CN108101403B - A kind of preparation method of environment-friendly type alkali-free liquid accelerator - Google Patents
A kind of preparation method of environment-friendly type alkali-free liquid accelerator Download PDFInfo
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- CN108101403B CN108101403B CN201711468534.7A CN201711468534A CN108101403B CN 108101403 B CN108101403 B CN 108101403B CN 201711468534 A CN201711468534 A CN 201711468534A CN 108101403 B CN108101403 B CN 108101403B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation methods of environment-friendly type alkali-free liquid accelerator.Preparation method of the invention is by carrying out acrylamide and unsaturated acids to be copolymerized obtained suspension stabilizer, it is used for preparing the synthesis of alkali-free liquid accelerator again, accelerator is optimized by introducing high-molecular copolymer, improve the coherency of liquid accelerator, effectively inhibit the generation of precipitating, the stability of mother liquor storage is substantially increased, stability can reach 1 year or more.Environment-friendly type alkali-free liquid accelerator prepared by the present invention is non-corrosive to construction worker's skin, pollution-free to production environment, belongs to green product without environmental pollution.
Description
Technical field
The invention belongs to building material technical fields, and in particular to a kind of preparation side of environment-friendly type alkali-free liquid accelerator
Method.
Background technique
With the acceleration of large-scale mining, tunnel excavation and network of highways and railway network engineering construction, so that fast
Solidifying agent dosage greatly increases, and to the performance quality of accelerator, higher requirements are also raised.Conventional powdered accelerator product can only
It constructs applied to dry pressure spray process, and that there are solution rates is slow, is not easy the defects of being uniformly dispersed.
Currently, the development trend of gunite concrete accelerator is changed from traditional solid powdery to liquid, and
Low alkali, alkali-free just gradually replace traditional accelerator.There are alkali content height, later strength for domestic currently used liquid accelerator
The problems such as loss is big, maturing is impervious poor.The high environmental pollution of alkali content is serious, and big, coagulation is injured to construction personnel
The problems such as native unstable quality, develops a kind of environment-friendly type to improve injury of the accelerator to constructor and concrete quality
Alkali-free liquid accelerator is of great significance.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of preparation side of environment-friendly type alkali-free liquid accelerator is provided
Method.
Technical scheme is as follows:
A kind of preparation method of environment-friendly type alkali-free liquid accelerator, includes the following steps:
(1) by acrylamide aqueous solution, unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides aqueous solution, initiator solution and molecule
Amount regulator aqueous solution, which instills in water, to be reacted, and reaction temperature is 50-90 DEG C, and time for adding 0.2-6.0h is added dropwise
After be added promotor, keep the temperature 0-3.0h, obtain suspension stabilizer；The total amount of water used in the step makes the quality of the suspension stabilizer
Concentration is 5-40%, the mass ratio of acrylamide solution and unsaturated acids solution is 1: 0.2-1, and the dosage of initiator is propylene
The 0.5-3.0% of the gross mass of amide aqueous solution and unsaturated carboxylic acid or the solute in unsaturated carboxylic acid anhydrides aqueous solution, molecular weight
The dosage of regulator is the gross mass of acrylamide aqueous solution and unsaturated carboxylic acid or the solute in unsaturated carboxylic acid anhydrides aqueous solution
0.2-3.0%, the dosage of promotor is in acrylamide aqueous solution and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides aqueous solution
The 0.1-1.0% of the gross mass of solute；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides are maleic anhydride, acrylic acid, methyl-prop
At least one of olefin(e) acid, fumaric acid, itaconic acid；
(2) hydramine and acid are reacted, 50-90 DEG C of reaction temperature, adds catalyst, reaction time 1-4h is obtained
To modified hydramine；The mass ratio of hydramine and acid is 1: 0.3-1, and the dosage of catalyst is the 0.3- of the gross mass of hydramine and acid
4.0%；In the step, above-mentioned hydramine is at least one of monoethanolamine, diethanol amine, triethanolamine and triisopropanolamine,
Above-mentioned acid is dihydromethyl propionic acid and/or dimethylolpropionic acid；
(3) by weight, suspension stabilizer made from 0.2-3.0 parts of steps (1) and 1-10 parts of pH adjusting agents are added
Enter and be stirred into water, reaction temperature is 10-60 DEG C, adds 30-60 parts of aluminum sulfate, adds 1-20 parts after 0.2-2.0h
Modified hydramine, reacts 0.2-1h, obtains the environment-friendly type alkali-free liquid accelerator made from step (2)；Water used in the step it is total
Amount is so that the mass concentration of the environment-friendly type alkali-free liquid accelerator is 40-70%.
