CN117383862A - Air entraining agent regulator and preparation method and application thereof - Google Patents
Air entraining agent regulator and preparation method and application thereof Download PDFInfo
- Publication number
- CN117383862A CN117383862A CN202311322587.3A CN202311322587A CN117383862A CN 117383862 A CN117383862 A CN 117383862A CN 202311322587 A CN202311322587 A CN 202311322587A CN 117383862 A CN117383862 A CN 117383862A
- Authority
- CN
- China
- Prior art keywords
- entraining agent
- hyperbranched polyester
- air entraining
- concrete
- air
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 102
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 89
- 239000004567 concrete Substances 0.000 claims abstract description 84
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006260 foam Substances 0.000 claims abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- 239000002562 thickening agent Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 67
- 238000002156 mixing Methods 0.000 claims description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229920005646 polycarboxylate Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 3
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 abstract description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 abstract description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 abstract 1
- 235000019345 sodium thiosulphate Nutrition 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000004568 cement Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 206010016807 Fluid retention Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention relates to the field of concrete, in particular to an air entraining agent regulator and a preparation method and application thereof; comprises the following components in parts by mass: 25-45 parts of modified hyperbranched polyester, 20-40 parts of triethanolamine, 40-65 parts of diethanol monoisopropanolamine, 10-30 parts of sodium thiosulfate, 120-150 parts of air entraining agent, 8-25 parts of foam stabilizer, 5-12 parts of thickener and 40-80 parts of water reducer; the obtained air entraining agent regulator can promote the super-doping of the air entraining agent, improve the workability of concrete, and has simple use and wide application prospect.
Description
Technical Field
The invention relates to the field of concrete, in particular to an air entraining agent regulator and a preparation method and application thereof.
Background
Among the many building materials, concrete is one of the most widely used materials with the greatest amount. The air entraining agent is used as one of the indispensable components of modern concrete, and can improve the flowability, cohesiveness and water retention of the concrete mixture, raise the flowability of the concrete, introduce a great amount of uniformly distributed, closed and stable micro bubbles during the mixing process of the concrete mixture, and is very critical for improving the performance of the concrete.
However, the mixing amount of the air entraining agent is generally very low, the mixing amount mass fraction of the air entraining agent in the conventional concrete is 0.1-0.12 per mill, and the excessive addition of the air entraining agent can reduce the working performance of the concrete, and further affect the compressive strength, impermeability and carbonization resistance of the concrete and the comprehensive performance of the concrete.
Disclosure of Invention
In order to solve the problems, the invention provides an air entraining agent regulator which is prepared from the following components in parts by mass:
preferably, the air entraining agent regulator comprises the following components in parts by mass:
the air entraining agent is rosin air entraining agent, and comprises one or two of rosin thermopolymer and rosin soap, preferably rosin thermopolymer.
The foam stabilizer comprises one or more of sodium carboxymethyl cellulose, polyvinyl alcohol and dodecyl dimethyl amine oxide, preferably one or two of sodium carboxymethyl cellulose and polyvinyl alcohol.
The thickener comprises one or more of polyacrylamide, cellulose ether, xanthan gum and temperature roller gum, preferably polyacrylamide.
The water reducing agent comprises one or more of lignin water reducing agent, naphthalene water reducing agent and polycarboxylate water reducing agent, and preferably polycarboxylate water reducing agent.
Wherein the hyperbranched polyester is carboxyl-terminated hyperbranched polyester.
The modified hyperbranched polyester is ionized modified hyperbranched polyester, and the modifying agent is strong alkali such as NaOH or KOH.
The method for modifying hyperbranched polyester comprises the following steps:
the hyperbranched polyester reacts with alkali liquor, and the modified hyperbranched polyester is obtained after purification.
Wherein the dosage of the alkali liquor is controlled so that the carboxyl part of the hyperbranched polyester is modified.
Preferably, the proportion of carboxyl modification of the hyperbranched polyester is from 20 to 80%, more preferably from 30 to 70%, most preferably from 40 to 60%.
Specifically, the modification method of the hyperbranched polyester comprises the following steps:
placing the hyperbranched polyester into a reaction vessel, adding a solvent, heating to 75-100 ℃, slowly dropwise adding alkali liquor under stirring, reacting for 1-3h after the addition is finished to obtain saponified hyperbranched polyester, adding a proper amount of NaCl solution, filtering, drying, washing, and drying again to obtain the modified hyperbranched polyester.
