CN106432627B - A kind of preparation method of ethers collapse protective poly-carboxylic acid water reducing agent - Google Patents
A kind of preparation method of ethers collapse protective poly-carboxylic acid water reducing agent Download PDFInfo
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- CN106432627B CN106432627B CN201610816605.7A CN201610816605A CN106432627B CN 106432627 B CN106432627 B CN 106432627B CN 201610816605 A CN201610816605 A CN 201610816605A CN 106432627 B CN106432627 B CN 106432627B
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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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- 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
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- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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Abstract
The invention discloses a kind of preparation methods of ethers collapse protective poly-carboxylic acid water reducing agent, include the following steps：(1) unsaturated carboxylic acid hydroxy ester is mixed with benzene dialkyl carboxylic acid, polymerization inhibitor, under nitrogen protection, is warming up to 40~60 DEG C; catalyst is added, is warming up to 100~140 DEG C, 0.5~3h of insulation reaction; period removes water, is down to room temperature after reaction, obtains the first mixture；(2) the first mixture, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, ether type monomer are mixed, and water is added and makes its dissolving, obtain copolymerized monomer mixture solution；(3) above-mentioned copolymerized monomer mixture solution is instilled with initiator solution and molecular weight regulator aqueous solution in water and is reacted, obtain copolymerization product；(4) by copolymerization product with alkali adjust pH to 5~7 to get.The present invention introduces the structure of benzene dialkyl carboxylic acid in polycarboxylate water-reducer molecule structure, and the water-reducing agent finally synthesized can be made to obtain superior diminishing and protect effect of collapsing.
Description
Technical field
The invention belongs to building material technical fields, and in particular to a kind of preparation side of ethers collapse protective poly-carboxylic acid water reducing agent
Method.
Background technology
The world today, social economy flourish, and urban construction is advanced by leaps and bounds, and the correlation engineerings such as traffic, water power, municipal administration are built
If also fast-developing therewith, also to build concrete, more stringent requirements are proposed for these engineerings, and to obtain high standard, height
The build concrete of quality and low-carbon, environmental protection, has excellent performance and environmentally protective poly carboxylic acid series water reducer is with regard to essential.
The excellent water-reducing property of polycarboxylate water-reducer is widely recognized as by industry, but the variation due to cement, sand, stone material
The factors such as the clay content of material so that also there is the too fast problem of slump-loss in practical applications in polycarboxylate water-reducer, this
No small trouble is brought to the construction of concrete.Therefore, collapse protective poly-carboxylic acid water reducing agent of the exploitation with excellent function of slump protection
Just have a very important significance.
Invention content
It is an object of the invention to overcome prior art defect, a kind of preparation of ethers collapse protective poly-carboxylic acid water reducing agent is provided
Method.
The specific technical solution of the present invention is as follows：
A kind of preparation method of ethers collapse protective poly-carboxylic acid water reducing agent, includes the following steps：
(1) benzene dialkyl carboxylic acid, the polymerization inhibitor of the unsaturated carboxylic acid hydroxy ester of molecular weight≤200, molecular weight≤300 are mixed
It closes, under nitrogen protection, is warming up to 40~60 DEG C, adds catalyst, be warming up to 100~140 DEG C, 0.5~3h of insulation reaction,
Period removes water with vacuumizing or lead to method of the nitrogen with water, is down to room temperature after reaction, obtains containing esterification products and not
First mixture of the unsaturated carboxylic acid hydroxy ester of reaction, unsaturated carboxylic acid hydroxy ester and the molar ratio of benzene dialkyl carboxylic acid are
1.5~6:1, the dosage of catalyst is the 0.5%~5.0% of unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid gross mass, resistance
Poly- agent dosage is the 0.5%~5.0% of unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid gross mass；
(2) by the first mixture, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides made from step (1), molecular weight 600~
5000 ether type monomer is with 1:1~5:12~60 mass ratio mixing, and water is added and makes its dissolving, obtain comonomer mixing
Object solution；
(3) above-mentioned copolymerized monomer mixture solution and initiator solution and molecular weight regulator aqueous solution are instilled in water
It is reacted, reaction temperature is 10~80 DEG C, and time for adding is 0.25~6.0h, 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) so that the mass concentration of the copolymerization product is 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) copolymerization product alkali made from step (3) pH to 5~7 is adjusted to get the ethers collapse protective poly-carboxylic acid to subtract
Aqua.
