CN108864375A - A kind of preparation method being retained anti-chamotte mould polycarboxylate water-reducer - Google Patents
A kind of preparation method being retained anti-chamotte mould polycarboxylate water-reducer Download PDFInfo
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- CN108864375A CN108864375A CN201810560901.4A CN201810560901A CN108864375A CN 108864375 A CN108864375 A CN 108864375A CN 201810560901 A CN201810560901 A CN 201810560901A CN 108864375 A CN108864375 A CN 108864375A
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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
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers 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
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
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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
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Abstract
The invention discloses a kind of preparation methods for being retained anti-chamotte mould polycarboxylate water-reducer, include the following steps：(1) esterification；(2) monomer blend；(3) copolyreaction；(4) neutralization reaction.Preparation method of the invention by by the esterification products copolymerized grafting of glucose, the first compound and the poly- alkyl diol of alkoxy into polycarboxylic acids strand, glucose ester structure, fluorobenzene based structures, phosphoric acid based structures, amino structure etc. are introduced in obtained polycarboxylate water-reducer molecule structure, under the mutual synergistic effect of these types of structure, so that polycarboxylate water-reducer of the invention has high-moisture-retention, the moisture content in concrete can effectively be lockked, control the hydrolysis rate of ester group, bleeding will not be lagged, and concrete flowability is stablized.
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of preparation for being retained anti-chamotte mould polycarboxylate water-reducer
Method.
Background technique
It is indispensable to have become preparation high performance concrete as a kind of chemical admixture for high performance water reducing agent of polyocarboxy acid
Component part, and make concrete material realize one of high performance and the important measures of greenization.It can be to greatest extent
Ground controls the water consumption of concrete, improves the durability of concrete, shortens setting time, improves normal concrete slump-loss
The disadvantages of too fast.But as infrastructure project quantity is by increase, cement, sand, stone material become increasingly complex in the market, at present quotient
The sandstone clay content used in product concrete is high, and polycarboxylate water-reducer is in application process to the quality fluctuation of concrete raw material
The phenomenon that very sensitive, especially winter low temperature is constructed, and lag bleeding occurs in the concrete of polycarboxylate water-reducer mixing is very general
Time.And it will affect the working performance, workability and endurance quality of concrete using the high sandstone material of this clay content.
Just to the performance of polycarboxylate water-reducer, more stringent requirements are proposed for this, it is desirable that develops a kind of while having high water conservation
The water-reducing agent of property and anti-mud.CN105669919A discloses a kind of high water conservation polycarboxylate water-reducer and preparation method thereof, the party
Water-reducing agent made from method has certain Water-saving effect, but without anti-mud effect.It is retained grinding for anti-chamotte mould polycarboxylate water-reducer
Study carefully there are also biggish space, in order to meet the market demand, develop a kind of anti-chamotte mould polycarboxylate water-reducer of water conservation have it is very great
Meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods for being retained anti-chamotte mould polycarboxylate water-reducer.