In a preferred embodiment of the invention, the initiator is ammonium persulfate and/or potassium peroxydisulfate.
In a preferred embodiment of the invention, the molecular weight regulator is thioacetic acid, mercaptopropionic acid, sulfydryl
At least one of ethyl alcohol, isopropanol and lauryl mercaptan.
In a preferred embodiment of the invention, the promotor is dihydroxytartaric acid, potassium hydrogen tartrate, winestone
At least one of sour hydrogen sodium.
In a preferred embodiment of the invention, the catalyst is p-methyl benzenesulfonic acid and/or the concentrated sulfuric acid.
The beneficial effects of the present invention are:
1, preparation method of the invention is copolymerized obtained suspension stabilizer by carrying out acrylamide and unsaturated acids, then will
Its synthesis for being used to prepare alkali-free liquid accelerator optimizes accelerator by introducing high-molecular copolymer, improves liquid
The coherency of body accelerator effectively inhibits the generation of precipitating, substantially increases the stability of mother liquor storage, stability can
Reach 1 year or more.
2, environment-friendly type alkali-free liquid accelerator prepared by the present invention is non-corrosive to construction worker's skin, to production environment without
Pollution, belongs to green product without environmental pollution.
3, modified hydramine is made by react with acid hydramine in preparation method method of the present invention, then is applied to
In the synthesis of alkali-free liquid accelerator, the early strength and later strength of concrete can be improved.
4, promotor is added after copolymerization in suspension stabilizer prepared by preparation method of the present invention, the introducing of the promotor
The conversion ratio of copolyreaction can not only be improved, moreover it is possible to the initial set of effective control alkali-free liquid accelerator and final setting time.
5, environment-friendly type alkali-free liquid accelerator prepared by the present invention can adapt to various cement, meet cement setting time
It is required that can be widely applied in the construction of gunite concrete.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment.
Embodiment 1
(1) preparation of suspension stabilizer: by acrylamide aqueous solution (its acrylamide 100.00g, water 80.00g), Malaysia
Acid anhydrides and acrylic acid aqueous solution (wherein maleic anhydride 22.00g, acrylic acid 13.00g and water 20.00g, ammonium persulfate aqueous solution
(wherein ammonium persulfate 1.20g, water 20.00g) and thioacetic acid aqueous solution (wherein thioacetic acid 0.90g, water 20.00g) instill
It is reacted in 160.00g water, is warming up to 70 DEG C of reactions, 0.50g dihydroxy base liquor is added in time for adding 5.0h after being added dropwise
Stone acid, keeps the temperature 3.0h, obtains suspension stabilizer；
(2) preparation of modified hydramine: 100.00g diethanol amine and 45.00g dihydromethyl propionic acid are uniformly mixed, heated up
To 65 DEG C, 2.00g p-methyl benzenesulfonic acid is added, reacts 2h, obtains modified hydramine；
(3) it stocks up by following mass ratio:
1.60g suspension stabilizer obtained above and 3.00g p-methyl benzenesulfonic acid are added in 60.00g water and are stirred,
Reaction temperature is 30 DEG C, then plus 40.00g enter aluminum sulfate, 10.00g appeal hydramine obtained modified, reaction are added after 1.0h
0.5h obtains a kind of environment-friendly type alkali-free liquid accelerator KZJ-1.
Embodiment 2
(1) preparation of suspension stabilizer: by acrylamide aqueous solution (its acrylamide 100.00g, water 80.00g), methyl
Acrylic acid and maleic anhydride aqueous solution (wherein methacrylic acid 32.00g, maleic anhydride 20.00g and water 20.00g, potassium peroxydisulfate
Aqueous solution (wherein potassium peroxydisulfate 1.80g, water 20.00g) and thioacetic acid aqueous solution (wherein thioacetic acid 0.80g, water
It 20.00g) instills in 130.00g water and is reacted, be warming up to 60 DEG C of reactions, time for adding 4.0h is added after being added dropwise
0.60g potassium hydrogen tartrate keeps the temperature 2.0h, obtains suspension stabilizer；
(2) preparation of modified hydramine: 100.00g triethanolamine and 40.00g dimethylolpropionic acid are uniformly mixed, heated up
To 70 DEG C, the 2.50g concentrated sulfuric acid is added, reacts 3h, obtains modified hydramine；
(3) it stocks up by following mass ratio:
0.80g suspension stabilizer obtained above and 4.00g citric acid are added in 60.00g water and are stirred, is reacted
Temperature is 40 DEG C, then plus 30.00g enter aluminum sulfate, 6.00g appeal hydramine obtained modified is added after 1.0h, 0.5h is reacted, obtains
To a kind of environment-friendly type alkali-free liquid accelerator KZJ-2.