In a preferred embodiment of the invention, the step (1) is：By the unsaturated carboxylic acid of molecular weight≤150
Hydroxy ester, the benzene dialkyl carboxylic acid of molecular weight≤250, polymerization inhibitor mixing are warming up to 50~60 DEG C, then add under nitrogen protection
Enter catalyst, be warming up to 105~130 DEG C, 1~3h of insulation reaction, during which removes water with vacuumizing or lead to method of the nitrogen with water,
It is down to room temperature after reaction, obtains the first mixture containing esterification products and unreacted unsaturated carboxylic acid hydroxy ester, no
The molar ratio of saturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid is 1.5~5:1, the dosage of catalyst is unsaturated carboxylic acid hydroxy ester
With the 0.5%~4.0% of benzene dialkyl carboxylic acid gross mass, polymerization inhibitor dosage is unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid
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),
Unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, molecular weight 600~5000 ether type monomer with 1:1~4:15~50 mass ratio
Mixing, and water is added and makes its dissolving, obtain 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 molecular weight regulator aqueous solution, which instill in water, to be reacted, and reaction temperature is 10~70 DEG C, time for adding
For 0.25~5.0h, 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 hydroxy ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl
At least one of butyl ester, hydroxyethyl methacrylate and hydroxy propyl methacrylate.
It is further preferred that the benzene dialkyl carboxylic acid be terephthalic acid (TPA), to phenylenediacetic Acid, to benzene dipropionic acid, isophthalic
At least one of dioctyl phthalate, phenylenediacetic Acid, isophthalic dipropionic acid, phthalic acid, phthalic acid and adjacent benzene dipropionic 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 unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides are acrylic acid, methacrylic acid and Malaysia
At least one of acid anhydrides.
It is further preferred that the ether type monomer is methyl allyl alcohol polyoxyethylene ether, methacrylic polyoxyethylene is poly-
Oxypropylene ether, isoamyl alcohol polyoxyethylene ether, prenol polyoxyethylene poly-oxygen propylene aether, allyl alcohol polyethenoxy ether, allyl
Base polyoxyethylene poly-oxygen propylene aether, 4- hydroxy butyl vinyl ethers polyoxyethylene ether, 4- hydroxy butyl vinyl ether polyoxyethylene polyoxies
At least one of propylene ether.
It is further preferred that the initiator is water-soluble inorganic peroxide initiator, water soluble, redox primosome
System or water-soluble azo initiator.Preferably, the water-soluble inorganic peroxide initiator is in ammonium persulfate, potassium peroxydisulfate
At least one, it is hydrogen peroxide-sodium formaldehyde sulfoxylate, hydrogen peroxide-ascorbic acid and persulfate-that the water soluble, redox, which causes system,
At least one of sodium hydrogensulfite, the water-soluble azo initiator are azo diisobutyl amidine hydrochloride, azo diisopropyl
At least one of base imidazoline hydrochloride, azo dicyano valeric acid and azo dicyclohexyl formonitrile HCN.
It is further preferred that the molecular weight regulator is thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, phosphoric acid
At least one of trisodium, sodium formate, sodium acetate and lauryl mercaptan.
The beneficial effects of the invention are as follows：
1, method of the invention by the esterification products of unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid by being used for poly- carboxylic
The copolymerization of sour water-reducing agent introduces the structure of benzene dialkyl carboxylic acid, due to drawing when initial in polycarboxylate water-reducer molecule structure
Phenyl ring is entered, has increased space steric effect so that the initial water-reducing rate of product is improved.
