CN107200817A - 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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- CN107200817A CN107200817A CN201710551006.1A CN201710551006A CN107200817A CN 107200817 A CN107200817 A CN 107200817A CN 201710551006 A CN201710551006 A CN 201710551006A CN 107200817 A CN107200817 A CN 107200817A
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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
Abstract
The invention discloses a kind of preparation method of stable type concrete slump controlling agent, ester group is introduced in the molecular structure by unsaturated carboxylic acid and compound A esterification products, phenyl ring and sulfonic acid based structures, due to introducing the sulfonic acid group with water-reducing effect and the phenyl ring with space steric effect when initial, so that the product of product has higher initial water-reducing rate, the ester group structure of introducing can be hydrolyzed gradually under the conditions of concrete alkalescence, and because the number change of the group with dispersion effect in products molecule structure before and after hydrolysis of ester group is little, be not in hydrolysis of ester group it is too fast and produce the delayed scale-up problem of concrete slump, also be not in the too fast problem of concrete slump loss produced because hydrolysis of ester group is excessively slow, therefore being difficult to be changed by use condition in use is influenceed, realize the stability contorting to concrete slump.
Description
Technical field
The invention belongs to building material technical field, and in particular to a kind of preparation of stable type concrete slump controlling agent
Method.
Background technology
As concrete technology is to high-strength, green, high-performance direction fast development, important component in concrete is used as
Water reducer be also suggested it is higher, more fully require.Traditional cement water reducing agent in the past, the lignin of such as first generation and
The water reducers such as naphthalene sulfonate system, sulfonated melamine system, amido sulfoacid series, the fatty family of the second generation, because volume is larger, subtract
Water rate is not high enough, enhancing effect not very notable, concrete slump loss is larger, can not gradually meet modern concrete skill
The development of art and modern concrete construction.Especially in process of production will using crude naphthalene, the concentrated sulfuric acid, formaldehyde, liquid caustic soda,
The harmful chemicals such as phenol, can cause necessarily to pollute unavoidably, the shortcomings of there is the problem of being unfavorable for sustainable development to environment,
So as to partly constrain its further popularization and application.
Polycarboxylate water-reducer due to its excellent performance, energy-conserving and environment-protective, good concrete durability the advantages of since 2006
Applied in key state projects such as high ferro, water power, nuclear powers.But as resource scarcity and concrete performance demand are lifted, gather
Carboxylic acid water reducer popularization and application process also often occur protect collapse effect not enough and protect collapse effect easily by asking that the factors such as temperature are influenceed
Topic, therefore, exploitation have function of slump protection excellent and the stable type concrete slump controlling agent insensitive to use condition just has
It is of great significance.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of system of stable type concrete slump controlling agent
Preparation Method.
Technical scheme is as follows：
A kind of preparation method of stable type concrete slump controlling agent, comprises 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 add
Enter catalyst, be warming up to 100~140 DEG C, during which 0.5~3h of insulation reaction is removed with vacuumizing or lead to method of the nitrogen with water
Water, reaction is down to room temperature after terminating, and obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid, unsaturated
Carboxylic acid and compound A mol ratio are 1.5~6: 1, and the consumption of catalyst is unsaturated carboxylic acid and compound A gross masses
0.5%~5.0%, polymerization inhibitor consumption is the 0.5%~5.0% of unsaturated carboxylic acid and compound A gross masses, compound A knot
Structure formula is as follows：
Wherein R1Alkyl for 1~4 carbon does not have, and R2 is the alkyl of 1~4 carbon or do not had；
(2) by the 4- hydroxyl butyl vinyl polyoxyethylene of the first mixture, molecular weight 600~5000 made from step (1)
Base ether is mixed with 1: 4~30 mass ratio, and adds water so that its dissolving, obtains copolymerized monomer mixture solution；
(3) above-mentioned copolymerized monomer mixture solution, initiator solution and the molecular weight regulator aqueous solution are instilled in water
Reacted, reaction temperature is 10~40 DEG C, time for adding is 0~3.0h of insulation after 0.2~6.0h, completion of dropping, obtains copolymerization
Product；The total amount of water used in the step and step (2) causes the mass concentration of the copolymerization product to be 20~80%, the use of initiator
Measure as 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, the consumption of molecular weight regulator is comonomer
The 0.2~3.0% of the gross mass of solute in mixture solution；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces the stable type concrete slump
Controlling agent.
