CN107200817B - A kind of preparation method of stable type concrete slump controlling agent - Google Patents
A kind of preparation method of stable type concrete slump controlling agent Download PDFInfo
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- CN107200817B CN107200817B CN201710551006.1A CN201710551006A CN107200817B CN 107200817 B CN107200817 B CN 107200817B CN 201710551006 A CN201710551006 A CN 201710551006A CN 107200817 B CN107200817 B CN 107200817B
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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Abstract
The invention discloses a kind of preparation methods of stable type concrete slump controlling agent, ester group is introduced in the molecular structure by the esterification products of unsaturated carboxylic acid and compound A, phenyl ring and sulfonic acid based structures, due to introducing sulfonic acid group with water-reducing effect and with the phenyl ring of space steric effect when initial, so that the product of product initial water-reducing rate with higher, the ester group structure of introducing can be hydrolyzed gradually under the conditions of concrete alkalinity, and since the variation of the quantity of the group with dispersion effect before and after hydrolysis of ester group in products molecule structure is little, be not in hydrolysis of ester group it is too fast and generate concrete slump lag scale-up problem, the too fast problem of concrete slump loss generated since hydrolysis of ester group is excessively slow will not occur, therefore the not influence vulnerable to use condition variation in use, realization collapses to concrete The stability contorting for degree of falling.
Description
Technical field
The invention belongs to building material technical fields, and in particular to a kind of preparation of stable type concrete slump controlling agent
Method.
Background technique
As concrete technology is grown rapidly to high-strength, green, high-performance direction, as important component in concrete
Water-reducing agent be also suggested it is higher, more fully require.Previous traditional cement water reducing agent, as the first generation lignin and
The water-reducing agents such as the naphthalene sulfonate system of the second generation, sulfonated melamine system, amido sulfoacid series, fatty family, since volume is larger, subtracts
Water rate is not high enough, reinforcing effect is not very significant, concrete slump loss is larger, is not able to satisfy modern concrete skill gradually
The development of art and modern concrete construction.Especially in process of production will using crude naphthalene, the concentrated sulfuric acid, formaldehyde, liquid alkaline,
The harmful chemicals such as phenol can inevitably cause environment centainly to pollute, there are problems that the disadvantages of being unfavorable for sustainable development,
To partly constrain its further popularization and application.
Polycarboxylate water-reducer is since the advantages that it has excellent performance, energy conservation and environmental protection, concrete durability are good, was since 2006
It is applied in key state projects such as high-speed rail, water power, nuclear powers.But as resource scarcity and concrete performance demand are promoted, gather
Carboxylic acid water reducer also often occurs protecting collapsing effect not enough and protecting effect of collapsing in popularization and application process asks vulnerable to what the factors such as temperature influenced
Topic, therefore, the stable type concrete slump controlling agent that developing has function of slump protection excellent and insensitive to use condition just have
It is of great significance.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of system of stable type concrete slump controlling agent is provided
Preparation Method.
Technical scheme is as follows:
A kind of preparation method of stable type concrete slump controlling agent, includes the following steps:
(1) unsaturated carboxylic acid, compound A and polymerization inhibitor are mixed, under nitrogen protection, is warming up to 40~60 DEG C, then plus
Enter catalyst, be warming up to 100~140 DEG C, 0.5~3h of insulation reaction, is during which removed with vacuumizing or lead to method of the nitrogen with water
Water is down to room temperature after reaction, obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid, unsaturated
The molar ratio of carboxylic acid and compound A are 1.5~6: 1, and the dosage of catalyst is unsaturated carboxylic acid and compound A gross mass
0.5%~5.0%, polymerization inhibitor dosage is the 0.5%~5.0% of unsaturated carboxylic acid and compound A gross mass, the knot of compound A
Structure formula is as follows:
Wherein R1There is no the alkyl or do not have that R2 is 1~4 carbon perhaps for the alkyl of 1~4 carbon；
(2) by the first mixture made from step (1), the 4- hydroxyl butyl vinyl polyoxyethylene of molecular weight 600~5000
Base ether is mixed with 1: 4~30 mass ratio, and water is added and makes its dissolution, obtains copolymerized monomer mixture solution；
(3) above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution are instilled in water
It is reacted, reaction temperature is 10~40 DEG C, and time for adding is 0.2~6.0h, and 0~3.0h is kept the temperature after being added dropwise, must be copolymerized
Product；The total amount of water used in the step and step (2) makes the mass concentration of the copolymerization product be 20~80%, the use of initiator
Amount is 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, and the dosage of molecular weight regulator is comonomer
The 0.2~3.0% of the gross mass of solute in mixture solution；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the stable type concrete slump
Controlling agent.