Embodiment 3
(1) preparation of suspension stabilizer: by acrylamide aqueous solution (its acrylamide 100.00g, water 80.00g), rich horse
(wherein fumaric acid 18.00g, methacrylic acid 40.00g and water 20.00g, ammonium persulfate are water-soluble with metering system aqueous acid for acid
Liquid (wherein ammonium persulfate 1.80g, water 20.00g) and thioacetic acid aqueous solution (wherein thioacetic acid 1.00g, water 20.00g) drop
Enter and reacted in 130.00g water, be warming up to 65 DEG C of reactions, 1.00g tartaric acid is added in time for adding 3.0h after being added dropwise
Hydrogen sodium keeps the temperature 1.0h, obtains suspension stabilizer；
(2) preparation of modified hydramine: 100.00g monoethanolamine and 50.00g dihydromethyl propionic acid are uniformly mixed, heated up
To 70 DEG C, 4.00g p-methyl benzenesulfonic acid is added, reacts 1h, obtains modified hydramine；
(3) it stocks up by following mass ratio:
1.20g suspension stabilizer obtained above and 5.00g tartaric acid are added in 60.00g water and are stirred, is reacted
Temperature is 45 DEG C, then plus 36.00g enter aluminum sulfate, 12.00g appeal hydramine obtained modified is added after 1.5h, reacts 0.5h,
Obtain a kind of environment-friendly type alkali-free liquid accelerator KZJ-3.
Embodiment 4
(1) preparation of suspension stabilizer: by acrylamide aqueous solution (its acrylamide 100.00g, water 80.00g), clothing health
(wherein itaconic acid 11.00g, acrylic acid 36.00g and water 20.00g, ammonium persulfate aqueous solution is (wherein with acrylic acid aqueous solution for acid
Ammonium persulfate 2.00g, water 20.00g) and mercaptoethanol aqueous solution (wherein mercaptoethanol 1.00g, water 20.00g) instillation
It is reacted in 260.00g water, is warming up to 80 DEG C of reactions, 1.10g dihydroxy base liquor is added in time for adding 2.0h after being added dropwise
Stone acid, keeps the temperature 0.5h, obtains suspension stabilizer；
(2) preparation of modified hydramine: 100.00g triisopropanolamine and 60.00g dimethylolpropionic acid are uniformly mixed, risen
Temperature adds the 3.00g concentrated sulfuric acid to 60 DEG C, reacts 4h, obtains modified hydramine；
(3) it stocks up by following mass ratio:
1.00g suspension stabilizer obtained above and 5.00g salicylic acid are added in 60.00g water and are stirred, is reacted
Temperature is 30 DEG C, then plus 33.00g enter aluminum sulfate, 10.00g appeal hydramine obtained modified is added after 1.0h, reacts 0.5h,
Obtain a kind of environment-friendly type alkali-free liquid accelerator KZJ-4.
Embodiment 5
(1) prepared by suspension stabilizer: by acrylamide aqueous solution (its acrylamide 100.00g, water 80.00g), methyl-prop
Olefin(e) acid and acrylic acid aqueous solution (wherein methacrylic acid 22.00g, acrylic acid 36.00g and water 20.00g, ammonium persulfate aqueous solution
(wherein ammonium persulfate 1.60g, water 20.00g) and isopropanol water solution (wherein isopropanol 0.70g, water 20.00g) instill
It is reacted in 460.00g water, is warming up to 90 DEG C of reactions, 0.40g dihydroxy base liquor is added in time for adding 1.0h after being added dropwise
Stone acid, keeps the temperature 1.5h, obtains suspension stabilizer；
(2) preparation of modified hydramine: 100.00g triethanolamine and 70.00g dihydromethyl propionic acid are uniformly mixed, heated up
To 75 DEG C, 5.00g p-methyl benzenesulfonic acid is added, reacts 3h, obtains modified hydramine；
(3) it stocks up by following mass ratio:
2.20g suspension stabilizer obtained above and 7.00g ethanedioic acid are added in 60.00g water and are stirred, is reacted
Temperature is 25 DEG C, then plus 43.00g enter aluminum sulfate, 15.00g appeal hydramine obtained modified is added after 1.0h, reacts 0.4h,
Obtain a kind of environment-friendly type alkali-free liquid accelerator KZJ-5.
