CN111825367B - Viscosity reducer for ultra-high performance concrete and preparation method thereof - Google Patents
Viscosity reducer for ultra-high performance concrete and preparation method thereof Download PDFInfo
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- CN111825367B CN111825367B CN202010590565.5A CN202010590565A CN111825367B CN 111825367 B CN111825367 B CN 111825367B CN 202010590565 A CN202010590565 A CN 202010590565A CN 111825367 B CN111825367 B CN 111825367B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 60
- 239000011374 ultra-high-performance concrete Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004567 concrete Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 19
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 11
- 230000026731 phosphorylation Effects 0.000 abstract description 10
- 238000006366 phosphorylation reaction Methods 0.000 abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 abstract description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 5
- 229920000137 polyphosphoric acid Polymers 0.000 abstract description 3
- 239000001488 sodium phosphate Substances 0.000 abstract description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract description 2
- 230000000865 phosphorylative effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910021487 silica fume Inorganic materials 0.000 description 12
- 239000004568 cement Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000001603 reducing effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- -1 ethylene glycol monobutyl ether acrylate-polyethylene glycol monomethyl ether ester Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011376 self-consolidating concrete Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- 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
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/045—Esters, e.g. lactones
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
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- 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
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0078—Sorbent materials
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/008—Flocking or deflocking agents
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- 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
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/008—Flocking or deflocking agents
- C04B2103/0081—Deflocking agents
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a viscosity reducer for ultra-high performance concrete, which is prepared by reacting phthalic anhydride, polyol polymer and a phosphorylation reagent serving as raw materials with a catalyst; the polyol polymer is polyethylene glycol or polypropylene glycol; the phosphorylation reagent is one of phosphoric acid, phosphorus pentoxide, polyphosphoric acid and sodium phosphate; the molar ratio of phthalic anhydride to polyol polymer to phosphorylating reagent is 1 (1.1-1.5): (1.1-1.7). The preparation method of the viscosity reducer comprises the following steps: step 1, adding a polyalcohol polymer into a four-neck flask, controlling the temperature to be 30-40 ℃, stirring, adding phthalic anhydride, adding a catalyst, and stirring for reaction for 1-2 hours; and 2, adding a phosphorylation reagent aqueous solution into the step 1, controlling the temperature to be 50-60 ℃, stirring for reaction for 2-3 hours, and cooling to room temperature to obtain the viscosity reducer. The viscosity reducer is applied to the ultra-high performance concrete with the water-to-gel ratio of 0.12-0.2, and can obviously reduce the viscosity of the concrete and improve the workability of the concrete.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a viscosity reducer for ultra-high performance concrete and a preparation method thereof.
Background
The ultra-high performance concrete has the characteristics of high strength, large load capacity, resource saving, excellent durability and the like. Can meet the requirements of light weight, high-rise, large span and durability of the building engineering, and is one of the important directions of the development of concrete technology. One of the characteristics of the composition of the ultra-high performance concrete is the ultra-low water-cement ratio (below 0.20). Along with the reduction of the water-cement ratio, the viscosity of the concrete mixture is increased, the construction problems of difficult stirring, difficult pumping and the like are caused, and the application of the concrete mixture is limited to a great extent. How to reduce the viscosity of concrete becomes a key problem for the development of ultra-high performance concrete.
The main methods for reducing the viscosity of the concrete at present comprise the design of the mix proportion of the concrete, the optimization of the composition of raw materials and the development of viscosity-reducing additives. Wherein the viscosity-reducing admixture has low mixing amount, simple use method and a large amount of research and application at home and abroad. For example, Japanese patent CN100402457C discloses a polycarboxylic acid polymer as a concrete viscosity reducer, which has slump-retaining ability while reducing the viscosity of concrete; hamada et al developed a novel polymer (NHBP type) with a multi-branched structure, which improves rheological properties and reduces viscosity by introducing two anionically acting monomers; wangyi et al synthesized a low-shrinkage and viscosity-reduction type polycarboxylate water reducer by Maleic Anhydride (MAH), ethylene glycol monobutyl ether acrylate-polyethylene glycol monomethyl ether ester macromonomer (MPEGnMA) according to a free radical copolymerization method; methyl methacrylate and alkylphenol ethoxylates containing hydrophobic groups are introduced into the main chain of the polycarboxylic acid molecule to adjust the hydrophilicity and lipophilicity of the molecular structure, and the polycarboxylic acid water reducer with the viscosity reduction effect is synthesized.