In a preferred embodiment of the invention, the step (1) is：By unsaturated carboxylic acid, compound A, inhibition
Agent is mixed, and under nitrogen protection, is warming up to 50~60 DEG C, is added catalyst, is warming up to 105~130 DEG C, and insulation reaction 1~
3h, during which removes water with vacuumizing or lead to method of the nitrogen with water, reaction is down to room temperature after terminating, obtain containing esterification products with
First mixture of unreacted unsaturated carboxylic acid, unsaturated carboxylic acid and compound A mol ratio are 1.5~5: 1, catalyst
Consumption is the 0.5%~4.0% of unsaturated carboxylic acid and compound A gross masses, and polymerization inhibitor consumption 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) is：By the first mixture made from step (1),
The 4- hydroxyl butyl vinyl polyoxyethylene ethers of molecular weight 600~5000 are mixed with 1: 5~20 mass ratio, and are added water and caused
It dissolves, and obtains copolymerized monomer mixture solution.
In a preferred embodiment of the invention, the step (3) is：By above-mentioned copolymerized monomer mixture solution with
Initiator solution and the molecular weight regulator aqueous solution are instilled to be reacted in water, and reaction temperature is 10~30 DEG C, time for adding
For 0.2~5.0h, 0~3.0h is incubated after completion of dropping, copolymerization product is obtained；The total amount of water causes used in the step and step (2)
The mass concentration of the copolymerization product is 20~70%, and the consumption of initiator is the gross mass of solute in copolymerized monomer mixture solution
0.5~2.0%, the consumption 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 is in ethylsulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and 98% concentrated sulfuric acid
It is at least one.
It is further preferred that the polymerization inhibitor is at least one of hydroquinones, phenthazine and diphenylamines.
It is further preferred that the initiator, which is water soluble, redox, triggers system or water-soluble azo initiator.
It is further preferred that the molecular weight regulator is TGA, 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：
1st, the present invention introduces ester group, phenyl ring in the molecular structure by unsaturated carboxylic acid and compound A esterification products
With sulfonic acid based structures, due to introducing the sulfonic acid group with water-reducing effect and the phenyl ring with space steric effect when initial,
So that the product of product has higher initial water-reducing rate.
2nd, when the stable type concrete slump controlling agent for preparing preparation method of the present invention is used for concrete, in concrete
Alkaline environment under, the ester bond in molecular structure can be hydrolyzed gradually, discharge the carboxyl with water-reducing effect, realize excellent collapse
Degree of falling keeps effect, and due to the change of the radical amount with dispersion effect in products molecule structure before and after hydrolysis of ester group not
Greatly, be not in hydrolysis of ester group it is too fast and produce concrete slump delayed amplification the problem of, be also not in due to ester group
The hydrolyzed too fast problem of concrete slump loss of generation, therefore be difficult what is changed by use condition in use slowly
Influence, realizes the stability contorting to concrete slump.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
(1) 240.00g acrylic acid, 200.00g p-hydroxybenzenyl sulfonates, 6.50g phenthazine are mixed, under nitrogen protection,
It is warming up to 60 DEG C, adds 8.23g p-methyl benzenesulfonic acid, 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, and reaction is down to room temperature after terminating, and obtains the first mixing containing esterification products and unreacted acrylic acid
Thing；
(2) by the first mixture, 185.00g molecular weight made from 20.00g steps (1) be 2400 4- hydroxyl butylethylenes
Base polyoxyethylene ether is mixed, and adds 120.00g water so that its dissolving, obtains 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), copperas solution (wherein, ferrous sulfate 0.40g,
Water 10.00g), the TGA aqueous solution (wherein, TGA 1.20g, water 20.00g) instill 60.00g water in reacted,
Reaction temperature is 30 DEG C, and time for adding is to be incubated 0.5h after 2.0h, completion of dropping, obtains copolymerization product；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces the stable type concrete slump
Controlling agent KZJ-1.