In a preferred embodiment of the invention, the step (1) are as follows: by unsaturated carboxylic acid, compound A, polymerization inhibitor
Agent mixing, under nitrogen protection, is warming up to 50~60 DEG C, adds catalyst, be warming up to 105~130 DEG C, and insulation reaction 1~
During which 3h removes water with vacuumizing or lead to method of the nitrogen with water, is down to room temperature after reaction, obtain containing esterification products with
The molar ratio of first mixture of unreacted unsaturated carboxylic acid, unsaturated carboxylic acid and compound A are 1.5~5: 1, catalyst
Dosage is the 0.5%~4.0% of unsaturated carboxylic acid and compound A gross mass, and polymerization inhibitor dosage is unsaturated carboxylic acid and compound A
The 0.5%~4.0% of gross mass.
In a preferred embodiment of the invention, the step (2) are as follows: by the first mixture made from step (1),
The 4- hydroxyl butyl vinyl polyoxyethylene ether of molecular weight 600~5000 is mixed with 1: 5~20 mass ratio, and water is added and makes
It is dissolved, and obtains copolymerized monomer mixture solution.
In a preferred embodiment of the invention, the step (3) are as follows: by above-mentioned copolymerized monomer mixture solution with
Initiator solution and molecular weight regulator aqueous solution, which instill in water, to be reacted, and reaction temperature is 10~30 DEG C, time for adding
For 0.2~5.0h, 0~3.0h is kept the temperature after being added dropwise, obtains copolymerization product；The total amount of water used in the step and step (2) makes
The mass concentration of the copolymerization product is 20~70%, and the dosage of initiator is the gross mass of solute in copolymerized monomer mixture solution
0.5~2.0%, the dosage of the molecular weight regulator be the gross mass of solute in copolymerized monomer mixture solution 0.2~
2.0%.
It is further preferred that the unsaturated carboxylic acid is at least one of acrylic acid and methacrylic acid.
It is further preferred that the catalyst be ethylsulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and 98% the concentrated sulfuric acid in
It is at least one.
It is further preferred that the polymerization inhibitor is at least one of hydroquinone, phenthazine and diphenylamines.
It is further preferred that the initiator is that water soluble, redox causes system or water-soluble azo initiator.
It is further preferred that the molecular weight regulator is thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, secondary phosphorus
At least one of sour sodium, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan.
Beneficial effects of the present invention:
1, the present invention introduces ester group, phenyl ring by the esterification products of unsaturated carboxylic acid and compound A in the molecular structure
With sulfonic acid based structures, due to introducing sulfonic acid group with water-reducing effect and with the phenyl ring of space steric effect when initial,
So that the product of product initial water-reducing rate with higher.
2, when stable type concrete slump controlling agent prepared by preparation method of the present invention being used for concrete, in concrete
Alkaline environment under, the ester bond in molecular structure can be hydrolyzed gradually, release the carboxyl with water-reducing effect, realize excellent collapse
Degree of falling keeps effect, and not due to the radical amount variation with dispersion effect before and after hydrolysis of ester group in products molecule structure
Greatly, be not in hydrolysis of ester group it is too fast and generate concrete slump lag amplification the problem of, will not occur due to ester group
Hydrolyzed slow and generation the too fast problem of concrete slump loss, therefore in use not vulnerable to use condition variation
It influences, realizes the stability contorting to concrete slump.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment.