The alkali liquor comprises one or two of NaOH solution or KOH solution, preferably NaOH solution.
Wherein the hyperbranched polyester is based on COOH content, the alkali liquor is based on OH content, and the molar ratio of the two is 100:20-80, more preferably 100:30-70, and most preferably 100:40-60.
In the hyperbranched polyester, the carboxyl number is 6-24/mol, the acid value is 220-360mgKOH/g, and the molecular weight is 950-6400g/mol.
More preferably, the hyperbranched polyester has a carboxyl number of 6 to 24 g/mol, an acid value of 220 to 320mgKOH/g and a molecular weight of 1000 to 6400g/mol.
Most preferably, the hyperbranched polyester has a carboxyl number of 6 to 12 g/mol, an acid value of 240 to 320mgKOH/g and a molecular weight of 1000 to 2600g/mol.
The hyperbranched polyester can be directly purchased, such as hyperbranched polyester C101, hyperbranched polyester C102, hyperbranched polyester C103, hyperbranched polyester C201, hyperbranched polyester C301 and the like of the Wuhan hyperbranched resin science and technology Co.
The formula is obtained by the inventor through continuous attempts, and the inventor finds that the modified hyperbranched polyester contains a large number of functional groups including carboxylate and carboxyl, and polyether chain segments, so that the modified hyperbranched polyester has good interface compatibility with air entraining agents and water reducing agents, and has special structure and good flow property. In addition, triethanolamine and diethanol monoisopropanolamine also contain a large number of functional groups, and intermolecular acting forces can be formed between the polar functional groups, so that the addition of the modified hyperbranched polyester can greatly improve the comprehensive performance of the air entraining agent regulator.
In addition, the invention provides a preparation method of the air entraining agent regulator, which comprises the following steps:
and uniformly mixing the components of the air entraining agent regulator to obtain the air entraining agent regulator.
Wherein the mixing may be sequential or disposable, and if necessary, the desired solvent may be added.
The invention also provides application of the air entraining agent regulator, and the air entraining agent regulator is used for preparing concrete.
The air entraining agent regulator is used in concrete to raise the mixing amount of air entraining agent and improve the workability of concrete.
Wherein, the dosage of the air entraining agent is 0.05 to 0.5 per mill, preferably 0.1 to 0.4 per mill, more preferably 0.2 to 0.3 per mill based on the whole mass of the concrete.
Wherein the super-mixing proportion of the air entraining agent is 50-200%, preferably 80-150%, more preferably 90-120%.
The invention also provides concrete, wherein the air entraining agent regulator is doped in the concrete.
Wherein, the dosage of the air entraining agent regulator is 0.01 to 0.3 per mill, preferably 0.05 to 0.2 per mill, more preferably 0.1 to 0.15 per mill based on the whole mass of the concrete.
Specifically, the invention also provides a formula of the concrete, which comprises the following components in parts by mass:
as described above, the regulator provided by the invention contains rich functional groups, and the air entraining agent and the water reducing agent are organically integrated, so that the air entraining agent added in the concrete exceeds the conventional limit mixing amount. The workability of the concrete can be improved after the air entraining agent is excessively doped, segregation can not occur, and the viscosity of the concrete is reduced. And the water reducer can be super-doped on the basis, so that the water consumption of the concrete is reduced, and the workability of the concrete is further improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention creatively prepares the air entraining agent regulator formula, wherein the air entraining agent and the water reducing agent are organically integrated, so that the air entraining agent added in the concrete exceeds the conventional limit doping amount, a large amount of tiny and uniform independent bubbles are introduced, the ball bearing function is realized, the friction force among aggregate particles is reduced, the volume of the cement paste is increased, the workability of the concrete can be obviously improved, and the workability of the concrete is not influenced by the change of sand materials.
(2) The air entraining agent regulator ensures that the strength of the concrete prepared under the condition of extreme sandstone materials reaches the standard, the difficulty in controlling the preparation of the concrete is obviously reduced, and the preparation of the concrete under special conditions (such as rescue and relief work) is convenient; meanwhile, the viscosity of the concrete can be obviously reduced through the super-doped air entraining agent, the pumping efficiency can be improved, the pipe is not easy to block during pumping, and the method is particularly suitable for super-high concrete pumping. The admixture can obviously increase fluidity and can be used for self-leveling construction of cement mortar.