Embodiment 2
(1) by 247.00g methacrylic acids, 200.00g to methylol benzene sulfonic acid, 5.60g hydroquinones, 2.00g fen thiophenes
Piperazine is mixed, under nitrogen protection, is warming up to 50 DEG C, adds the concentrated sulfuric acid that 8.20g mass fractions are 98%, is warming up to 115 DEG C, guarantor
Temperature reaction 3h, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is down to room temperature after terminating, obtained containing esterification
First mixture of product and unreacted methacrylic acid；
(2) by the first mixture, 260.00g molecular weight made from 20.00g steps (1) be 2400 4- hydroxyl butylethylenes
Base polyoxyethylene ether is mixed, and adds 150.00g water so that its dissolving, obtains 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),
The sodium formaldehyde sulfoxylate aqueous solution (wherein, sodium formaldehyde sulfoxylate 0.70g, water 20.00g), copperas solution (wherein, ferrous sulfate 0.50g, water
10.00g), the mercaptopropionic acid aqueous solution (wherein, mercaptopropionic acid 1.50g, water 20.00g) is instilled is reacted in 60.00g water, instead
It is 20 DEG C to answer temperature, and time for adding is to be incubated 1h after 1.0h, completion of dropping, obtains copolymerization product；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces the stable type concrete slump
Controlling agent KZJ-2.
Embodiment 3
(1) 156g acrylic acid, 86g methacrylic acids, 200.00g are mixed to hydroxyethylbenzene sulfonic acid, 4.20g hydroquinones
Close, under nitrogen protection, be warming up to 60 DEG C, add 6.30g ethylsulfonic acids, be warming up to 110 DEG C, insulation reaction 2h, during which with taking out
The method of vacuum or logical nitrogen with water removes water, and reaction is down to room temperature after terminating, obtained containing esterification products and unreacted third
First mixture of olefin(e) acid and methacrylic acid；
(2) by the first mixture, 233.00g molecular weight made from 20.00g steps (1) be 2400 4- hydroxyl butylethylenes
Base polyoxyethylene ether is mixed, and adds 150.00g water so that its dissolving, obtains 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), copperas 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 is to be incubated 1h after 1.5h, completion of dropping, obtains copolymerization product；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces the stable type concrete slump
Controlling agent KZJ-3.
Embodiment 4
(1) 177.00g acrylic acid, 200.00g4- hydroxy phenyls methanesulfonic acid, 6.60g diphenylamines are mixed, in nitrogen protection
Under, it is warming up to 60 DEG C, adds the concentrated sulfuric acid that 5.50g mass fractions are 98%, is warming up to 105 DEG C, insulation reaction 3h, during which with taking out
The method of vacuum or logical nitrogen with water removes water, and reaction is down to room temperature after terminating, obtained containing esterification products and unreacted third
First mixture of olefin(e) acid；
(2) by the first mixture 244.00g molecular weight made from 20.00g steps (1) be 3000 4- hydroxyl butyl vinyls
Polyoxyethylene ether is mixed, and adds 150.00g water so that its dissolving, obtains 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),
The sodium formaldehyde sulfoxylate aqueous solution (wherein, sodium formaldehyde sulfoxylate 1.20g, water 20.00g), copperas solution (wherein, ferrous sulfate 0.70g, water
10.00g), isopropanol water solution (wherein, isopropanol 1.50g, water 20.00g) is instilled is reacted in 60.00g water, reaction temperature
Spend for 25 DEG C, time for adding is to be incubated 1.5h after 0.5h, completion of dropping, obtains copolymerization product；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces the stable type concrete slump
Controlling agent KZJ-4.
Embodiment 5
(1) by 140.00g acrylic acid, 87.00g p-hydroxybenzenyl sulfonates, 113g to methylol benzene sulfonic acid, 3.40g to benzene two
Phenol is mixed, under nitrogen protection, is warming up to 50 DEG C, adds 4.60g benzene sulfonic acids, is warming up to 120 DEG C, during which insulation reaction 2h uses
Vacuumize or lead to method of the nitrogen with water and remove water, reaction is down to room temperature after terminating, obtain containing esterification products and unreacted
First mixture of acrylic acid；
(2) by the first mixture, 220.00g molecular weight made from 20.00g steps (1) be 3000 4- hydroxyl butylethylenes
Base polyoxyethylene ether is mixed, and adds 150.00g water so that its dissolving, obtains 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), the lauryl mercaptan aqueous solution (wherein, lauryl mercaptan 2.30g, water 30.00g) instill
Reacted in 70.00g water, reaction temperature is 30 DEG C, time for adding is to be incubated 1.0h after 3.0h, completion of dropping, obtain copolymerization production
Thing；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces the stable type concrete slump
Controlling agent KZJ-5.