Embodiment 1
(1) 240.00g acrylic acid, 200.00g p-hydroxybenzenyl sulfonate, 6.50g phenthazine are mixed, under nitrogen protection,
It is warming up to 60 DEG C, 8.23g p-methyl benzenesulfonic acid is added, is warming up to 110 DEG C, insulation reaction 2h, during which with vacuumizing or lead to nitrogen band
The method of water removes water, is down to room temperature after reaction, obtains the first mixing containing esterification products and unreacted acrylic acid
Object；
(2) by the first mixture made from 20.00g step (1), the 4- hydroxyl butylethylene that 185.00g molecular weight is 2400
The mixing of base polyoxyethylene ether, and 120.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) by above-mentioned copolymerized monomer mixture solution and aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 1.20g, water 20.00g),
Aqueous ascorbic acid (wherein, ascorbic acid 0.40g, water 20.00g), ferrous sulfate solution (wherein, ferrous sulfate 0.40g,
Water 10.00g), thioacetic acid aqueous solution (wherein, thioacetic acid 1.20g, water 20.00g) instill 60.00g water in reacted,
Reaction temperature is 30 DEG C, and time for adding 2.0h keeps the temperature 0.5h after being added dropwise, obtains copolymerization product；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the stable type concrete slump
Controlling agent KZJ-1.
Embodiment 2
(1) by 247.00g methacrylic acid, 200.00g to methylol benzene sulfonic acid, 5.60g hydroquinone, 2.00g pheno thiophene
Piperazine mixing is warming up to 50 DEG C under nitrogen protection, and the concentrated sulfuric acid that 8.20g mass fraction is 98% is added, is warming up to 115 DEG C, protects
Temperature reaction 3h is down to room temperature after reaction, obtains containing esterification during which with vacuumizing or leading to method removing water of the nitrogen with water
First mixture of product and unreacted methacrylic acid；
(2) by the first mixture made from 20.00g step (1), the 4- hydroxyl butylethylene that 260.00g molecular weight is 2400
The mixing of base polyoxyethylene ether, and 150.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) by above-mentioned copolymerized monomer mixture solution and aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 1.10g, water 20.00g),
Sodium formaldehyde sulfoxylate aqueous solution (wherein, sodium formaldehyde sulfoxylate 0.70g, water 20.00g), ferrous sulfate solution (wherein, ferrous sulfate 0.50g, water
10.00g), mercaptopropionic acid aqueous solution (wherein, mercaptopropionic acid 1.50g, water 20.00g) is instilled in 60.00g water and is reacted, instead
Answering temperature is 20 DEG C, and time for adding 1.0h keeps the temperature 1h after being added dropwise, obtains copolymerization product；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the stable type concrete slump
Controlling agent KZJ-2.
Embodiment 3
(1) 156g acrylic acid, 86g methacrylic acid, 200.00g mix hydroxyethylbenzene sulfonic acid, 4.20g hydroquinone
It closes, under nitrogen protection, is warming up to 60 DEG C, 6.30g ethylsulfonic acid is added, is warming up to 110 DEG C, insulation reaction 2h, during which with pumping
The method of vacuum or logical nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted third
First mixture of olefin(e) acid and methacrylic acid；
(2) by the first mixture made from 20.00g step (1), the 4- hydroxyl butylethylene that 233.00g molecular weight is 2400
The mixing of base polyoxyethylene ether, and 150.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) by above-mentioned copolymerized monomer mixture solution and aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 1.30g, water 20.00g),
Aqueous ascorbic acid (wherein, ascorbic acid 0.30g, water 20.00g), ferrous sulfate solution (wherein, ferrous sulfate 0.50g,
Water 10.00g), trisodium phosphate aqueous solution (wherein, tertiary sodium phosphate 2.00g, water 20.00g) instill 60.00g water in reacted,
Reaction temperature is 10 DEG C, and time for adding 1.5h keeps the temperature 1h after being added dropwise, obtains copolymerization product；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the stable type concrete slump
Controlling agent KZJ-3.