When 2, water-reducing agent prepared by preparation method of the present invention will be used to be used for concrete, under the alkaline environment of concrete,
Ester bond in molecular structure can be hydrolyzed gradually, release the carboxyl with water-reducing effect, realize that excellent guarantor is collapsed effect, and due to
The rate of each structure hydrolysis is different, therefore protects the effect duration that collapses and can be adjusted according to actual conditions, better adaptability.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode.
Embodiment 1
(1) 239.80g hydroxy-ethyl acrylates, 100.00g terephthalic acid (TPA)s, 2.21g phenthazine are mixed, in nitrogen protection
Under, it is warming up to 60 DEG C, 4.23g p-methyl benzenesulfonic acid is added, is warming up to 120 DEG C, insulation reaction 1h, during which with vacuumizing or lead to nitrogen
Method with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted hydroxy-ethyl acrylate
First mixture；
(2) it is 2400 by the first mixture made from 10.00g steps (1), 14.50g acrylic acid, 200.00g molecular weight
Methyl allyl alcohol polyoxyethylene ether mixes, and 130.00g water is added and makes its dissolving, obtains copolymerized monomer mixture solution；
(3) by above-mentioned copolymerized monomer mixture solution and ammonium persulfate aqueous solution (wherein, ammonium persulfate 1.63g, water
30.00g), thioacetic acid aqueous solution (wherein, thioacetic acid 1.10g, water 30.00g) is instilled in 150.00g water and is reacted, instead
It is 70 DEG C to answer temperature, and time for adding 4.0h keeps the temperature 0.5h after being added dropwise, obtains copolymerization product；
(4) copolymerization product alkali made from step (3) pH to 5~7 is adjusted to get the ethers collapse protective poly-carboxylic acid to subtract
Aqua.
Embodiment 2
(1) by 110.00g hydroxy-ethyl acrylates, 110.00g hydroxypropyl acrylates, 100.00g to phenylenediacetic Acid, 1.60g
Hydroquinone, the mixing of 2.00g phenthazine are warming up to 50 DEG C under nitrogen protection, be added 4.20g mass fractions be 98% it is dense
Sulfuric acid is warming up to 115 DEG C, insulation reaction 3h, during which with vacuumizing or leading to method removing water of the nitrogen with water, drops after reaction
To room temperature, the first mixture containing esterification products and unreacted hydroxy-ethyl acrylate and hydroxypropyl acrylate is obtained；
(2) by the first mixture, 16.00g acrylic acid, 4.00g maleic anhydrides, 142.00g made from 5.00g steps (1)
The methacrylic polyoxyethylene poly-oxygen propylene aether that molecular weight is 2400 mixes, and 90.00g water is added and makes 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 0.30g, water 20.00g), mercaptopropionic acid aqueous solution (wherein, mercaptopropionic acid
1.20g, water 20.00g) it instills in 100.00g water and is reacted, reaction temperature is 40 DEG C, and time for adding 3.0h is added dropwise
After keep the temperature 1h, obtain copolymerization product；
(4) copolymerization product alkali made from step (3) pH to 5~7 is adjusted to get the ethers collapse protective poly-carboxylic acid to subtract
Aqua.
Embodiment 3
(1) 240g hydroxyethyl methacrylates, 100.00g mix benzene dipropionic acid, 3.20g hydroquinones, in nitrogen
Under protection, it is warming up to 60 DEG C, 7.30g ethylsulfonic acids are added, are warming up to 110 DEG C, insulation reaction 2h, during which with vacuumizing or lead to nitrogen
Method of the gas with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted hydroxyethyl methacrylate
First mixture of ethyl ester；
(2) it is 2400 by the first mixture made from 5.00g steps (1), 12.00g maleic anhydrides, 111.00g molecular weight
Allyl alcohol polyethenoxy ether mixing, and 90.00g water is added and makes its dissolving, obtain copolymerized monomer mixture solution；
(3) by above-mentioned copolymerized monomer mixture solution and persulfate aqueous solution (wherein, potassium peroxydisulfate 3.00g, water
30.00g), trisodium phosphate aqueous solution (wherein, tertiary sodium phosphate 1.30g, water 30.00g) is instilled in 100.00g water and is reacted, instead
It is 80 DEG C to answer temperature, and time for adding 3.0h keeps the temperature 1h after being added dropwise, obtains copolymerization product；
(4) copolymerization product alkali made from step (3) pH to 5~7 is adjusted to get the ethers collapse protective poly-carboxylic acid to subtract
Aqua.