To embodiment 1 to obtained by embodiment 5 stable type concrete slump controlling agent (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, the concrete performance of different temperatures
Compare.Using Fujian good fortune cement (P.O42.5R), concrete mix is：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
KZJ-1, KZJ-2, KZJ-3, KZJ-4, KZJ-5 and PCE concrete performance 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 in the range of 550 ± 10mm
1h, 2h and 3h slump (TL) and divergence (TK), 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 the condition of different temperatures of table 2
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 poly- carboxylic of commercially available collapse protection type
Greatly, i.e., it is when experiment condition changes the embodiment that the slump-loss change of sour water reducer (PCE) is synthesized compared with this patent pair
The slump control ability of concrete is weak compared with the embodiment that this patent is synthesized.
Those of ordinary skill in the art understand, when technical parameter and raw material components of the invention changes in following ranges,
Remain to access technique effect same as the previously described embodiments or close, still belong to and protection scope of the present invention：
A kind of preparation method of stable type concrete slump controlling agent, comprises 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 add
Enter catalyst, be warming up to 100~140 DEG C, during which 0.5~3h of insulation reaction is removed with vacuumizing or lead to method of the nitrogen with water
Water, reaction is down to room temperature after terminating, and obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid, unsaturated
Carboxylic acid and compound A mol ratio are 1.5~6: 1, and the consumption of catalyst is unsaturated carboxylic acid and compound A gross masses
0.5%~5.0%, polymerization inhibitor consumption is the 0.5%~5.0% of unsaturated carboxylic acid and compound A gross masses, compound A knot
Structure formula is as follows：
Wherein R1Alkyl for 1~4 carbon does not have, R2Alkyl for 1~4 carbon does not have；
(2) by the 4- hydroxyl butyl vinyl polyoxyethylene of the first mixture, molecular weight 600~5000 made from step (1)
Base ether is mixed with 1: 4~30 mass ratio, and adds water so that its dissolving, obtains copolymerized monomer mixture solution；
(3) above-mentioned copolymerized monomer mixture solution, initiator solution and the molecular weight regulator aqueous solution are instilled in water
Reacted, reaction temperature is 10~40 DEG C, time for adding is 0~3.0h of insulation after 0.2~6.0h, completion of dropping, obtains copolymerization
Product；The total amount of water used in the step and step (2) causes the mass concentration of the copolymerization product to be 20~80%, the use of initiator
Measure as 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, the consumption of molecular weight regulator is comonomer
The 0.2~3.0% of the gross mass of solute in mixture solution；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces 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 hydroquinones, phenthazine and hexichol
At least one of amine.The initiator is that water soluble, redox triggers system or water-soluble azo initiator.The molecule
Amount conditioning agent be TGA, 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, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (9)
1. a kind of preparation method of stable type concrete slump controlling agent, it is characterised in that：Comprise 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 removes water with vacuumizing or lead to method of the nitrogen with water, instead
Room temperature is down to after should terminating, the first mixture containing esterification products and unreacted unsaturated carboxylic acid, unsaturated carboxylic acid is obtained
Be 1.5~6: 1 with compound A mol ratio, the consumption of catalyst for unsaturated carboxylic acid and compound A gross masses 0.5%~
5.0%, polymerization inhibitor consumption is the 0.5%~5.0% of unsaturated carboxylic acid and compound A gross masses, and compound A structural formula is such as
Under：
Wherein R1Alkyl for 1~4 carbon does not have, R2Alkyl for 1~4 carbon does not have；
(2) by the 4- hydroxyl butyl vinyl polyoxyethylene ethers of the first mixture, molecular weight 600~5000 made from step (1)
Mixed with 1: 4~30 mass ratio, and add water so that its dissolving, obtains copolymerized monomer mixture solution；
(3) above-mentioned copolymerized monomer mixture solution, initiator solution and the molecular weight regulator aqueous solution are instilled in water and carried out
Reaction, reaction temperature is 10~40 DEG C, and time for adding is 0~3.0h of insulation after 0.2~6.0h, completion of dropping, obtains copolymerization product；
The total amount of water used in the step and step (2) make it that the mass concentration of the copolymerization product is 20~80%, and the consumption of initiator is
The 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, the consumption of molecular weight regulator mixes for comonomer
The 0.2~3.0% of the gross mass of solute in thing solution；
(4) copolymerization product made from step (3) is adjusted into pH to 5~7 with alkali, produces the stable type concrete slump control
Agent.