However, the research results are applicable to high-medium water-gel ratio systems, and only a few patents report on the research of low water-gel ratio systems (the water-gel ratio is less than 0.28). Patent ZL201810601948 mentions that polyethylene glycol maleate is polymerized with unsaturated acid to obtain the viscosity reducer, and the viscosity reducer can be applied to concrete with the water-to-gel ratio of 0.28. The patent ZL201410770317.3 mentions that the particle characteristics of metal salt are utilized to enhance the dispersibility of ultra-low water-to-gel ratio system and reduce the viscosity of slurry, and the application example reported in the patent adopts concrete with the water-to-gel ratio of 0.27. Patent ZL201610331188.7 discloses a short-side-chain viscosity reducer prepared by polymerizing 4-hydroxybutyl vinyl ether, unsaturated amide and unsaturated phosphate ester serving as raw materials, which has good adaptability with a polycarboxylic acid water reducer, can reduce the viscosity of concrete at a low mixing amount, and can improve the workability of the concrete. The patent mentions in application examples that the viscosity reducer can be applied to concrete with a water-gel ratio of 0.23, and whether the viscosity reducer can be applied to a system with a lower water-gel ratio is not reported. Patent ZL201710887711.9 discloses a high-strength concrete viscosity reducer prepared from ultrafine particles, which can be applied to concrete with a water-gel ratio of at least 0.21 and has an obvious viscosity reducing effect. The application range of the viscosity reducer reported above is that the water-gel ratio is between 0.2 and 0.28, and is rarely reported for an ultra-low water-gel ratio system of 0.2 and less than 0.2, and most of the water-gel ratio of the ultra-high performance concrete is less than 0.2 in the mix proportion design in order to improve the strength and durability of the concrete, so that the development of the viscosity reducer suitable for the ultra-high performance concrete is necessary.
Disclosure of Invention
The invention aims to provide a viscosity reducer for ultra-high performance concrete and a preparation method thereof, aiming at the defect that the conventional viscosity reducer is difficult to be applied to ultra-high performance concrete with the water-to-gel ratio of 0.2 and less than 0.2. The viscosity reducer can be used as an adsorption carrier for ultrafine materials such as silica fume in ultrahigh-performance concrete, and can improve the particle size effect of admixtures such as silica fume under low doping amount, enhance the dispersing capacity of the admixtures to cement particles, and improve the content of free water in slurry, thereby reducing the viscosity.
The viscosity reducer for the ultra-high performance concrete is synthesized by taking phthalic anhydride, polyol polymer and a phosphorylation reagent as raw materials through an esterification reaction under the action of a catalyst.
Wherein the polyalcohol polymer is polyethylene glycol or polypropylene glycol, and the weight average molecular weight is 200-4000 g/mol. Preferably, the weight average molecular weight is any one of 200g/mol, 400g/mol, 600g/mol,800g/mol,1000g/mol, 2000g/mol, and 4000 g/mol.
The phosphorylation reagent is one of phosphoric acid, phosphorus pentoxide, polyphosphoric acid and sodium phosphate. When in use, the phosphorylation reagent is prepared into phosphorylation reagent aqueous solution with the mass percentage concentration of 20-60%.
The weight ratio of phthalic anhydride, polyalcohol polymer and phosphorylation reagent substance is 1 (1.1-1.5): (1.1-1.7). The catalyst is one of concentrated sulfuric acid, p-toluenesulfonic acid, citric acid and concentrated hydrochloric acid. The catalyst is used in an amount of 0.1 to 1% by mass, preferably 0.2 to 0.8% by mass, based on the polyol polymer.
The preparation method of the ultra-high performance concrete viscosity reducer comprises the following steps:
(1) adding a polyalcohol polymer into a four-neck flask, heating to 30-40 ℃, stirring, adding phthalic anhydride and a catalyst, and stirring for reaction for 1-2 hours.
(2) And (3) adding a phosphorylation reagent aqueous solution into the step (1), heating to 50-60 ℃, stirring for reaction for 1-3 hours, and cooling to room temperature to obtain the viscosity reducer. The viscosity reducer is a mixture of polypolyol dibenzoate and phosphorylated polypolyol monobenzoate.
The chemical reaction processes involved in the preparation method are as follows in sequence (taking polyethylene glycol and phosphoric acid as examples):
wherein n is an integer selected from 6 to 40. Preferably n is 6-10. The prepared viscosity reducer is a mixture of phthalic anhydride polyethylene glycol phosphate shown in a molecular structural formula I and polyethylene glycol diester shown in a formula II:
if the polyalcohol polymer adopts polypropylene glycol, the prepared viscosity reducer is analogized in turn.
