CN108484842A - Low responsive type polycarboxylate water-reducer of a kind of esters and preparation method thereof - Google Patents
Low responsive type polycarboxylate water-reducer of a kind of esters and preparation method thereof Download PDFInfo
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- CN108484842A CN108484842A CN201810414348.3A CN201810414348A CN108484842A CN 108484842 A CN108484842 A CN 108484842A CN 201810414348 A CN201810414348 A CN 201810414348A CN 108484842 A CN108484842 A CN 108484842A
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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
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers 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
- C04B2103/302—Water reducers
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Abstract
The invention discloses low responsive type polycarboxylate water-reducer of a kind of esters and preparation method thereof, the molecular weight of active ingredient is 10000~15000, and the structural formula of the active ingredient is：
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of low responsive type polycarboxylate water-reducer of esters and its
Preparation method.
Background technology
Polycarboxylate water-reducer is as novel high-performance water reducing agent, with volume is low, water-reducing rate is high, slump-retaining
It is good, shrinking percentage is small, it is opposite with cement and admixture adaptability preferably, a series of enhancing effect performances outstanding such as obviously.Meanwhile
Production process environmental protection, is widely used at present in every engineering field.
It is more and more wider with the application surface of polycarboxylate water-reducer, due to the difference of raw material during ready-mixed concrete
Property, the understanding limitation of the difference of territorial environment and technical staff, use habit and theoretical human-subject test height, lead
Also there are some problems during using polycarboxylate water-reducer in cause, directly affects the use effect of poly carboxylic acid series water reducer
Fruit.The mechanism of action of polycarboxylate water-reducer, autosensitization etc. can not be controlled completely at home at present.Especially in reality
It is since cement type is various, many reasons such as sandstone clay content in concrete raw material, poly carboxylic acid series water reducer is straight in engineering
When scooping out for concrete, often will appear with cement adaptability is bad, expected, damage of collapsing is not achieved in working performance of concrete may
The problems such as larger, leads to not meet construction site requirement.Therefore, a kind of polycarboxylate water-reducer with hyposensitivity is developed
With very great meaning.
Invention content
It is an object of the invention to overcome prior art defect, provide a kind of esters low responsive type polycarboxylate water-reducer.
Another object of the present invention is to provide the preparation methods of the low responsive type polycarboxylate water-reducer of above-mentioned esters.
Technical scheme is as follows：
The molecular weight of a kind of low responsive type polycarboxylate water-reducer of esters, active ingredient is 10000~15000, and this has
Effect ingredient structural formula be：
Wherein, R1For H or CH3, R2For SO3M、NH2Or CONH2, R3For H or COOM, R4For H or CH3, R5For H or COOM, R6
For H or CH3, R7For empty or 1~4 carbon alkyl, above-mentioned M is H, Na, K or NH4。
The preparation method of the low responsive type polycarboxylate water-reducer of above-mentioned esters, includes the following steps：
(1) esterification：The methoxy poly (ethylene glycol) for being 200~1000 by dicarboxylic acids and molecular weight, in nitrogen protection
Under, 60~100 DEG C are warming up to, adds the first catalyst, 0.4~2.5h of insulation reaction, it is 200~1000 to add molecular weight
Polyethylene glycol and the second catalyst, 0.4~3.0h of insulation reaction adds unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, inhibition
Agent and third catalyst, 0.4~3.5h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is tied
It is down to room temperature after beam, obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides；
Above-mentioned dicarboxylic acids is at least one of ethanedioic acid, malonic acid, succinic acid, glutaric acid and adipic acid, above-mentioned unsaturated carboxylic acid
Or unsaturated carboxylic acid anhydrides are at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic anhydride, above-mentioned the
One catalyst is periodic acid, and at least one of dinitrobenzoic acid and ethylenediamine tetra-acetic acid, above-mentioned second catalyst is high iodine
Acid, dinitrobenzoic acid, at least one of ethylenediamine tetra-acetic acid, above-mentioned third catalyst are the concentrated sulfuric acid, benzene sulfonic acid, to toluene
At least one of sulfonic acid, ethylsulfonic acid；
(2) monomer blend：First mixture made from step (1) and copolymerization minor comonomer is mixed with 200: 1~5 mass ratio
It closes, obtains copolymerized monomer mixture solution, above-mentioned copolymerization minor comonomer is in methylpropene sodium sulfonate, acrylamide, allylamine
It is at least one；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill water in reacted, reaction temperature be 10~63 DEG C, time for adding be 0.2~6.5h, after being added dropwise keep the temperature 0~
3.5h obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get a kind of esters
Low responsive type polycarboxylate water-reducer.