2. preparation method as claimed in claim 1, it is characterised in that：The step (1) is：By unsaturated carboxylic acid, compound
A, polymerization inhibitor mixing, under nitrogen protection, are warming up to 50~60 DEG C, add catalyst, are warming up to 105~130 DEG C, insulation is anti-
1~3h is answered, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is down to room temperature after terminating, obtained containing esterification
First mixture of product and unreacted unsaturated carboxylic acid, the mol ratio of unsaturated carboxylic acid and compound A is 1.5~5: 1, is urged
The consumption of agent is the 0.5%~4.0% of unsaturated carboxylic acid and compound A gross masses, polymerization inhibitor consumption be unsaturated carboxylic acid with
The 0.5%~4.0% of compound A gross masses.
3. preparation method as claimed in claim 1, it is characterised in that：The step (2) is：By first made from step (1)
Mixture, the 4- hydroxyl butyl vinyl polyoxyethylene ethers of molecular weight 600~5000 are mixed with 1: 5~20 mass ratio, and added
Enter water so that its dissolving, obtains copolymerized monomer mixture solution.
4. preparation method as claimed in claim 1, it is characterised in that：The step (3) is：By above-mentioned copolymerized monomer mixture
Solution is instilled with initiator solution and the molecular weight regulator aqueous solution to be reacted in water, and reaction temperature is 10~30 DEG C, drop
It is 0~3.0h of insulation after 0.2~5.0h, completion of dropping between added-time, obtains copolymerization product；Water is total used in the step and step (2)
Amount causes the mass concentration of the copolymerization product to be 20~70%, and the consumption of initiator is solute in copolymerized monomer mixture solution
The 0.5~2.0% of gross mass, the consumption of the molecular weight regulator is 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 unsaturated carboxylic acid is
At least one of acrylic acid and methacrylic acid.
6. 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.
7. 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.
8. 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.
9. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The molecular weight regulator
For TGA, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan
At least one of.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107868187A (en) * | 2017-12-07 | 2018-04-03 | 科之杰新材料集团有限公司 | A kind of preparation method of low hydration heat polycarboxylate water-reducer |
| CN107903361A (en) * | 2017-12-07 | 2018-04-13 | 科之杰新材料集团有限公司 | A kind of preparation method of high-adaptability concrete flowability stabilizer |
| CN107955106A (en) * | 2017-12-07 | 2018-04-24 | 科之杰新材料集团有限公司 | A kind of preparation method of concrete flowability stabilizer |
| CN107987235A (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 crack resistance type polycarboxylate water-reducer |
| CN107987228A (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 Early-strength polycarboxylate superplasticizer |
| 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 |
| CN108047389A (en) * | 2017-12-07 | 2018-05-18 | 科之杰新材料集团有限公司 | A kind of preparation method of low responsive type concrete flowability stabilizer |
| CN109111147A (en) * | 2018-08-16 | 2019-01-01 | 科之杰新材料集团有限公司 | A kind of multi-functional ethers 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047389A (en) * | 2017-12-07 | 2018-05-18 | 科之杰新材料集团有限公司 | A kind of preparation method of low responsive type concrete flowability stabilizer |
| CN107987228B (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 early-strength polycarboxylate superplasticizer |
| CN107955106A (en) * | 2017-12-07 | 2018-04-24 | 科之杰新材料集团有限公司 | A kind of preparation method of concrete flowability stabilizer |
| CN107987235A (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 crack resistance type polycarboxylate water-reducer |
| CN107987228A (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 Early-strength polycarboxylate superplasticizer |
| 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 |
| CN107903361A (en) * | 2017-12-07 | 2018-04-13 | 科之杰新材料集团有限公司 | A kind of preparation method of high-adaptability concrete flowability stabilizer |
| 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 |
| CN107868187A (en) * | 2017-12-07 | 2018-04-03 | 科之杰新材料集团有限公司 | A kind of preparation method of low hydration heat polycarboxylate water-reducer |
| 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 |
| CN107868187B (en) * | 2017-12-07 | 2020-05-08 | 科之杰新材料集团有限公司 | Preparation method of low-hydration-heat polycarboxylate superplasticizer |
| 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 |
| CN109111147A (en) * | 2018-08-16 | 2019-01-01 | 科之杰新材料集团有限公司 | A kind of multi-functional ethers 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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