylic acid high-performance water reducer provided by the invention is obviously better than the strength performance of the polycarboxylic acid water reducer sold in the market in both early strength performance and medium strength performance.
It should be noted that, compared with the compressive strength test effect of the embodiment 5 in the protection scope of the present invention, the compressive strength test effect of the embodiment 5 in the protection scope of the present invention is far from that of the embodiment, probably because when the alkylamine functional group in the excessive N-diethyl-N-hexadecylamine adsorbs the surface of the cement particle, the cement particle is agglomerated in a large range, so that the dispersibility and compatibility of the modified graphene oxide cannot exert an effect, and the early strength function of the concrete is further affected.
More specifically, the early strength and the middle strength of the concrete prepared in the comparative example 3 are better than those of the concrete prepared in the comparative examples 1, 2 and 4, which shows that the modified graphene oxide has an outstanding effect on improving the early strength performance of the polycarboxylate water reducer; furthermore, the early strength of the comparative example 2 is better than that of the comparative examples 1 and 4, which shows that the self-made polycarboxylate superplasticizer mother liquor also has an optimization effect on improving the strength of the concrete.
Comprehensive analysis: the graphene oxide modified by the alkylamine can meet the requirement of good improvement effect on the early strength performance of concrete under the condition of low doping amount; the tetrahedral molecular mechanism generated by transesterification in the self-made polycarboxylate superplasticizer mother solution can also improve the compactness and strength of the concrete.
Application test example 2
Testing the fluidity of cement paste: the method comprises the steps of referring to GB/T8077-2012 Standard of concrete admixture homogeneity test method, measuring the fluidity of cement paste on plate glass after stirring; the experimental results are shown in Table 2.
Table 2 net pulp fluidity test
Analysis of test results: note that the only difference of comparative example 2 from example 2 is that comparative example 2 was not added with the modified graphene oxide component; comparative example 3 the only difference over example 3 is that comparative example 3 replaces the self-made polycarboxylate superplasticizer stock solution with a commercially available common polycarboxylate superplasticizer; comparative example 4 the only difference from example 4 is that comparative example 4 replaces modified graphene oxide with unmodified graphene oxide; from the test data, the dispersibility and dispersibility retention of example 2 were better than those of the other test groups; the net pulp fluidity test effect of example 5, in which the ratios of the raw materials were all outside the protection range of the present invention, exhibited a cliff-like drop as compared with the net pulp fluidity test effect within the protection range of the present invention.
More specifically, the test effect shows that the dispersibility of comparative example 3 approaches that of example 3, indicating that the modified graphene oxide has nearly the same effect on optimizing the dispersibility of the self-made polycarboxylate superplasticizer mother liquor and the commercial polycarboxylate superplasticizer;
from the test data, the dispersibility effect of comparative example 3 was increased by 14% relative to comparative example 1, by 9% relative to comparative example 2, and by 12% relative to comparative example 4, and it was revealed that the dispersibility of graphene oxide after the epoxy ring-opening reaction of amino group with epoxy group using N-diethyl-N-hexadecylamine was significantly increased, and it was also seen from the test data after 60min and 120min that the dispersibility retention of the test group after the modified graphene oxide was significantly better than that of the test group without addition.
Comprehensive analysis: the graphene oxide subjected to the epoxy ring-opening reaction of the amino group and the epoxy group can reduce the surface tension of the graphene nano sheet, increase the dispersibility of the graphene nano sheet, and improve the compatibility of the graphene nano sheet with a water reducer and other additives in the water reducer to a certain extent, so that the graphene oxide modified by the alkylamine can meet the condition of low doping amount, and has a good effect of improving the dispersibility of concrete.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The polycarboxylic acid high-performance water reducer is characterized in that: the polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 40-80 parts of self-made polycarboxylate superplasticizer mother liquor, 19-30 parts of modified graphene oxide, 0.1-0.5 part of foam stabilizer, 0.9-1.7 parts of expanding agent and 220-270 parts of water.
2. The polycarboxylic acid high-performance water reducing agent according to claim 1, characterized in that: the self-made polycarboxylate superplasticizer mother liquor comprises the following components in parts by weight: 10-25 parts of conventional polyether macromonomer, 2.5-5 parts of unsaturated acid, 6.4-7.2 parts of mercaptoethanol, 5-10 parts of hydrogen peroxide, 0.2-0.5 part of lithium hydroxide, 1-8 parts of methanol, 10-15 parts of butyl acetate and 18-23 parts of water.
3. The polycarboxylic acid high-performance water reducing agent according to claim 1, characterized in that: the polycarboxylic acid high-performance water reducer comprises the following components in parts by weight: 60 parts of self-made polycarboxylate superplasticizer mother liquor, 24 parts of modified graphene oxide, 0.2 part of foam stabilizer, 1.2 parts of expanding agent and 240 parts of water.
4. The polycarboxylic acid high-performance water reducing agent according to claim 2, characterized in that: the conventional polyether macromonomer is isopentenyl polyethylene glycol ether.
5. The polycarboxylic acid high-performance water reducing agent according to claim 2, characterized in that: the unsaturated acid is acrylic acid.
6. The polycarboxylic acid high-performance water reducing agent according to claim 1, characterized in that: the foam stabilizer is one or more of sodium abietate, polyvinyl alcohol and polyacrylamide; the expanding agent is one of sulfoaluminate or calcium sulfoaluminate.
7. The polycarboxylic acid high-performance water reducing agent according to claim 1, characterized in that: the preparation method of the modified graphene oxide comprises the following steps:
adding graphene oxide into absolute ethyl alcohol to prepare graphene oxide ethanol solution in a dispersing way, carrying out ultrasonic dispersion on the graphene oxide ethanol solution, and then heating to 50 ℃ for storage for later use; adding the treated graphene oxide ethanol solution into a tetrafluoroethylene reaction kettle at 50 ℃, simultaneously adding N-N-diethyl-N-hexadecylamine, carrying out ultrasonic treatment at 50 ℃ for 20min, placing into a blast drying box for reacting for 5h at 100 ℃, centrifuging to obtain a precipitate, washing with ethanol for 3 times, and carrying out vacuum drying for 10h to obtain the modified graphene oxide.
8. The polycarboxylic acid high-performance water reducing agent according to claim 2, characterized in that: the preparation method of the self-made polycarboxylate superplasticizer mother solution comprises the following steps:
adding methanol and butyl acetate into a high-temperature reaction kettle, heating to 130-150 ℃, and starting stirring; sequentially adding isopentenyl polyethylene glycol ether, acrylic acid and mercaptoethanol into a reaction kettle, stirring after the temperature is raised to 200 ℃, sequentially adding hydrogen peroxide and lithium hydroxide after the reaction is carried out for 30min, continuously stirring for 10min at 200 ℃, cooling after the reaction temperature is lowered to 60 ℃, continuously stirring for 5min, and obtaining the self-made polycarboxylate superplasticizer mother liquor after the reaction liquid is completely cooled.
9. The polycarboxylic acid high-performance water reducing agent according to any one of claims 1 to 8, which is prepared by the following method: sequentially adding self-made polycarboxylate superplasticizer mother liquor and modified graphene oxide into a reaction vessel, stirring for 30-45min, adding a foam stabilizer, stirring for 10min, finally adding an expanding agent, and stirring for 5min to obtain the polycarboxylate superplasticizer.
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