In a preferred embodiment of the invention, the step (1) is：By dicarboxylic acids and molecular weight be 200~
1000 methoxy poly (ethylene glycol) is warming up to 60~90 DEG C under nitrogen protection, adds the first catalyst, insulation reaction 0.5
~2.5h, adds polyethylene glycol and the second catalyst that molecular weight is 200~1000, and 0.5~3.0h of insulation reaction is added
Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, polymerization inhibitor and third catalyst, 0.5~3.5h of insulation reaction, during which with vacuumizing or
Logical method of the nitrogen with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted unsaturated carboxylic
First mixture of acid or unsaturated carboxylic acid anhydrides, above-mentioned dicarboxylic acids, methoxy poly (ethylene glycol), polyethylene glycol and unsaturated carboxylic acid
Or the molar ratio of unsaturated carboxylic acid anhydrides is 1: 1: 1: 2~10, the dosage of the first catalyst is dicarboxylic acids and the poly- second of methoxyl group two
The 0.2~4.2% of alcohol gross mass, the dosage of the second catalyst are the 0.2~4.2% of polyethylene glycol quality, third catalyst
Dosage is the 0.2~4.2% of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality, and polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturation
The 0.2~6.0% of carboxylic acid anhydrides quality.
It is further preferred that the dicarboxylic acids, methoxy poly (ethylene glycol), polyethylene glycol and unsaturated carboxylic acid or unsaturation
The molar ratio of carboxylic acid anhydrides is 1: 1: 1: 3~8, and the dosage of the first catalyst is dicarboxylic acids and methoxy poly (ethylene glycol) gross mass
0.3~4.0%, the dosage of the second catalyst is the 0.3~4.0% of polyethylene glycol quality, and the dosage of third catalyst is insatiable hunger
With the 0.3~4.0% of carboxylic acid or unsaturated carboxylic acid anhydrides quality, polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality
0.5~5.0%.
In a preferred embodiment of the invention, the step (2) is：By the first mixture made from step (1)
It is mixed with 200: 1~4 mass ratio with copolymerization minor comonomer, obtains copolymerized monomer mixture solution.
In a preferred embodiment of the invention, the step (3) is：By above-mentioned copolymerized monomer mixture solution,
Initiator solution and molecular weight regulator aqueous solution, which instill in water, to be reacted, and reaction temperature is 10~60 DEG C, time for adding
For 0.2~6.0h, 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 20~80%, and the dosage of initiator is the gross mass of solute in copolymerized monomer mixture solution
0.5~3.2%, the dosage of molecular weight regulator be the gross mass of solute in copolymerized monomer mixture solution 0.2~
3.0%.
It is further preferred that the total amount of water used in step (3) and step (2) so that the mass concentration of the copolymerization product is 20
~70%, the dosage of initiator is 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, molecular-weight adjusting
The dosage of agent is 0.2~2.0% of the gross mass of solute in copolymerized monomer mixture solution.
In a preferred embodiment of the invention, the polymerization inhibitor is in hydroquinone, phenthazine and diphenylamines
It is at least one.
In a preferred embodiment of the invention, the initiator is that water soluble, redox causes system or water-soluble
Property azo initiator.