Compared with the prior art, the invention has the advantages that:
(1) the invention utilizes the esterification reaction of high-activity phthalic anhydride with certain rigidity and polyalcohol polymer under the action of a catalyst to obtain a mixture of poly-polyalcohol monobenzoate and poly-polyalcohol bibenzoate; wherein, the polymeric polylol monobenzoate reacts with a phosphorylation reagent with strong adsorption to prepare a polymer with certain molecular weight and structural rigidity, and finally the viscosity reducer is obtained. The viscosity reducer is a mixture of polypolyol dibenzoate and phosphorylated polypolyol monobenzoate. Both polymers in the viscosity reducer have the effect of reducing the viscosity of concrete. The viscosity reducer has carboxyl and phosphate groups which can be adsorbed on the surface of silica fume, and the phthalic anhydride structure has certain rigidity. The molecular weight of a final product can be controlled by selecting the molecular weight of a polyalcohol polymer, benzene rings in the structure can increase the molecular rigidity, the self dispersing performance of the silica fume is enhanced after the polymer is adsorbed on the surface of the silica fume, the particle size effect is combined, the aggregation structure of cement particles is broken in an ultralow water-cement ratio system, free water is released, and therefore, the slurry viscosity is reduced, and the preparation method is suitable for ultrahigh-performance concrete with the water-cement ratio of 0.2 to less than 0.2. The inventor researches to find that the viscosity reducing effect of the phosphorylated polyatomic alcohol monobenzoate is greater than that of the polyatomic alcohol bibenzoate, namely, the phosphorylated polyatomic alcohol monobenzoate plays a main viscosity reducing role, and the polyatomic alcohol bibenzoate is used as an auxiliary.
(2) The viscosity reducer prepared by the invention has a certain adsorption effect on the silica fume, and the silica fume adsorbing the viscosity reducer can better reduce the aggregation tendency among cement particles in a low water-gel ratio system and enhance the dispersion among the cement particles.
(3) In the process of preparing the polyol monoester, the content of the polyol diester is effectively controlled by controlling the reaction temperature, the proportion of reaction substances and the charging sequence, and the separation and purification are not needed in the reaction process.
(4) The viscosity reducer prepared by the invention is designed based on an ultra-low water-to-gel ratio system, and can obviously reduce the viscosity of ultra-high performance concrete and improve the working performance of the ultra-high performance concrete.
(5) The raw materials related by the invention are cheap and easy to obtain, the synthesis process is simple and convenient, no additional reaction solvent is required to be added, no separation and purification is required, and the method is environment-friendly and suitable for popularization and application.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1
Adding 500g of polyethylene glycol (with the weight average molecular weight of 200g/mol) into a four-neck flask, heating to 30 ℃, stirring, adding 185g of phthalic anhydride, adding 0.1g of concentrated sulfuric acid, stirring for reaction for 2 hours, adding 100g of phosphoric acid and 50g of water, heating to 60 ℃, and stirring for 2 hours to obtain a reddish brown liquid, namely the viscosity reducer (the solid content is 94.0%). The end of the reaction was monitored by HPLC for phthalic anhydride content of less than 5% and by titration for phosphate content of less than 6%, as in the examples which follow. (HPLC detection method and titration method for measuring phosphate radical content are conventional standard methods, and will not be repeated here)
Example 2
500g of polypropylene glycol (with the weight average molecular weight of 800g/mol) is added into a four-neck flask, the mixture is heated to 40 ℃ and stirred, 46g of phthalic anhydride and 0.1g of concentrated sulfuric acid are added, the mixture is stirred and reacted for 1 hour, a phosphoric acid aqueous solution (a mixture of 25g of phosphoric acid and 20g of water) is added, the mixture is heated to 50 ℃ and stirred for 3 hours, and a reddish brown liquid, namely the viscosity reducer (the solid content is 96.6%) is obtained.
Example 3
500g of polypropylene glycol (with a weight average molecular weight of 2000g/mol) is added into a four-neck flask, the mixture is heated to 40 ℃, stirred, then 18.5g of phthalic anhydride is added, 0.1g of p-toluenesulfonic acid is added, the mixture is stirred and reacted for 2 hours, a phosphoric acid aqueous solution (a mixture of 10g of polyphosphoric acid and 10g of water) is added, the mixture is heated to 60 ℃, and stirred for 2 hours, so that a reddish brown liquid, namely the viscosity reducer (solid content is 98%) is obtained.
Example 4
Adding 500g of polyethylene glycol (with the weight average molecular weight of 800g/mol) into a four-neck flask, heating to 40 ℃, stirring, adding 31g of maleic anhydride, adding 0.2g of concentrated sulfuric acid, stirring for reaction for 1 hour, adding 25g of phosphorus pentoxide and 20g of water, heating to 50 ℃, and stirring for 3 hours to obtain a reddish brown liquid, namely the viscosity reducer (the solid content is 96.1%).