Embodiment 4
(1) 177.00g acrylic acid, 200.00g4- hydroxy phenyl methanesulfonic acid, 6.60g diphenylamines are mixed, in nitrogen protection
Under, 60 DEG C are warming up to, the concentrated sulfuric acid that 5.50g mass fraction is 98% is added, is warming up to 105 DEG C, insulation reaction 3h, during which with pumping
The method of vacuum or logical nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted third
First mixture of olefin(e) acid；
(2) the 4- hydroxyl butyl vinyl for being 3000 by the first mixture 244.00g molecular weight made from 20.00g step (1)
Polyoxyethylene ether mixing, and 150.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) by above-mentioned copolymerized monomer mixture solution and aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 2.00g, water 20.00g),
Sodium formaldehyde sulfoxylate aqueous solution (wherein, sodium formaldehyde sulfoxylate 1.20g, water 20.00g), ferrous sulfate solution (wherein, ferrous sulfate 0.70g, water
10.00g), isopropanol water solution (wherein, isopropanol 1.50g, water 20.00g) is instilled in 60.00g water and is reacted, reaction temperature
Degree is 25 DEG C, and time for adding 0.5h keeps the temperature 1.5h after being added dropwise, obtains copolymerization product；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the stable type concrete slump
Controlling agent KZJ-4.
Embodiment 5
(1) by 140.00g acrylic acid, 87.00g p-hydroxybenzenyl sulfonate, 113g to methylol benzene sulfonic acid, 3.40g to benzene two
Phenol mixing is warming up to 50 DEG C under nitrogen protection, and 4.60g benzene sulfonic acid is added, is warming up to 120 DEG C, insulation reaction 2h, during which uses
It vacuumizes or leads to method of the nitrogen with water and remove water, be down to room temperature after reaction, obtain containing esterification products and unreacted
First mixture of acrylic acid；
(2) by the first mixture made from 20.00g step (1), the 4- hydroxyl butylethylene that 220.00g molecular weight is 3000
The mixing of base polyoxyethylene ether, and 150.00g water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) by above-mentioned copolymerized monomer mixture solution, (wherein azo two is different with azo diisobutyl amidine hydrochloric acid saline solution
Butyl Amidine HCl salt 1.80g, water 30.00g), lauryl mercaptan aqueous solution (wherein, lauryl mercaptan 2.30g, water 30.00g) instill
It is reacted in 70.00g water, reaction temperature is 30 DEG C, and time for adding 3.0h keeps the temperature 1.0h after being added dropwise, and must be copolymerized production
Object；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the stable type concrete slump
Controlling agent KZJ-5.
To embodiment 1 to stable type concrete slump controlling agent obtained by embodiment 5 (KZJ-1, KZJ-2, KZJ-3,
KZJ-4 and KZJ-5) and commercially available collapse protective poly-carboxylic acid water reducing agent (PCE) carry out different materials, different temperatures concrete performance
Compare.Using Fujian good fortune cement (P.O42.5R), concrete mix are as follows: cement 280kg/m3, flyash 80kg/m3, sand 770kg/
m3, stone 1040kg/m3, water 160kg/m3, surveyed respectively under the conditions of sand clay content is 1%, 5% and 5 DEG C, 35 DEG C of temperature respectively
The concrete performance of KZJ-1, KZJ-2, KZJ-3, KZJ-4, KZJ-5 and PCE are mixed in examination, in order to observe the slump of different additives
Damage control ability, by adjusting volume, so that concrete initial extension degree tests each additive within the scope of 550 ± 10mm
The slump (TL) and divergence (TK) of 1h, 2h and 3h, acquired results are as shown in table 1 and table 2:
The concrete performance of each additive under the conditions of the different sand clay contents of table 1
The concrete performance of each additive under 2 condition of different temperatures of table
It can be seen from the results above that the initial water-reducing rate of commercially available collapse protective poly-carboxylic acid water reducing agent (PCE) is in different realities
The embodiment of this patent synthesis is below under the conditions of testing, and in sand clay content and temperature change, the commercially available poly- carboxylic of collapse protection type
Sour water-reducing agent (PCE) slump-loss variation compared with this patent synthesis embodiment greatly, i.e., its experiment condition change when pair
The slump control ability of concrete is weak compared with the embodiment that this patent synthesizes.