In a preferred embodiment of the invention, the molecular weight regulator is thioacetic acid, mercaptopropionic acid, sulfydryl
At least one of ethyl alcohol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan.
The beneficial effects of the invention are as follows：The low responsive type polycarboxylate water-reducer of esters made from preparation method of the present invention, branch
For the both ends twin-stage polyether structure of ester group connection, the sensibility of product can be significantly reduced, realizes that product is used in environment temperature, folk prescription
Concrete performance is unaffected when the variations of concrete productions factor such as water, aggregate clay content, water-reducing agent volume, and coagulation is autochthonal
Produce it is easily controllable, to promote the stability of concrete performance.And since branch with main chain is connected in the form of ester group, product phase
It is that workability is more preferable when the product connected in the form of ehter bond is used for concrete compared with branch and main chain.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode.
The molecular weight of the active ingredient of the low responsive type polycarboxylate water-reducer of esters prepared in following embodiments be 10000~
15000, and the structural formula of the active ingredient is：
Wherein, R1For H or CH3, R2For SO3M、NH2Or CONH2, R3For H or COOM, R4For H or CH3, R5For H or COOM, R6
For H or CH3, R7For empty or 1~4 carbon alkyl, above-mentioned M is H, Na, K or NH4。
Embodiment 1
(1) esterification：The methoxy poly (ethylene glycol) for being 200 by 100.00g ethanedioic acids and 222.10g molecular weight, in nitrogen
Under gas shielded, 65 DEG C are warming up to, adds the first catalyst of 2.50g, insulation reaction 2.0h, adding 222.10g molecular weight is
200 the second catalyst of polyethylene glycol and 2.20g, insulation reaction 1.0h, add 80.00g acrylic acid, 1.00g polymerization inhibitors and
1.60g third catalyst, insulation reaction 1.0h, during which with vacuumizing or leading to method removing water of the nitrogen with water, after reaction
It is down to room temperature, obtains the first mixture containing esterification products and unreacted acrylic acid；
(2) monomer blend：By the first mixture made from 200.00 steps (1), 2.00g methylpropene sodium sulfonates and
80.00g water mixes, and obtains copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein hydrogen peroxide 1.80g, water
20.00g), aqueous ascorbic acid (wherein 0.60g, water 20.00g) and thioacetic acid aqueous solution (wherein thioacetic acid 1.00g,
Water 20.00g) it instills in 60.00g water and is reacted, reaction temperature is 40 DEG C, and time for adding 3.0h is kept the temperature after being added dropwise
1.0h obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the esters muting sensitive
Sense type polycarboxylate water-reducer PCE-1.
Embodiment 2
(1) esterification：The methoxy poly (ethylene glycol) for being 400 by 100.00g malonic acid and 384.40g molecular weight, in nitrogen
Under gas shielded, 70 DEG C are warming up to, adds the first catalyst of 3.00g, insulation reaction 1.5h, adding 288.30g molecular weight is
300 the second catalyst of polyethylene glycol and 3.00g, insulation reaction 1.0h add 82.60g methacrylic acids, 1.10g inhibitions
Agent and 2.00g third catalyst, insulation reaction 1.Sh, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is tied
It is down to room temperature after beam, obtains the first mixture containing esterification products and unreacted methacrylic acid；
(2) monomer blend：First mixture made from 200.00 steps (1), 3.00g acrylamides and 80.00g water is mixed
It closes, obtains copolymerized monomer mixture solution；
(3) copolyreaction：(wherein by above-mentioned copolymerized monomer mixture solution, azo diisobutyl amidine hydrochloric acid saline solution
Azo diisobutyl amidine hydrochloride 3.00g, water 40.00g) and sodium hypophosphite aqueous solution (wherein sodium hypophosphite 2.20g, water
It 20.00g) instills in 60.00g water and is reacted, reaction temperature is 50 DEG C, and time for adding 2.5h is kept the temperature after being added dropwise
1.0h obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the esters muting sensitive
Sense type polycarboxylate water-reducer PCE-2.