(3) The invention also utilizes the special structure of the hyperbranched polyester, comprehensively improves the integral state of air entraining agents, water reducing agents and the like, ensures that all the components of the concrete are integrated, largely avoids the great reduction of the strength of the concrete, and ensures the basic use requirement.
(4) The air entraining agent regulator is prepared by simple modification, is simple to use, can obtain a remarkable effect by adding a small amount of the air entraining agent regulator, is low in cost, has a wide application prospect, and has a very remarkable industrial value.
Drawings
FIG. 1 is a concrete pattern diagram prepared in application example 1 of the present invention;
FIG. 2 is a schematic view of concrete prepared in application example 2 of the present invention;
FIG. 3 is a schematic view of concrete prepared in application example 3 of the present invention;
FIG. 4 is a schematic view of concrete prepared in application example 4 of the present invention;
FIG. 5 is a concrete pattern diagram prepared in application example 5 of the present invention;
FIG. 6 is a schematic view of concrete prepared in comparative application example 1 of the present invention;
FIG. 7 is a schematic view of concrete prepared in comparative application example 2 of the present invention;
FIG. 8 is a schematic representation of the concrete pattern prepared in comparative application example 3 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The air entraining agent regulator comprises the following components in parts by mass:
preferably, the air entraining agent regulator comprises the following components in parts by mass:
the air entraining agent is rosin air entraining agent, and comprises one or two of rosin thermopolymer and rosin soap, preferably rosin thermopolymer.
The foam stabilizer comprises one or more of sodium carboxymethyl cellulose, polyvinyl alcohol and dodecyl dimethyl amine oxide, preferably one or two of sodium carboxymethyl cellulose and polyvinyl alcohol.
The thickener comprises one or more of polyacrylamide, cellulose ether, xanthan gum and temperature roller gum, preferably polyacrylamide.
The water reducing agent comprises one or more of lignin water reducing agent, naphthalene water reducing agent and polycarboxylate water reducing agent, and preferably polycarboxylate water reducing agent.
Wherein the hyperbranched polyester is carboxyl-terminated hyperbranched polyester.
The modified hyperbranched polyester is ionized modified hyperbranched polyester, and the modifying agent is strong alkali such as NaOH or KOH.
The method for modifying hyperbranched polyester comprises the following steps:
the hyperbranched polyester reacts with alkali liquor, and the modified hyperbranched polyester is obtained after purification.
Wherein the dosage of the alkali liquor is controlled so that the carboxyl part of the hyperbranched polyester is modified.
Preferably, the proportion of carboxyl modification of the hyperbranched polyester is from 20 to 80%, more preferably from 30 to 70%, most preferably from 40 to 60%.
Specifically, the modification method of the hyperbranched polyester comprises the following steps:
placing the hyperbranched polyester into a reaction vessel, adding a solvent, heating to 75-100 ℃, slowly dropwise adding alkali liquor under stirring, reacting for 1-3h after the addition is finished to obtain saponified hyperbranched polyester, adding a proper amount of NaCl solution, filtering, drying, washing, and drying again to obtain the modified hyperbranched polyester.
The alkali liquor comprises one or two of NaOH solution or KOH solution, preferably NaOH solution.
Wherein the hyperbranched polyester is based on COOH content, the alkali liquor is based on OH content, and the molar ratio of the two is 100:20-80, more preferably 100:30-70, and most preferably 100:40-60.
In the hyperbranched polyester, the carboxyl number is 6-24/mol, the acid value is 220-360mgKOH/g, and the molecular weight is 950-6400g/mol.
More preferably, the hyperbranched polyester has a carboxyl number of 6 to 24 g/mol, an acid value of 220 to 320mgKOH/g and a molecular weight of 1000 to 6400g/mol.
Most preferably, the hyperbranched polyester has a carboxyl number of 6 to 12 g/mol, an acid value of 240 to 320mgKOH/g and a molecular weight of 1000 to 2600g/mol.
The hyperbranched polyester can be directly purchased, such as hyperbranched polyester C101, hyperbranched polyester C102, hyperbranched polyester C103, hyperbranched polyester C201, hyperbranched polyester C301 and the like of the Wuhan hyperbranched resin science and technology Co.
In addition, the invention provides a preparation method of the air entraining agent regulator, which comprises the following steps:
and uniformly mixing the components of the air entraining agent regulator to obtain the air entraining agent regulator.
Wherein the mixing may be sequential or disposable, and if necessary, the desired solvent may be added.
The invention also provides application of the air entraining agent regulator, and the air entraining agent regulator is used for preparing concrete.