Embodiment 4
(1) by phenylenediacetic Acid, 2.60g hexichol between 137.00g hydroxy-ethyl acrylates, 50.00g phthalic acids, 50.00g
Amine mixes, and under nitrogen protection, is warming up to 60 DEG C, and the concentrated sulfuric acid that 3.50g mass fractions are 98% is added, is warming up to 105 DEG C, protects
Temperature reaction 3h is down to room temperature, obtains containing esterification after reaction during which with vacuumizing or leading to method removing water of the nitrogen with water
First mixture of product and unreacted hydroxy-ethyl acrylate；
(2) the first mixture made from 5.00g steps (1), 9.00g acrylic acid, 2.00g maleic anhydrides, 130.00g are divided
Son amount mixes for 3000 isoamyl alcohol polyoxyethylene ether, and 90.00g water is added and makes its dissolving, obtains comonomer mixing
Object solution；
(3) by above-mentioned copolymerized monomer mixture solution and aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 1.00g, water 20.00g),
Sodium formaldehyde sulfoxylate aqueous solution (wherein, sodium formaldehyde sulfoxylate 0.60g, water 20.00g), isopropanol water solution (wherein, isopropanol 2.00g, water
It 20.00g) instills in 100.00g water and is reacted, reaction temperature is 50 DEG C, and time for adding 2.5h is kept the temperature after being added dropwise
1.5h obtains copolymerization product；
(4) copolymerization product alkali made from step (3) pH to 5~7 is adjusted to get the ethers collapse protective poly-carboxylic acid to subtract
Aqua.
Embodiment 5
(1) 282.00g hydroxypropyl acrylates, 100.00g terephthalic acid (TPA)s, 4.40g hydroquinones are mixed, is protected in nitrogen
Under shield, it is warming up to 50 DEG C, 5.60g benzene sulfonic acids are added, are warming up to 120 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 containing esterification products and unreacted hydroxypropyl acrylate
One mixture；
(2) by the first mixture made from 5.00g steps (1), 9.30g acrylic acid, 115.00g molecular weight be 3000 it is different
Pentenol polyoxyethylene poly-oxygen propylene aether mixes, and 90.00g water is added and makes 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 0.80g, water 30.00g), lauryl mercaptan aqueous solution (wherein, lauryl mercaptan 1.50g, water 30.00g) instill
It is reacted in 100.00g water, reaction temperature is 40 DEG C, and time for adding 3.0h keeps the temperature 3.0h after being added dropwise, and must be copolymerized production
Object；
(4) copolymerization product alkali made from step (3) pH to 5~7 is adjusted to get the ethers collapse protective poly-carboxylic acid to subtract
Aqua.
Ethers collapse protective poly-carboxylic acid water reducing agent obtained by embodiment 1 to embodiment 5 is tested, cement used is China
Moisten 42.5 Portland cements of P.O.According to GB/T8077-2012《Methods for testing uniformity of concrete admixture》To gained
Collapse protective poly-carboxylic acid water reducing agent carries out flowing degree of net paste of cement test, and W/C=0.29 rolls over (opposite when solid volume is 0.15wt%
In cement consumption), paste flowing degree is all higher than 220mm, and after 1h through when paste flowing degree be all higher than 200mm, and after 2h through when
Paste flowing degree is all higher than 170mm；According to GB/T8076-2008《Concrete admixture》To the ethers collapse protective poly-carboxylic acid of gained
Water-reducing agent carries out concrete test, rolls over when solid volume is 0.15wt% (relative to cement consumption), water-reducing rate is above 40%, collapses
Degree of falling 1h gradual loss amounts, which are respectively less than, is equal to 30mm, and slump 2h gradual loss amounts, which are respectively less than, is equal to 60mm.