Environment-friendly type alkali-free liquid accelerator obtained by embodiment 1 to embodiment 5 is tested, three representativenesses are selected
Cement is tested, cement be respectively 42.5 ordinary portland cement of Fujian good fortune P.O, 42.5 ordinary portland cement of conch P.O,
42.5 ordinary portland cement of Taurus P.O.According to JC477-2005 " gunite concrete accelerator " to gained environment-friendly type alkali-free
Liquid accelerator carries out cement paste condensed water time and strength of cement mortar test.Wherein accelerator dosage is according to cement weight
Percentage calculate.
The test of cement paste setting time
Cement 400
Water 160
Strength of cement mortar test
Cement 900
Normal sand 1350
Water 450
Accelerator is added in cement slurry according to the 5% of cement weight, while above-mentioned water consumption contains liquid accelerator
Contained in water.As a comparison with presently commercially available alkali-free liquid accelerator (sample 1), cement paste setting time, sand have been carried out
Slurry intensity and stability are tested.Test result such as table 1 and 2.
1 cement paste setting time test result of table
The test of 2 strength of cement mortar of table and stability
The presetting period of environment-friendly type alkali-free liquid accelerator of the invention and final setting time be all as can be seen from Table 1 and Table 2
More shorter than commercially available alkali-free liquid accelerator, 1d compression strength and 28d compressive strength rate are higher, and stability is more preferable.
Those of ordinary skill in the art still are able to it is found that when technical solution of the present invention changes in following ranges
To same as the previously described embodiments or similar technical effect, protection scope of the present invention is still fallen within:
A kind of preparation method of environment-friendly type alkali-free liquid accelerator, includes the following steps:
(1) by acrylamide aqueous solution, unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides aqueous solution, initiator solution and molecule
Amount regulator aqueous solution, which instills in water, to be reacted, and reaction temperature is 50-90 DEG C, and time for adding 0.2-6.0h is added dropwise
After be added promotor, keep the temperature 0-3.0h, obtain suspension stabilizer；The total amount of water used in the step makes the quality of the suspension stabilizer
Concentration is 5-40%, the mass ratio of acrylamide solution and unsaturated acids solution is 1: 0.2-1, and the dosage of initiator is propylene
The 0.5-3.0% of the gross mass of amide aqueous solution and unsaturated carboxylic acid or the solute in unsaturated carboxylic acid anhydrides aqueous solution, molecular weight
The dosage of regulator is the gross mass of acrylamide aqueous solution and unsaturated carboxylic acid or the solute in unsaturated carboxylic acid anhydrides aqueous solution
0.2-3.0%, the dosage of promotor is in acrylamide aqueous solution and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides aqueous solution
The 0.1-1.0% of the gross mass of solute；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides are maleic anhydride, acrylic acid, methyl-prop
At least one of olefin(e) acid, fumaric acid, itaconic acid；
(2) hydramine and acid are reacted, 50-90 DEG C of reaction temperature, adds catalyst, reaction time 1-4h is obtained
To modified hydramine；The mass ratio of hydramine and acid is 1: 0.3-1, and the dosage of catalyst is the 0.3- of the gross mass of hydramine and acid
4.0%；In the step, above-mentioned hydramine is at least one of monoethanolamine, diethanol amine, triethanolamine and triisopropanolamine,
Above-mentioned acid is dihydromethyl propionic acid and/or dimethylolpropionic acid；
(3) by weight, suspension stabilizer made from 0.2-3.0 parts of steps (1) and 1-10 parts of pH adjusting agents are added
Enter and be stirred into water, reaction temperature is 10-60 DEG C, adds 30-60 parts of aluminum sulfate, adds 1-20 parts after 0.2-2.0h
Modified hydramine, reacts 0.2-1h, obtains the environment-friendly type alkali-free liquid accelerator made from step (2)；Water used in the step it is total
Amount is so that the mass concentration of the environment-friendly type alkali-free liquid accelerator is 40-70%.