The air entraining agent regulator is used in concrete to raise the mixing amount of air entraining agent and improve the workability of concrete.
Wherein, the dosage of the air entraining agent is 0.05 to 0.5 per mill, preferably 0.1 to 0.4 per mill, more preferably 0.2 to 0.3 per mill based on the whole mass of the concrete.
Wherein the super-mixing proportion of the air entraining agent is 50-200%, preferably 80-150%, more preferably 90-120%.
The invention also provides concrete, wherein the air entraining agent regulator is doped in the concrete.
Wherein, the dosage of the air entraining agent regulator is 0.01 to 0.3 per mill, preferably 0.05 to 0.2 per mill, more preferably 0.1 to 0.15 per mill based on the whole mass of the concrete.
Specifically, the invention also provides a formula of the concrete, which comprises the following components in parts by mass:
examples raw materials
The raw materials used in the examples and comparative examples are as follows, unless otherwise specified:
water reducing agent, LG Chem CP-WBK50, available from LG Chem limited;
hyperbranched polyester C101, with a carboxyl number of 6/mol, an acid value of 320mgKOH/g, a molecular weight of 1000g/mol, obtained from the company WUHan hyperbranched resin technology Co., ltd;
hyperbranched polyester C102, with a carboxyl number of 12/mol, an acid value of 240mgKOH/g and a molecular weight of 2600g/mol, obtained from the company WUHan hyperbranched resin technology Co., ltd;
hyperbranched polyester C103, with a carboxyl number of 24/mol, an acid value of 220mgKOH/g, a molecular weight of 6400g/mol, obtained from the company Bhan hyperbranched resin technology Co., ltd;
hyperbranched polyester C201, with a carboxyl number of 6/mol, an acid value of 360mgKOH/g and a molecular weight of 950g/mol, is obtained from the company WUHan hyperbranched resin technology Co., ltd;
hyperbranched polyester C301, having a carboxyl number of 6/mol, an acid number of 340mgKOH/g and a molecular weight of 950g/mol, was obtained from the company WUHan hyperbranched resin technology Co.
Preparation example 1
100g of hyperbranched polyester C101 is placed in a reaction vessel, DMF is added, the temperature is raised to 85 ℃, 10% NaOH solution is slowly added dropwise under stirring, the total concentration of the NaOH solution is 120g, the reaction is carried out for 2 hours after the addition is finished, a proper amount of NaCl solution is added, the filtration and the drying are carried out, the washing is carried out, and the obtained product is marked as modified C101-1.
Preparation example 2
100g of hyperbranched polyester C102 is placed in a reaction vessel, DMF is added, the temperature is raised to 85 ℃, 10% NaOH solution is slowly added dropwise under stirring, 92.3g of NaOH solution is added, the reaction is carried out for 2 hours after the addition, and the saponified hyperbranched polyester is marked as modified C102.
Preparation example 3
100g of hyperbranched polyester C103 is placed in a reaction vessel, DMF is added, the temperature is raised to 85 ℃, 10% NaOH solution is slowly added dropwise under stirring, 75 parts of NaOH solution is added, and after the addition is finished, the reaction is carried out for 2 hours, so that saponified hyperbranched polyester is obtained, and the saponified hyperbranched polyester is marked as modified C103.
Preparation example 4
100 parts of hyperbranched polyester C201 are placed in a reaction vessel, DMF is added, the temperature is raised to 85 ℃, 10% NaOH solution is slowly added dropwise under stirring, 126 parts of NaOH solution are added, and after the addition is finished, the reaction is carried out for 2 hours, so that saponified hyperbranched polyester is obtained, and the saponified hyperbranched polyester is marked as modified C201.
Preparation example 5
100 parts of hyperbranched polyester C301 are placed in a reaction vessel, DMF is added, the temperature is raised to 85 ℃, 10% NaOH solution is slowly added dropwise under stirring, 126 parts of NaOH solution are added, and after the addition is finished, the reaction is carried out for 2 hours, so that saponified hyperbranched polyester is obtained, and the saponified hyperbranched polyester is marked as modified C301.
Preparation example 6
100 parts of hyperbranched polyester C101 is placed in a reaction vessel, DMF is added, the temperature is raised to 85 ℃, 10% NaOH solution is slowly added dropwise under stirring, 240 parts of NaOH solution is added, and after the addition is finished, the reaction is carried out for 2 hours, so that saponified hyperbranched polyester is obtained, and the saponified hyperbranched polyester is marked as modified C101-2.