Those of ordinary skill in the art it is found that the technical parameter and raw material components of present invention when changing in following ranges,
It remains to access same as the previously described embodiments or similar technique effect, still belong to and protection scope of the present invention：
A kind of preparation method of ethers collapse protective poly-carboxylic acid water reducing agent, includes the following steps：
(1) benzene dialkyl carboxylic acid, the polymerization inhibitor of the unsaturated carboxylic acid hydroxy ester of molecular weight≤200, molecular weight≤300 are mixed
It closes, under nitrogen protection, is warming up to 40~60 DEG C, adds catalyst, be warming up to 100~140 DEG C, 0.5~3h of insulation reaction,
Period removes water with vacuumizing or lead to method of the nitrogen with water, is down to room temperature after reaction, obtains containing esterification products and not
First mixture of the unsaturated carboxylic acid hydroxy ester of reaction, unsaturated carboxylic acid hydroxy ester and the molar ratio of benzene dialkyl carboxylic acid are
1.5~6:1, the dosage of catalyst is the 0.5%~5.0% of unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid gross mass, resistance
Poly- agent dosage is the 0.5%~5.0% of unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid gross mass；Preferably, by molecular weight
≤ 150 unsaturated carboxylic acid hydroxy ester, the benzene dialkyl carboxylic acid of molecular weight≤250, polymerization inhibitor mixing rise under nitrogen protection
Temperature adds catalyst to 50~60 DEG C, is warming up to 105~130 DEG C, 1~3h of insulation reaction, during which with vacuumizing or lead to nitrogen
Method with water removes water, is down to room temperature after reaction, obtains containing esterification products and unreacted unsaturated carboxylic acid hydroxyl
The molar ratio of first mixture of ester, unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid is 1.5~5:1, the dosage of catalyst
For unsaturated carboxylic acid hydroxy ester and the 0.5%~4.0% of benzene dialkyl carboxylic acid gross mass, polymerization inhibitor dosage is unsaturated carboxylic acid hydroxyl
Base ester and the 0.5%~4.0% of benzene dialkyl carboxylic acid gross mass.
(2) by the first mixture, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides made from step (1), molecular weight 600~
5000 ether type monomer is with 1:1~5:12~60 mass ratio mixing, and water is added and makes its dissolving, obtain comonomer mixing
Object solution；Preferably, by the first mixture, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, molecular weight 600 made from step (1)
~5000 ether type monomer is with 1:1~4:15~50 mass ratio mixing, and water is added and makes its dissolving, it is mixed to obtain comonomer
Polymer solution.
(3) above-mentioned copolymerized monomer mixture solution and initiator solution and molecular weight regulator aqueous solution are instilled in water
It is reacted, reaction temperature is 10~80 DEG C, and time for adding is 0.25~6.0h, 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) so that the mass concentration of the copolymerization product is 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；Preferably, by above-mentioned copolymerized monomer mixture solution and initiator
Aqueous solution and molecular weight regulator aqueous solution, which instill in water, to be reacted, and reaction temperature is 10~70 DEG C, time for adding 0.25
~5.0h keeps the temperature 0~3.0h, obtains copolymerization product after being added dropwise；The total amount of water used in the step and step (2) makes the copolymerization
The mass concentration of product is 20~70%, and the dosage of initiator is 0.5 of the gross mass of solute in copolymerized monomer mixture solution
~2.0%, the dosage of the molecular weight regulator is 0.2~2.0% of the gross mass of solute in copolymerized monomer mixture solution.
(4) copolymerization product alkali made from step (3) pH to 5~7 is adjusted to get the ethers collapse protective poly-carboxylic acid to subtract
Aqua.
The unsaturated carboxylic acid hydroxy ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, metering system
At least one of sour hydroxyl ethyl ester and hydroxy propyl methacrylate.