Technical scheme is as follows：
A kind of preparation method being retained anti-chamotte mould polycarboxylate water-reducer, includes the following steps：
(1) esterification：By glucose, the first compound, molecular weight be 400~5000 the poly- alkyl diol of alkoxy,
Polymerization inhibitor and catalyst, which are added in reaction kettle, to be mixed, and under nitrogen protection, 0.5~6h of constant temperature is reacted at 100~120 DEG C,
Period with vacuumizing or leading to method removing water of the nitrogen with water, is down to room temperature after reaction to get to esterification products and not anti-
The mixture for the first compound answered；Above-mentioned first compound is 2- amino -4- methyl -5- phosphorus -3- penetenoic acid, 2- amino -4-
Methyl -5- phosphorus -3- pentenoic acid ethyl ester, 2- amino -4- methyl -5- phosphorus -3- amylene-4 acid methyl ester, 2- amino -4- methyl -5- phosphorus -3-
Amylene propyl propionate, 2- amino -4- ethyl -5- phosphorus -3- pentenoic acid ethyl ester, 2- amino -4- ethyl -5- phosphorus -3- amylene propyl propionate, 2-
Amino -4- ethyl -5- phosphorus -3- amylene-4 acid methyl ester, the amyl- 3- olefin(e) acid of 2- amino -4- methyl -5- phosphono, 2- amino -5- phosphono are amyl-
3- olefin(e) acid, 1- amino -3- phosphono -2- cyclopentene -1- carboxylic acid, at least one in 1- amino -3- phosphono -3- cyclopentene -1- carboxylic acid
Kind；The above-mentioned poly- alkyl diol of alkoxy is methoxy poly (ethylene glycol), methoxy poly (ethylene glycol) polypropylene glycol copolymers, ethyoxyl are poly-
At least one of ethylene glycol and ethyoxyl polyethylene glycol polypropylene glycol copolymers；
(2) monomer blend：By mixture made from step (1), unsaturated fluorine-containing minor comonomer, unsaturated carboxylic acid or unsaturation
Carboxylic acid anhydrides and esters of unsaturated carboxylic acids mixing, and water is added and makes its dissolution, obtain copolymerized monomer mixture solution；Above-mentioned unsaturation
Fluorine-containing minor comonomer is 3- fluoro cinnamic acid methyl esters, 4- fluoro cinnamic acid methyl esters, 3- (2- fluorophenyl) propyl- 2- olefin(e) acid ethyl ester, 3- (4- fluorobenzene
Base)-ethyl acrylate, 3- (3- fluorophenyl) ethyl acrylate, 3- (3- fluorophenyl) ethyl acrylate, 4- amino -3- fluorine allyl
Yl benzoic acid ester, 5- (4- fluoro-phenyl) -2- amylene-4 acid methyl ester, the fluoro- 4- p-Methoxymethylcinnamate of 2-, 2,3- cinnamic acid difluoride
Ethyl ester, 3- (2,4- difluorophenyl) ethyl acrylate, 3- (3,5- difluorophenyl) ethyl acrylate, 3- (2- ethyl -4- fluorobenzene
At least one of base) ethyl acrylate；Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides be acrylic acid, methacrylic acid, fumaric acid,
At least one of itaconic acid, maleic anhydride, itaconic anhydride；Above-mentioned esters of unsaturated carboxylic acids is hydroxy-ethyl acrylate, metering system
Sour hydroxyl ethyl ester, hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, Isooctyl acrylate monomer, methacrylic acid are different
At least one of monooctyl ester and methyl methacrylate；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill water in reacted, reaction temperature be 10~60 DEG C, time for adding be 0.8~5.0h, after being added dropwise keep the temperature 0~
4.2h obtains copolymerization product；The total amount of water used in the step and step (2) make the copolymerization product mass concentration be 20~
80%；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the anti-mud of water conservation
Type polycarboxylate water-reducer.
In a preferred embodiment of the invention, in the step (1), glucose, the first compound and molecular weight
Molar ratio for 400~5000 poly- alkyl diol of alkoxy is 1: 3~10: 0.5~5, catalyst amount be the first compound,
The 0.6~5.0% of glucose and the poly- alkyl diol gross mass of alkoxy, polymerization inhibitor dosage are the first compound, glucose and alkane
The 0.5~4.0% of the poly- alkyl diol gross mass of oxygroup.
In a preferred embodiment of the invention, in the step (2), mixture, unsaturation made from step (1)
The mass ratio of fluorine-containing minor comonomer, unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and esters of unsaturated carboxylic acids be 200: 1.0~2.6: 6.5~
30: 2.5~15.
In a preferred embodiment of the invention, in the step (3), the dosage of initiator is comonomer mixing
The 0.5~4.0% of the gross mass of solute in object solution, the dosage of molecular weight regulator are solute in copolymerized monomer mixture solution
Gross mass 0.3~3.0%.