Example 1
The air entraining agent regulator comprises the following raw materials in parts by mass:
and mixing the components according to the proportion to obtain the air entraining agent regulator.
Example 2
The air entraining agent regulator comprises the following raw materials in parts by mass:
and mixing the components according to the proportion to obtain the air entraining agent regulator.
Example 3
The air entraining agent regulator comprises the following raw materials in parts by mass:
and mixing the components according to the proportion to obtain the air entraining agent regulator.
Example 4
The air entraining agent regulator comprises the following raw materials in parts by mass:
and mixing the components according to the proportion to obtain the air entraining agent regulator.
Example 5
The air entraining agent regulator comprises the following raw materials in parts by mass:
and mixing the components according to the proportion to obtain the air entraining agent regulator.
Comparative example 1
The air entraining agent regulator comprises the following raw materials in parts by mass:
and mixing the components according to the proportion to obtain the air entraining agent regulator.
Comparative example 2
The air entraining agent regulator comprises the following raw materials in parts by mass:
and mixing the components according to the proportion to obtain the air entraining agent regulator.
The air entraining agent regulator is prepared according to the method, then cement, fly ash, mineral powder, sand, stone, water, polycarboxylate water reducer, air entraining agent and air entraining agent regulator are mixed and stirred, the state of concrete is observed, and relevant performance tests are carried out, and relevant applications are as follows.
Application example 1
A concrete comprises the following components (parts by mass)
Wherein the air entraining agent regulator was prepared in example 1.
Mixing and stirring the components to prepare the concrete.
Application example 2
A concrete comprises the following components (parts by mass)
Wherein the air entraining agent regulator was prepared as in example 2.
Mixing and stirring the components to prepare the concrete.
Application example 3
A concrete comprises the following components (parts by mass)
Wherein the air entraining agent regulator was prepared in example 3.
Mixing and stirring the components to prepare the concrete.
Application example 4
A concrete comprises the following components (parts by mass)
Wherein the air entraining agent regulator was prepared in example 4.
Mixing and stirring the components to prepare the concrete.
Application example 5
A concrete comprises the following components (parts by mass)
Wherein the air entraining agent regulator was prepared in example 5.
Mixing and stirring the components to prepare the concrete.
Comparative application example 1
A concrete comprises the following components (parts by mass)
Mixing and stirring the components to prepare the concrete.
Comparative application example 2
A concrete comprises the following components (parts by mass)
Wherein the air entraining agent regulator is prepared in comparative example 1.
Mixing and stirring the components to prepare the concrete.
Comparative application example 3
A concrete comprises the following components (parts by mass)
Wherein the air entraining agent regulator is prepared in comparative example 2.
Mixing and stirring the components to prepare the concrete.
The concrete obtained was tested for the following properties and criteria:
the air content, slump and slump fall time are tested according to the standard GB/T50080-2016 common concrete mixture performance test method, and the cement paste fluidity is tested according to the standard GB/T8077-2012 concrete additive homogeneity test method.
The test results are shown in Table 1 below
Table 1:
as can be seen from the above table, the use of the air entraining agent regulator in examples 1 to 5, which has an air entraining agent itself, can allow the air entraining agent added to the concrete to exceed the conventional limit doping amount, as compared to comparative application example 1. In the comparative examples, the air entraining agent was added only marginally, but the effect was not good. The workability of the concrete can be improved after the air entraining agent is excessively doped, segregation can not occur, and the viscosity of the concrete is reduced. And the air content of the concrete is greatly increased, a large amount of tiny and uniform independent air bubbles are introduced, the ball bearing function is realized, the friction force among aggregate particles is reduced, the volume of the cement paste is increased, the workability of the concrete is improved, and the slump and the cement paste fluidity of the concrete are obviously improved. Although the strength of the concrete is reduced, the modified hyperbranched polyester is used in the air entraining agent regulator, so that the great reduction of the strength of the concrete can be avoided to a great extent, and the basic use requirement is ensured.
The slump can be used for representing the flowing speed of the concrete mixture through the flowing time, and indirectly representing the cohesiveness of the concrete mixture. The flowing time is long, the flowing speed is low, the viscosity of the mixture is high, the flowing time is short, and the flowing speed is high, so that the viscosity of the mixture is low.