Application example
In practical use, the performance effects of the viscosity reducers of examples 1 to 4 were tested. The concrete viscosity is measured according to the V-shaped leak passing time specified in the technical Specification for self-compacting concrete application CECS 203-2006. Wherein the longer the passage time, the greater the viscosity. The compressive strength of the concrete is in accordance with GBT50081-2002 standard for testing mechanical properties of ordinary concrete. Table 1 shows the composition of the ultra-high performance concrete raw materials. The water reducing agent is a high-water-reducing water reducing agent of Xika. Table 2 shows the results of the viscosity and strength tests of the ultra-high performance concrete.
TABLE 1 composition of ultra high Performance concrete raw materials(kg/m3)
| Test sample | Cement | Silica fume | Fly ash | Steel fiber | Quartz sand | Water (W) | Water reducing agent | Viscosity reducer |
| Blank control sample | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0 |
| Example 1 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
| Example 2 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
| Example 3 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
| Example 4 | 648 | 174 | 196 | 12.96 | 1018 | 203.6 | 10.2 | 0.8 |
TABLE 2 viscosity and Strength test results for ultra high Performance concrete
From the above examples, the viscosity reducer has no side effects on the strength of the concrete. The molecular weight of the polyalcohol polymer has obvious influence on the viscosity reduction effect, ultrafine particles with overlarge molecular weight cannot completely enter gaps of cement particles, and the viscosity of slurry is increased, so the viscosity reduction effect is not obvious; the dispersing effect of the silica fume is weakened when the molecular weight is too small, and the synthesized viscosity reducer has the best effect when the molecular weight is 800; compared with maleic anhydride, the rigidity of the whole molecule is improved after the phthalic anhydride is introduced, the dispersibility of ultrafine particles is enhanced, the viscosity reduction effect is improved to a certain extent, and the viscosity reducer is suitable for ultra-high performance concrete with the water-to-gel ratio of 0.2 and less than 0.2.
In conclusion, the viscosity reducer is prepared by reacting phthalic anhydride with certain rigidity with dihydric alcohol polymers with different molecular weights and phosphoric acid with strong adsorption. The viscosity reducer has carboxyl and phosphate groups which can be adsorbed on the surface of silica fume, and the phthalic anhydride structure has certain rigidity, and the chain length of the polymer can be adjusted by selecting dihydric alcohol polymers with different molecular weights. The viscosity reducer can be used for taking ultrafine materials such as silica fume and the like in ultrahigh-performance concrete as adsorption carriers, improving the particle size effect of admixtures such as silica fume and the like under low doping amount, enhancing the dispersing capacity of the admixtures to cement particles, and improving the content of free water in slurry, thereby reducing the viscosity.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The viscosity reducer for the ultra-high performance concrete is characterized by being prepared by esterification reaction of phthalic anhydride, polyethylene glycol and phosphoric acid serving as raw materials under the action of a catalyst; wherein the mass ratio of phthalic anhydride, polyethylene glycol and phosphoric acid is 1 (1.1-1.5): (1.1 to 1.7);
the viscosity reducer prepared is a mixture of two substances shown in molecular structural formulas I and II:
in the formula, n is an integer and takes a value of 6-40.
2. The viscosity reducer for ultra-high performance concrete according to claim 1, wherein phosphoric acid is prepared into an aqueous solution of phosphoric acid with a mass percentage concentration of 20-60% when in use.
3. The viscosity reducer for ultra-high performance concrete according to claim 1, wherein n is 6-10.
4. The viscosity reducer for ultra-high performance concrete according to claim 1, wherein the catalyst is one of concentrated sulfuric acid, p-toluenesulfonic acid, citric acid and concentrated hydrochloric acid, and the amount of the catalyst is 0.1-1% of the mass of the polyol polymer.
5. The viscosity reducer for ultra-high performance concrete according to claim 1, wherein the viscosity reducer is used in the ultra-high performance concrete with a water-to-gel ratio of 0.12-0.2, and the mixing amount of the viscosity reducer is 0.02-0.1% of the mass of the concrete cementing material.
6. A method for preparing the viscosity reducer for ultra-high performance concrete according to any one of claims 1 to 5, characterized by comprising the steps of:
step 1: adding polyethylene glycol into a four-neck flask, controlling the temperature to be 30-40 ℃, stirring, adding phthalic anhydride, adding a catalyst, and stirring for reacting for 1-2 hours;
step 2: and (3) adding a phosphoric acid aqueous solution into the step (1), controlling the temperature to be 50-60 ℃, stirring for reaction for 2-3 hours, and cooling to room temperature to obtain the viscosity reducer.
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