The benzene dialkyl carboxylic acid be terephthalic acid (TPA), to phenylenediacetic Acid, to benzene dipropionic acid, M-phthalic acid, isophthalic two
At least one of acetic acid, isophthalic dipropionic acid, phthalic acid, phthalic acid and adjacent benzene dipropionic acid.
The catalyst be ethylsulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and 98% at least one of the concentrated sulfuric acid.
The polymerization inhibitor is at least one of hydroquinone, phenthazine and diphenylamines.
The unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides be in acrylic acid, methacrylic acid and maleic anhydride at least
It is a kind of.
The ether type monomer is methyl allyl alcohol polyoxyethylene ether, methacrylic polyoxyethylene poly-oxygen propylene aether, isoamyl
Enol polyoxyethylene ether, prenol polyoxyethylene poly-oxygen propylene aether, allyl alcohol polyethenoxy ether, allyl polyethenoxy polyoxy
At least the one of propylene ether, 4- hydroxy butyl vinyl ethers polyoxyethylene ether, 4- hydroxy butyl vinyl ether polyoxyethylene poly-oxygen propylene aethers
Kind.
The initiator is water-soluble inorganic peroxide initiator, water soluble, redox initiation system or water-soluble azo
Initiator.Preferably, the water-soluble inorganic peroxide initiator is ammonium persulfate, at least one of potassium peroxydisulfate, described
It is in hydrogen peroxide-sodium formaldehyde sulfoxylate, hydrogen peroxide-ascorbic acid and persulphate-bisulphite sodium that water soluble, redox, which causes system,
At least one, the water-soluble azo initiator be azo diisobutyl amidine hydrochloride, azo dicyclohexyl formonitrile HCN hydrochloric acid
At least one of salt, azo dicyano valeric acid and azo dicyclohexyl formonitrile HCN.
The molecular weight regulator be thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, tertiary sodium phosphate, sodium formate,
At least one of 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 (12)
1. a kind of preparation method of ethers collapse protective poly-carboxylic acid water reducing agent, it is characterised in that：Include the following steps：
(1) the unsaturated carboxylic acid hydroxy ester of molecular weight≤200, the benzene dialkyl carboxylic acid of molecular weight≤300, polymerization inhibitor are mixed,
Under nitrogen protection, 40~60 DEG C are warming up to, catalyst is added, is warming up to 100~140 DEG C, 0.5~3h of insulation reaction, the phase
Between remove water with vacuumizing or lead to method of the nitrogen with water, be down to room temperature after reaction, obtain containing esterification products and not instead
The molar ratio of first mixture of the unsaturated carboxylic acid hydroxy ester answered, unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid is 1.5
~6:1, the dosage of catalyst is the 0.5%~5.0% of unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid gross mass, polymerization inhibitor
Dosage is the 0.5%~5.0% of unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid gross mass；
(2) by the first mixture, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, molecular weight 600~5000 made from step (1)
Ether type monomer with 1:1~5:12~60 mass ratio mixing, and water is added and makes its dissolving, it is molten to obtain copolymerized monomer mixture
Liquid；
(3) above-mentioned copolymerized monomer mixture solution is instilled with initiator solution and molecular weight regulator aqueous solution in water and is carried out
Reaction, reaction temperature are 10~80 DEG C, and time for adding is 0.25~6.0h, and 0~3.0h is kept the temperature after being added dropwise, must be copolymerized production
Object；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
It is 0.5~3.0% of the gross mass of solute in copolymerized monomer mixture solution, the dosage of molecular weight regulator is mixed for comonomer
The 0.2~3.0% of the gross mass of solute in polymer solution；
(4) alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the ethers collapse protective poly-carboxylic acid diminishing
Agent.