As can be seen from the comparison of the data, the super-doped air entraining agent in the application examples 1-5 can obviously reduce the viscosity of concrete, the collapse time can reach about 4 seconds at the lowest, and the collapse time in the comparison examples is 11-14 seconds, the collapse time in the application examples 1-5 is fast, the viscosity is low, the pumping efficiency can be effectively improved, and the construction efficiency is further improved.
Those skilled in the art will appreciate that the above-described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art without making any inventive effort, are intended to be within the scope of the present invention based on the above embodiments.
Claims (10)
1. The air entraining agent regulator is technically characterized by comprising the following components in parts by mass:
2. the air entraining agent according to claim 1, characterized in that the air entraining agent is a rosin air entraining agent, comprising one or two of rosin thermopolymer and rosin soap, preferably rosin thermopolymer.
3. The air entraining agent regulator according to claim 1, characterized in that the foam stabilizer comprises one or more of sodium carboxymethyl cellulose, polyvinyl alcohol and dodecyl dimethyl amine oxide, preferably one or two of sodium carboxymethyl cellulose and polyvinyl alcohol.
4. The air entraining agent regulator according to claim 1, characterized in that the thickener comprises one or more of polyacrylamide, cellulose ether, xanthan gum, and hotplate gum, preferably polyacrylamide.
5. The air entraining agent regulator according to claim 1, characterized in that the water reducing agent comprises one or more of lignin water reducing agent, naphthalene water reducing agent and polycarboxylate water reducing agent, preferably polycarboxylate water reducing agent.
6. The air entraining agent regulator according to claim 1, characterized in that the modified hyperbranched polyester is an ionized modified hyperbranched polyester, and the modifying agent is NaOH or KOH;
the hyperbranched polyester is carboxyl-terminated hyperbranched polyester;
preferably, the method for modifying the hyperbranched polyester comprises the following steps:
the hyperbranched polyester reacts with alkali liquor, and the modified hyperbranched polyester is obtained after purification;
preferably, the amount of lye is controlled such that the carboxyl moiety of the hyperbranched polyester is modified;
preferably, the proportion of carboxyl modification of the hyperbranched polyester is from 20 to 80%, more preferably from 30 to 70%, most preferably from 40 to 60%.
7. The air-entraining agent regulator according to claim 1, characterized in that the modification method of the modified hyperbranched polyester comprises the following steps:
placing hyperbranched polyester in a reaction vessel, adding a solvent, heating to 75-100 ℃, slowly dripping alkali liquor under stirring, reacting for 1-3h after the addition is finished to obtain saponified hyperbranched polyester, adding a proper amount of NaCl solution, filtering, drying, washing, and drying again to obtain modified hyperbranched polyester;
wherein the alkali liquor comprises one or two of NaOH solution or KOH solution, preferably NaOH solution;
preferably, the hyperbranched polyester has a COOH content and the lye has an OH content, the molar ratio of the two being 100:20 to 80, more preferably 100:30 to 70, most preferably 100:40 to 60.
8. The air-entraining agent regulator according to claim 1, characterized in that,
the carboxyl number of the hyperbranched polyester is 6-24/mol, the acid value is 220-360mgKOH/g, and the molecular weight is 950-6400g/mol;
more preferably, the hyperbranched polyester has a carboxyl number of 6-24/mol, an acid value of 220-320mgKOH/g and a molecular weight of 1000-6400g/mol;
most preferably, the hyperbranched polyester has a carboxyl number of 6-12 g/mol, an acid value of 240-320mgKOH/g and a molecular weight of 1000-2600g/mol.
9. The method for preparing an air-entraining agent regulator according to any one of claims 1 to 8, characterized in that the method comprises the following steps:
and uniformly mixing the components of the air entraining agent regulator to obtain the air entraining agent regulator.
10. The use of an air-entraining agent regulator according to claim 1, characterized in that the air-entraining agent regulator is used for the preparation of concrete.
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| CN112028541A (en) * | 2020-09-09 | 2020-12-04 | 江西省建筑材料工业科学研究设计院 | Concrete nano reinforcing modifier and preparation method thereof |
| CN114315219A (en) * | 2022-01-14 | 2022-04-12 | 中国葛洲坝集团水泥有限公司 | Workability regulator for machine-made sand concrete |
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| WO2002022520A1 (en) * | 2000-09-18 | 2002-03-21 | Rhodia Chimie | Cement material comprising a dendritic polymer |
| CN101712752A (en) * | 2009-11-03 | 2010-05-26 | 上海大学 | Hyperbranched polymer template material and application thereof in preparing organic nanoparticles |
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