Embodiment 3
(1) esterification：The methoxy poly (ethylene glycol) for being 600 by 100.00g succinic acid and 508.00g molecular weight, in nitrogen
Under gas shielded, 65 DEG C are warming up to, adds the first catalyst of 3.20g, insulation reaction 2.0h, adding 338.70g molecular weight is
400 the second catalyst of polyethylene glycol and 3.50g, insulation reaction 2.0h, add 98.20g fumaric acid, 1.20g polymerization inhibitors and
1.00g third catalyst, insulation reaction 2.0h, during which with vacuumizing or leading to method removing water of the nitrogen with water, after reaction
It is down to room temperature, obtains the first mixture containing esterification products and unreacted fumaric acid；
(2) monomer blend：First mixture made from 200.00 steps (1), 2.50g allylamines and 80.00g water is mixed
It closes, obtains copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein azo two
Cyanopentanoic acid 3.20g, water 40.00g) and trisodium phosphate aqueous solution (wherein tertiary sodium phosphate 3.50g, water 20.00g) instillation 60.00g
It is reacted in water, reaction temperature is 60 DEG C, and time for adding 2.0h keeps the temperature 0.5h after being added dropwise, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the esters muting sensitive
Sense type polycarboxylate water-reducer PCE-3.
Embodiment 4
(1) esterification：The methoxy poly (ethylene glycol) for being 800 by 100.00g glutaric acids and 605.50g molecular weight, in nitrogen
Under gas shielded, 75 DEG C are warming up to, adds the first catalyst of 5.20g, insulation reaction 1.5h, adding 378.50g molecular weight is
500 the second catalyst of polyethylene glycol and 3.80g, insulation reaction 1.0h, add 98.40g itaconic acids, 1.80g polymerization inhibitors and
1.50g third catalyst, insulation reaction 2.0h, during which with vacuumizing or leading to method removing water of the nitrogen with water, after reaction
It is down to room temperature, obtains the first mixture containing esterification products and unreacted itaconic acid；
(2) monomer blend：By the first mixture made from 200.00 steps (1), 3.00g methylpropene sodium sulfonates and
80.00g water mixes, and obtains copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 1.30g, water
20.00g), trisodium phosphate aqueous solution (wherein, tertiary sodium phosphate 1.80g, water 20.00g), aqueous ascorbic acid are (wherein, anti-bad
Hematic acid 0.50, water 20.00g) it instills in 60.00g water and is reacted, reaction temperature is 30 DEG C, and time for adding 4.0h is dripped
2.0h is kept the temperature after finishing, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the esters muting sensitive
Sense type polycarboxylate water-reducer PCE-4.
Embodiment 5
(1) esterification：The methoxy poly (ethylene glycol) for being 1000 by 100.00g adipic acids and 684.30g molecular weight, in nitrogen
Under gas shielded, 80 DEG C are warming up to, adds the first catalyst of 4.50g, insulation reaction 1.0h, adding 410.60g molecular weight is
600 the second catalyst of polyethylene glycol and 4.20g, insulation reaction 1.0h add 67.00g maleic anhydrides, 1.40g polymerization inhibitors
With 1.50g third catalyst, insulation reaction 1.5h, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction terminates
After be down to room temperature, obtain the first mixture containing esterification products and unreacted maleic anhydride；
(2) monomer blend：First mixture made from 200.00 steps (1), 4.00g acrylamides and 80.00g water is mixed
It closes, obtains copolymerized monomer mixture solution；
(3) copolyreaction：(wherein, by above-mentioned copolymerized monomer mixture solution, azo diisobutyl amidine hydrochloric acid saline solution
Azo diisobutyl amidine hydrochloride 4.00g, water 40.00g), aqueous sodium acetate solution (wherein, sodium acetate 2.00g, water 20.00g) drop
Enter and reacted in 60.00g water, reaction temperature is 35 DEG C, and time for adding 4.0h keeps the temperature 0.5h after being added dropwise, and must be copolymerized
Product；
(4) neutralization reaction：It is low to get the low esters that the alkali of copolymerization product made from step (3) is adjusted into pH to 5~7
Responsive type polycarboxylate water-reducer PCE-5.