2. preparation method as described in claim 1, it is characterised in that：The step (1) is：By the insatiable hunger of molecular weight≤150
With carboxylic hydroxy group's ester, the benzene dialkyl carboxylic acid of molecular weight≤250, polymerization inhibitor mixing, under nitrogen protection, it is warming up to 50~60
DEG C, catalyst is added, is warming up to 105~130 DEG C, 1~3h of insulation reaction, during which with vacuumizing or the method with water of leading to nitrogen
Water is removed, is down to room temperature after reaction, it is mixed to obtain first containing esterification products and unreacted unsaturated carboxylic acid hydroxy ester
The molar ratio of conjunction object, unsaturated carboxylic acid hydroxy ester and benzene dialkyl carboxylic acid is 1.5~5:1, the dosage of catalyst is unsaturated carboxylic
Sour hydroxy ester and the 0.5%~4.0% of benzene dialkyl carboxylic acid gross mass, polymerization inhibitor dosage are unsaturated carboxylic acid hydroxy ester and benzene two
The 0.5%~4.0% of alkyl carboxylic acid gross mass.
3. preparation method as described in claim 1, it is characterised in that：The step (2) is：It will be first made from step (1)
Mixture, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, molecular weight 600~5000 ether type monomer with 1:1~4:15~50
Mass ratio mixes, and water is added and makes its dissolving, obtains copolymerized monomer mixture solution.
4. preparation method as described in claim 1, it is characterised in that：The step (3) is：By above-mentioned copolymerized monomer mixture
Solution, which is instilled with initiator solution and molecular weight regulator aqueous solution in water, to be reacted, and reaction temperature is 10~70 DEG C, drop
It is 0.25~5.0h between added-time, 0~3.0h is kept the temperature after being added dropwise, obtains copolymerization product；Water is total used in the step and step (2)
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 dosage of the 0.5~2.0% of gross mass, 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 hydroxyl
Base ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate and methacrylic acid hydroxypropyl
At least one of ester.
6. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The benzene dialkyl carboxylic acid
For terephthalic acid (TPA), to phenylenediacetic Acid, to benzene dipropionic acid, M-phthalic acid, phenylenediacetic Acid, isophthalic dipropionic acid, O-phthalic
At least one of acid, phthalic acid and adjacent benzene dipropionic acid.
7. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The catalyst is ethyl
Sulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and 98% at least one of the concentrated sulfuric acid.
8. 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.
9. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The unsaturated carboxylic acid and/
Or unsaturated carboxylic acid anhydrides are at least one of acrylic acid, methacrylic acid and maleic anhydride.
10. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The ether type monomer is first
Base allyl alcohol polyethenoxy ether, methacrylic polyoxyethylene poly-oxygen propylene aether, isoamyl alcohol polyoxyethylene ether, prenol are poly-
Ethylene oxide polyethenoxy ether, allyl alcohol polyethenoxy ether, allyl polyethenoxy polyethenoxy ether, 4- hydroxy butyl vinyl ethers are poly-
At least one of ethylene oxide ether, 4- hydroxy butyl vinyl ether polyoxyethylene poly-oxygen propylene aethers.
11. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The initiator is water-soluble
Property inorganic peroxy class initiator, water soluble, redox cause system or water-soluble azo initiator.
12. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The molecular weight regulator
For in thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan at least
It is a kind of.
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| 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 |
| 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 |
| CN108218282B (en) * | 2017-12-28 | 2020-03-06 | 科之杰新材料集团有限公司 | Preparation method of anti-mud viscosity-reducing polycarboxylic acid plasticizer |
| CN108047393B (en) * | 2017-12-28 | 2020-03-06 | 科之杰新材料集团有限公司 | Preparation method of viscosity-reduction-enhanced polycarboxylic acid plasticizer |
| CN109251279B (en) * | 2018-08-16 | 2020-09-04 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN109336447B (en) * | 2018-09-25 | 2021-05-11 | 上海东大化学有限公司 | Stable slump retaining agent and preparation and use methods thereof |
| CN111234095B (en) * | 2020-03-11 | 2021-07-16 | 安徽森普新型材料发展有限公司 | Method for preparing polycarboxylate superplasticizer by using C6 monomer |
| CN114316143B (en) * | 2021-12-28 | 2023-07-25 | 科之杰新材料集团有限公司 | Preparation method of chitosan-polyglycerol compound ether polycarboxylate water reducer |
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