The initiator is ammonium persulfate and/or potassium peroxydisulfate.The molecular weight regulator is thioacetic acid, sulfydryl third
At least one of acid, mercaptoethanol, isopropanol and lauryl mercaptan.The promotor be dihydroxytartaric acid, potassium hydrogen tartrate,
At least one of sodium hydrogen tartrate.The catalyst is p-methyl benzenesulfonic acid and/or the concentrated sulfuric acid.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (4)
1. a kind of preparation method of environment-friendly type alkali-free liquid accelerator, characterized by the following steps:
(1) by acrylamide aqueous solution, unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides aqueous solution, initiator solution and molecular weight tune
Section agent aqueous solution, which instills in water, to be reacted, and reaction temperature is 50-90 DEG C, time for adding 0.2-6.0h, is added after being added dropwise
Enter promotor, keeps the temperature 1.0-3.0h, obtain suspension stabilizer；The total amount of water used in the step makes the quality of the suspension stabilizer dense
Spending is 5-40%, and the mass ratio of acrylamide solution and unsaturated carboxylic acid solution is 1:0.2-1, and the dosage of initiator is acryloyl
The 0.5-3.0% of the gross mass of amine aqueous solution and unsaturated carboxylic acid or the solute in unsaturated carboxylic acid anhydrides aqueous solution, molecular-weight adjusting
The dosage of agent is the gross mass of acrylamide aqueous solution and unsaturated carboxylic acid or the solute in unsaturated carboxylic acid anhydrides aqueous solution
0.2-3.0%, the dosage of promotor are the solute in acrylamide aqueous solution and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides aqueous solution
Gross mass 0.1-1.0%；Above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides be maleic anhydride, acrylic acid, methacrylic acid,
At least one of fumaric acid, itaconic acid；Above-mentioned promotor is dihydroxytartaric acid, in potassium hydrogen tartrate, sodium hydrogen tartrate
It is at least one；
(2) hydramine and acid are reacted, 50-90 DEG C of reaction temperature, adds catalyst, reaction time 1-4h is changed
Property hydramine；The mass ratio of hydramine and acid is 1:0.3-1, and the dosage of catalyst is the 0.3-4.0% of the gross mass of hydramine and acid；It should
In step, above-mentioned hydramine is at least one of monoethanolamine, diethanol amine, triethanolamine and triisopropanolamine, and above-mentioned acid is
Dihydromethyl propionic acid and/or dimethylolpropionic acid；
(3) by weight, suspension stabilizer made from 0.2-3.0 parts of steps (1) and 1-10 parts of pH adjusting agents are added to
It is stirred in water, reaction temperature is 10-60 DEG C, adds 30-60 parts of aluminum sulfate, 1-20 parts of steps are added after 0.2-2.0h
(2) modified hydramine, reacts 0.2-1h, obtains the environment-friendly type alkali-free liquid accelerator made from；The total amount of water used in the step makes
The mass concentration for obtaining the environment-friendly type alkali-free liquid accelerator is 40-70%.
2. preparation method as described in claim 1, it is characterised in that: the initiator is ammonium persulfate and/or potassium peroxydisulfate.
3. preparation method as described in claim 1, it is characterised in that: the molecular weight regulator is thioacetic acid, sulfydryl third
At least one of acid, mercaptoethanol, isopropanol and lauryl mercaptan.
4. preparation method as described in claim 1, it is characterised in that: the catalyst is p-methyl benzenesulfonic acid and/or the concentrated sulfuric acid.
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| CN108793811B (en) * | 2018-08-16 | 2020-06-09 | 科之杰新材料集团有限公司 | Preparation method of durability-enhanced alkali-free liquid accelerator |
| CN109020292B (en) * | 2018-08-16 | 2020-04-10 | 科之杰新材料集团有限公司 | Preparation method of environment-friendly enhanced alkali-free liquid accelerator |
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| CN109399999B (en) * | 2018-10-25 | 2021-08-06 | 江苏奥莱特新材料股份有限公司 | Green high-early-strength low-alkali liquid accelerator and preparation method thereof |
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| CN112608065B (en) * | 2019-12-13 | 2022-07-15 | 科之杰新材料集团(贵州)有限公司 | Liquid alkali-free accelerator for sprayed concrete and preparation method thereof |
| CN111646728B (en) * | 2020-07-01 | 2021-11-09 | 中建材中岩科技有限公司 | Quick-setting high-strength alkali-free liquid accelerator |
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| CN102219425B (en) * | 2011-04-15 | 2013-06-26 | 中铁隧道集团有限公司 | Alkali-free liquid accelerating agent and preparation method thereof |
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| CN107200496B (en) * | 2017-07-17 | 2019-11-01 | 云南交投公路建设第五工程有限公司 | A kind of environment-friendly type alkali-free accelerator and preparation method thereof |
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