Using 42.5 Portland cements of China Resources P.O, concrete mix is：Cement 300kg/m3, flyash
80kg/m3, miberal powder 80kg/m3, sand 735kg/m3, stone 1040kg/m3, water 165kg/m3 arrive embodiment to embodiment 1 respectively
The low responsive type polycarboxylate water-reducer of ethers and commercially available polycarboxylate water-reducer (PCE) obtained by 5 are according under the conditions of same points
It is other that varying environment temperature, folk prescription water consumption, aggregate clay content, water-reducing agent volume are tested for the property, test result such as table 1,
Shown in table 2, table 3 and table 4.
1 environment temperature sensibility of table
2 folk prescription water consumption sensibility of table
3 aggregate clay content sensibility of table
4 water-reducing agent volume sensibility of table
The embodiment that this patent synthesizes, which is can be seen that, from table 1-4 compares commercially available polycarboxylate water-reducer (PCE), water-reducing rate
Higher, concrete slump holding capacity is more preferable, to environment temperature, folk prescription water consumption, aggregate clay content, water-reducing agent volume it is quick
Perception is lower.
Those of ordinary skill in the art still can it is found that when the raw materials used in the present invention and parameter change in following ranges
Same as the previously described embodiments or similar technique effect is accessed, protection scope of the present invention is still fallen within：
The molecular weight of a kind of low responsive type polycarboxylate water-reducer of esters, active ingredient is 10000~15000, and this has
Effect ingredient structural formula be：
Wherein, R1For H or CH3, R2For SO3M、NH2Or CONH2, R3For H or COOM, R4For H or CH3, R5For H or COOM, R6
For H or CH3, R7For empty or 1~4 carbon alkyl, above-mentioned M is H, Na, K or NH4。
The preparation method of the low responsive type polycarboxylate water-reducer of above-mentioned esters, includes the following steps：
(1) esterification：The methoxy poly (ethylene glycol) for being 200~1000 by dicarboxylic acids and molecular weight, in nitrogen protection
Under, 60~100 DEG C are warming up to, adds the first catalyst, 0.4~2.5h of insulation reaction, it is 200~1000 to add molecular weight
Polyethylene glycol and the second catalyst, 0.4~3.0h of insulation reaction adds unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, inhibition
Agent and third catalyst, 0.4~3.5h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, reaction is tied
It is down to room temperature after beam, obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides；
Above-mentioned dicarboxylic acids is at least one of ethanedioic acid, malonic acid, succinic acid, glutaric acid and adipic acid, above-mentioned unsaturated carboxylic acid
Or unsaturated carboxylic acid anhydrides are at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic anhydride, above-mentioned the
One catalyst is periodic acid, and at least one of dinitrobenzoic acid and ethylenediamine tetra-acetic acid, above-mentioned second catalyst is high iodine
Acid, dinitrobenzoic acid, at least one of ethylenediamine tetra-acetic acid, above-mentioned third catalyst are the concentrated sulfuric acid, benzene sulfonic acid, to toluene
At least one of sulfonic acid, ethylsulfonic acid；
(2) monomer blend：First mixture made from step (1) and copolymerization minor comonomer is mixed with 200: 1~5 mass ratio
It closes, obtains copolymerized monomer mixture solution, above-mentioned copolymerization minor comonomer is in methylpropene sodium sulfonate, acrylamide, allylamine
It is at least one；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill water in reacted, reaction temperature be 10~63 DEG C, time for adding be 0.2~6.5h, after being added dropwise keep the temperature 0~
3.5h obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get a kind of esters
Low responsive type polycarboxylate water-reducer.