Those of ordinary skill in the art it is found that when technical parameter and raw material components of the invention changes in following ranges,
It remains to access same as the previously described embodiments or similar technical effect, still belong to and protection scope of the present invention:
A kind of preparation method of stable type concrete slump controlling agent, includes the following steps:
(1) unsaturated carboxylic acid, compound A and polymerization inhibitor are mixed, under nitrogen protection, is warming up to 40~60 DEG C, then plus
Enter catalyst, be warming up to 100~140 DEG C, 0.5~3h of insulation reaction, is during which removed with vacuumizing or lead to method of the nitrogen with water
Water is down to room temperature after reaction, obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid, unsaturated
The molar ratio of carboxylic acid and compound A are 1.5~6: 1, and the dosage of catalyst is unsaturated carboxylic acid and compound A gross mass
0.5%~5.0%, polymerization inhibitor dosage is the 0.5%~5.0% of unsaturated carboxylic acid and compound A gross mass, the knot of compound A
Structure formula is as follows:
Wherein R1For 1~4 carbon alkyl or do not have, R2For 1~4 carbon alkyl or do not have；
(2) by the first mixture made from step (1), the 4- hydroxyl butyl vinyl polyoxyethylene of molecular weight 600~5000
Base ether is mixed with 1: 4~30 mass ratio, and water is added and makes its dissolution, obtains copolymerized monomer mixture solution；
(3) above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution are instilled in water
It is reacted, reaction temperature is 10~40 DEG C, and time for adding is 0.2~6.0h, and 0~3.0h is kept the temperature after being added dropwise, must be copolymerized
Product；The total amount of water used in the step and step (2) makes the mass concentration of the copolymerization product be 20~80%, the use of initiator
Amount is 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, and the dosage of molecular weight regulator is comonomer
The 0.2~3.0% of the gross mass of solute in mixture solution；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the stable type concrete slump
Controlling agent.
The unsaturated carboxylic acid is at least one of acrylic acid and methacrylic acid.The catalyst be ethylsulfonic acid,
At least one of benzene sulfonic acid, p-methyl benzenesulfonic acid and 98% concentrated sulfuric acid.The polymerization inhibitor is hydroquinone, phenthazine and hexichol
At least one of amine.The initiator is that water soluble, redox causes system or water-soluble azo initiator.The molecule
Amount regulator be thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and
At least one of lauryl mercaptan.
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 (8)
1. a kind of preparation method of stable type concrete slump controlling agent, characterized by the following steps:
(1) unsaturated carboxylic acid, compound A and polymerization inhibitor are mixed, under nitrogen protection, is warming up to 40~60 DEG C, adds and urge
Agent is warming up to 100~140 DEG C, 0.5~3h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, instead
It is down to room temperature after answering, obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid, unsaturated carboxylic acid
Be 1.5~6: 1 with the molar ratio of compound A, the dosage of catalyst be unsaturated carboxylic acid and compound A gross mass 0.5%~
5.0%, polymerization inhibitor dosage is the 0.5%~5.0% of unsaturated carboxylic acid and compound A gross mass, and the structural formula of compound A is such as
Under:
Wherein R1There is no the alkyl or do not have that R2 is 1~4 carbon perhaps for the alkyl of 1~4 carbon；Above-mentioned unsaturated carboxylic acid is
At least one of acrylic acid and methacrylic acid；
(2) by the first mixture made from step (1), the 4- hydroxyl butyl vinyl polyoxyethylene ether of molecular weight 600~5000
It is mixed with 1: 4~30 mass ratio, and water is added and makes its dissolution, obtain copolymerized monomer mixture solution；
(3) above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution are instilled in water and is carried out
Reaction, reaction temperature are 10~40 DEG C, and time for adding is 0.2~6.0h, and 0~3.0h is kept the temperature after being added dropwise, obtains copolymerization product；
The total amount of water used in the step and step (2) makes the mass concentration of the copolymerization product be 20~80%, and the dosage of initiator is
The 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, the dosage of molecular weight regulator are comonomer mixing
The 0.2~3.0% of the gross mass of solute in object solution；
(4) alkali of copolymerization product made from step (3) pH to 5~7 is adjusted to control to get the stable type concrete slump
Agent.