Preferably, the step (1) is：The methoxy poly (ethylene glycol) for being 200~1000 by dicarboxylic acids and molecular weight,
Under nitrogen protection, 60~90 DEG C are warming up to, adds the first catalyst, 0.5~2.5h of insulation reaction, adding molecular weight is
200~1000 polyethylene glycol and the second catalyst, 0.5~3.0h of insulation reaction add unsaturated carboxylic acid or unsaturated carboxylic
During which acid anhydrides, polymerization inhibitor and third catalyst, 0.5~3.5h of insulation reaction are removed with vacuumizing or lead to method of the nitrogen with water
Water is down to room temperature after reaction, obtains containing esterification products and unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides
Mole of one mixture, above-mentioned dicarboxylic acids, methoxy poly (ethylene glycol), polyethylene glycol and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides
Than being 1: 1: 1: 2~10, the dosage of the first catalyst is the 0.2~4.2% of dicarboxylic acids and methoxy poly (ethylene glycol) gross mass,
The dosage of second catalyst is the 0.2~4.2% of polyethylene glycol quality, and the dosage of third catalyst is unsaturated carboxylic acid or insatiable hunger
With the 0.2~4.2% of carboxylic acid anhydrides quality, polymerization inhibitor dosage be unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality 0.2~
6.0%.It is further preferred that the dicarboxylic acids, methoxy poly (ethylene glycol), polyethylene glycol and unsaturated carboxylic acid or unsaturated carboxylic
The molar ratio of acid anhydrides is 1: 1: 1: 3~8, and the dosage of the first catalyst is dicarboxylic acids and methoxy poly (ethylene glycol) gross mass
0.3~4.0%, the dosage of the second catalyst is the 0.3~4.0% of polyethylene glycol quality, and the dosage of third catalyst is insatiable hunger
With the 0.3~4.0% of carboxylic acid or unsaturated carboxylic acid anhydrides quality, polymerization inhibitor dosage is unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality
0.5~5.0%.
Preferably, the step (2) is：By the first mixture made from step (1) and copolymerization minor comonomer with 200: 1~4
Mass ratio mixing, obtain copolymerized monomer mixture solution.
Preferably, the step (3) is：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight tune
Section agent aqueous solution, which instills in water, to be reacted, and reaction temperature is 10~60 DEG C, and time for adding is 0.2~6.0h, after being added dropwise
0~3.0h is kept the temperature, copolymerization product is obtained；The total amount of water used in the step and step (2) so that the mass concentration of the copolymerization product is
20~80%, the dosage of initiator is 0.5~3.2% of the gross mass of solute in copolymerized monomer mixture solution, molecular weight tune
The dosage for saving agent is 0.2~3.0% of the gross mass of solute in copolymerized monomer mixture solution.It is further preferred that step (3)
So that the mass concentration of the copolymerization product is 20~70% with the total amount of water used in step (2), the dosage of initiator is that copolymerization is single
The dosage of the 0.5~3.0% of the gross mass of solute in body mixture solution, molecular weight regulator is copolymerized monomer mixture solution
The 0.2~2.0% of the gross mass of middle solute.