2. preparation method as described in claim 1, it is characterised in that: the step (1) are as follows: by unsaturated carboxylic acid, compound
A, polymerization inhibitor mixes, and under nitrogen protection, is warming up to 50~60 DEG C, adds catalyst, is warming up to 105~130 DEG C, heat preservation is anti-
1~3h is answered, during which with vacuumizing or leading to method removing water of the nitrogen with water, room temperature is down to after reaction, obtains containing esterification
The molar ratio of first mixture of product and unreacted unsaturated carboxylic acid, unsaturated carboxylic acid and compound A are 1.5~5: 1, are urged
The dosage of agent is the 0.5%~4.0% of unsaturated carboxylic acid and compound A gross mass, polymerization inhibitor dosage be unsaturated carboxylic acid with
The 0.5%~4.0% of compound A gross mass.
3. preparation method as described in claim 1, it is characterised in that: the step (2) are as follows: will be first made from step (1)
Mixture, molecular weight 600~5000 4- hydroxyl butyl vinyl polyoxyethylene ether with 1: 5~20 mass ratio mix, and add
Enter water and make its dissolution, obtains copolymerized monomer mixture solution.
4. preparation method as described in claim 1, it is characterised in that: the step (3) are as follows: by above-mentioned copolymerized monomer mixture
Solution instills in water with initiator solution and molecular weight regulator aqueous solution to be reacted, and reaction temperature is 10~30 DEG C, drop
It is 0.2~5.0h between added-time, 0~3.0h is kept the temperature after being added dropwise, obtains copolymerization product；Water used in the step and step (2) it is total
For amount so that the mass concentration of the copolymerization product is 20~70%, the dosage of initiator is solute in copolymerized monomer mixture solution
The 0.5~2.0% of gross mass, the dosage of the molecular weight regulator are the gross mass of solute in copolymerized monomer mixture solution
0.2~2.0%.
5. the preparation method as described in any claim in Claims 1-4, it is characterised in that: the catalyst is ethyl
At least one of sulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and 98% concentrated sulfuric acid.
6. the preparation method as described in any claim in Claims 1-4, it is characterised in that: the polymerization inhibitor is to benzene
At least one of diphenol, phenthazine and diphenylamines.
7. the preparation method as described in any claim in Claims 1-4, it is characterised in that: the initiator is water-soluble
Property redox initiation system or water-soluble azo initiator.
8. the preparation method as described in any claim in Claims 1-4, it is characterised in that: the molecular weight regulator
For thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan
At least one of.
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| CN107955106B (en) * | 2017-12-07 | 2020-12-29 | 科之杰新材料集团有限公司 | Preparation method of concrete fluidity stabilizer |
| CN108047389B (en) * | 2017-12-07 | 2020-07-03 | 科之杰新材料集团有限公司 | Preparation method of low-sensitivity concrete fluidity stabilizer |
| CN107987227A (en) * | 2017-12-07 | 2018-05-04 | 科之杰新材料集团有限公司 | A kind of preparation method of low hydration heat extra retarded set type polycarboxylate water-reducer |
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| CN107987235B (en) * | 2017-12-07 | 2020-03-06 | 科之杰新材料集团有限公司 | Preparation method of low-hydration-heat anti-cracking polycarboxylate superplasticizer |
| CN107903361B (en) * | 2017-12-07 | 2020-12-29 | 科之杰新材料集团有限公司 | Preparation method of high-adaptability concrete fluidity stabilizer |
| CN109111147B (en) * | 2018-08-16 | 2020-08-11 | 科之杰新材料集团有限公司 | Multifunctional ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN109824307A (en) * | 2019-04-04 | 2019-05-31 | 湖北合力久盛混凝土有限公司 | A kind of novel expansive concrete |
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