The polymerization inhibitor is at least one of hydroquinone, phenthazine and diphenylamines.The initiator is water-soluble oxygen
Change reduction initiating system or water-soluble azo initiator.The molecular weight regulator is thioacetic acid, mercaptopropionic acid, sulfydryl second
At least one of alcohol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (10)
1. a kind of low responsive type polycarboxylate water-reducer of esters, it is characterised in that：The molecular weight of its active ingredient be 10000~
15000, and the structural formula of the active ingredient is：
Wherein, R1For H or CH3, R2For S03M、NH2Or CONH2, R3For H or COOM, R4For H or CH3, R5For H or COOM, R6For H
Or CH3, R7For empty or 1~4 carbon alkyl, above-mentioned M is H, Na, K or NH4。
2. a kind of preparation method of the low responsive type polycarboxylate water-reducer of esters described in claim 1, it is characterised in that：Including such as
Lower step：
(1) esterification：The methoxy poly (ethylene glycol) for being 200~1000 by dicarboxylic acids and molecular weight rises under nitrogen protection
Temperature adds the first catalyst to 60~100 DEG C, 0.4~2.5h of insulation reaction, add molecular weight be 200~1000 it is poly-
Ethylene glycol and the second catalyst, 0.4~3.0h of insulation reaction, add unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, polymerization inhibitor and
Third catalyst, 0.4~3.5h of insulation reaction, during which with vacuumizing or leading to method removing water of the nitrogen with water, after reaction
It is down to room temperature, obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides；It is above-mentioned
Dicarboxylic acids is at least one of ethanedioic acid, malonic acid, succinic acid, glutaric acid and adipic acid, above-mentioned unsaturated carboxylic acid or not
Saturated carboxylic acid acid anhydride is at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic anhydride, and above-mentioned first urges
Agent is periodic acid, at least one of dinitrobenzoic acid and ethylenediamine tetra-acetic acid, and above-mentioned second catalyst is periodic acid, two
Nitrobenzoic acid, at least one of ethylenediamine tetra-acetic acid, above-mentioned third catalyst be the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid,
At least one of ethylsulfonic acid；
(2) monomer blend：By the first mixture made from step (1) and copolymerization minor comonomer with 200：1~5 mass ratio mixing,
Obtain copolymerized monomer mixture solution, above-mentioned copolymerization minor comonomer be in methylpropene sodium sulfonate, acrylamide, allylamine at least
It is a kind of；
(3) copolyreaction：Above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution are instilled
It is reacted in water, reaction temperature is 10~63 DEG C, and time for adding is 0.2~6.5h, and 0~3.5h is kept the temperature after being added dropwise, is obtained
Copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get a kind of esters muting sensitive
Sense type polycarboxylate water-reducer.
3. preparation method as claimed in claim 2, it is characterised in that：The step (1) is：It is by dicarboxylic acids and molecular weight
200~1000 methoxy poly (ethylene glycol) is warming up to 60~90 DEG C under nitrogen protection, adds the first catalyst, and heat preservation is anti-
Answer 0.5~2.5h, add molecular weight be 200~1000 polyethylene glycol and the second catalyst, 0.5~3.0h of insulation reaction,
Add unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides, polymerization inhibitor and third catalyst, 0.5~3.5h of insulation reaction, during which with pumping
Method with water of vacuum or logical nitrogen removes water, is down to room temperature after reaction, obtain containing esterification products and it is unreacted not
First mixture of saturated carboxylic acid or unsaturated carboxylic acid anhydrides, above-mentioned dicarboxylic acids, methoxy poly (ethylene glycol), polyethylene glycol and insatiable hunger
It is 1: 1: 1: 2~10 with the molar ratio of carboxylic acid or unsaturated carboxylic acid anhydrides, the dosage of the first catalyst is dicarboxylic acids and methoxyl group
The 0.2~4.2% of polyethylene glycol gross mass, the dosage of the second catalyst are the 0.2~4.2% of polyethylene glycol quality, and third is urged
The dosage of agent is the 0.2~4.2% of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality, polymerization inhibitor dosage be unsaturated carboxylic acid or
The 0.2~6.0% of unsaturated carboxylic acid anhydrides quality.
4. preparation method as claimed in claim 3, it is characterised in that：The dicarboxylic acids, methoxy poly (ethylene glycol), poly- second two
The molar ratio of alcohol and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides is 1: 1: 1: 3~8, the dosage of the first catalyst be dicarboxylic acids and
The 0.3~4.0% of methoxy poly (ethylene glycol) gross mass, the dosage of the second catalyst are the 0.3~4.0% of polyethylene glycol quality,
The dosage of third catalyst is the 0.3~4.0% of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides quality, and polymerization inhibitor dosage is unsaturation
The 0.5~5.0% of carboxylic acid or unsaturated carboxylic acid anhydrides quality.
5. preparation method as claimed in claim 2, it is characterised in that：The step (2) is：It will be first made from step (1)
Mixture and copolymerization minor comonomer are mixed with 200: 1~4 mass ratio, obtain copolymerized monomer mixture solution.
6. preparation method as claimed in claim 2, it is characterised in that：The step (3) is：By above-mentioned copolymerized monomer mixture
Solution, initiator solution and molecular weight regulator aqueous solution, which instill in water, to be reacted, and reaction temperature is 10~60 DEG C, is added dropwise
Time 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)
So that the mass concentration of the copolymerization product is 20~80%, the dosage of initiator is the total of solute in copolymerized monomer mixture solution
The 0.5~3.2% of quality, the dosage of molecular weight regulator be the gross mass of solute in copolymerized monomer mixture solution 0.2~
3.0%.
7. preparation method as claimed in claim 6, it is characterised in that：The total amount of water used in step (3) and step (2) makes this
The mass concentration of copolymerization product is 20~70%, and the dosage of initiator is the gross mass of solute in copolymerized monomer mixture solution
0.5~3.0%, the dosage of molecular weight regulator is 0.2~2.0% of the gross mass of solute in copolymerized monomer mixture solution.
8. the preparation method as described in any claim in claim 2 to 7, it is characterised in that：The polymerization inhibitor is to benzene
At least one of diphenol, phenthazine and diphenylamines.
9. the preparation method as described in any claim in claim 2 to 7, it is characterised in that：The initiator is water-soluble
Property redox initiation system or water-soluble azo initiator.
10. the preparation method as described in any claim in claim 2 to 7, 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020048083A1 (en) * | 2018-09-07 | 2020-03-12 | 科之杰新材料集团有限公司 | Preparation method for crosslinked viscosity-reducing polycarboxylic acid water reducer |
| CN112175129A (en) * | 2020-09-28 | 2021-01-05 | 中建商品混凝土有限公司 | Concrete workability regulator and preparation method thereof |
| CN112708050A (en) * | 2020-08-24 | 2021-04-27 | 重庆建研科之杰建材有限公司 | Concrete water reducing agent and preparation method thereof |
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|---|---|---|---|---|
| EP0738703A2 (en) * | 1995-02-28 | 1996-10-23 | Nippon Shokubai Co., Ltd. | Acrylic acid derivatives, method for preparing the acrylic acid derivatives, and acrylic acid polymers |
| CN107602781A (en) * | 2017-09-20 | 2018-01-19 | 科之杰新材料集团有限公司 | A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer |
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2018
- 2018-05-03 CN CN201810414348.3A patent/CN108484842B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0738703A2 (en) * | 1995-02-28 | 1996-10-23 | Nippon Shokubai Co., Ltd. | Acrylic acid derivatives, method for preparing the acrylic acid derivatives, and acrylic acid polymers |
| CN107602781A (en) * | 2017-09-20 | 2018-01-19 | 科之杰新材料集团有限公司 | A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020048083A1 (en) * | 2018-09-07 | 2020-03-12 | 科之杰新材料集团有限公司 | Preparation method for crosslinked viscosity-reducing polycarboxylic acid water reducer |
| CN112708050A (en) * | 2020-08-24 | 2021-04-27 | 重庆建研科之杰建材有限公司 | Concrete water reducing agent and preparation method thereof |
| CN112175129A (en) * | 2020-09-28 | 2021-01-05 | 中建商品混凝土有限公司 | Concrete workability regulator and preparation method thereof |
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