It is further preferred that the catalyst is in the concentrated sulfuric acid, periodic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and ethylsulfonic acid
At least one.
It is further preferred that the polymerization inhibitor is at least one of phenthazine, hydroquinone and diphenylamines.
It is further preferred that the initiator is that water soluble, redox causes system or water-soluble azo initiator.
It is further preferred that the molecular weight regulator is thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, secondary phosphorus
At least one of sour sodium, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan.
The beneficial effects of the invention are as follows：
1, preparation method of the invention is by by the esterification products of glucose, the first compound and the poly- alkyl diol of alkoxy
Copolymerized grafting introduces glucose ester structure, fluorobenzene into polycarboxylic acids strand in obtained polycarboxylate water-reducer molecule structure
Based structures, phosphoric acid based structures, amino structure etc., under the mutual synergistic effect of these types of structure, so that polycarboxylic acids of the invention
Water-reducing agent has high-moisture-retention, can effectively lock the moisture content in concrete, control the hydrolysis rate of ester group, will not lag and secrete
Water, and concrete flowability is stablized.
2, preparation method of the invention is by by the esterification products of glucose, the first compound and the poly- alkyl diol of alkoxy
It is copolymerized in polycarboxylic acids molecule containing phosphate and glucose ester structure with fluorophenyl collective effect, there is better robust layer
Effect can be such that mud and mountain flour in concrete is sufficiently spread out, and have excellent anti-mud effect.
3, the parent that the glucose ester structure that polycarboxylate water-reducer molecule structure made from preparation method of the present invention introduces contains
Water base group is more, and glucose ester structure is interspersed in fluorobenzene based structures, phosphoric acid based structures, amino structure and carboxylate structure, energy
Enough increase space steric effect, makes cement that there is better dispersion effect, and water-reducing rate is high, workability is good.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment.
Embodiment 1
(1) esterification：By 180.00g glucose, 758.00g2- amino -4- methyl -5- phosphorus -3- pentenoic acid ethyl ester,
Methoxy poly (ethylene glycol), 15.00g phenthazine and the 18.00g p-methyl benzenesulfonic acid that 1000.00g molecular weight is 1000 are added to reaction
It is mixed in kettle, under nitrogen protection, constant temperature 4.0h is reacted at 110 DEG C, during which removed with the method for water with vacuumizing or lead to nitrogen
Water is removed, is down to room temperature after reaction to get esterification products and unreacted 2- amino -4- methyl -5- phosphorus -3- penetenoic acid second is arrived
The mixture of ester；
(2) monomer blend：：By mixture made from 200.00g step (1), 1.20g 3- (2- fluorophenyl) propyl- 2- olefin(e) acid
Ethyl ester, 12.00g acrylic acid, the mixing of 8.00g hydroxy-ethyl acrylate, and 100.00g water is added and makes its dissolution, it is single to obtain copolymerization
Body 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 0.40g, water 20.00g) and thioacetic acid aqueous solution (wherein thioacetic acid 0.90g,
Water 20.00g) it instills in 60.00g water and is reacted, reaction temperature is 50 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 (1) is adjusted into pH to 5~7 to get the anti-mud of water conservation
Type polycarboxylate water-reducer PCE-1.
Embodiment 2
(1) esterification：By 180.00g glucose, 731.00g2- amino -4- methyl -5- phosphorus -3- penetenoic acid,
Methoxy poly (ethylene glycol) polypropylene glycol copolymers, 12.00g phenthazine and the 15.00g ethylsulfonic acid that 960.00g molecular weight is 800
It is added in reaction kettle and mixes, under nitrogen protection, constant temperature 5.0h is reacted at 120 DEG C, during which with vacuumizing or lead to nitrogen band
The method of water removes water, is down to room temperature after reaction to get esterification products and unreacted 2- amino -4- methyl -5- phosphorus-is arrived
The mixture of 3- penetenoic acid；
(2) monomer blend：：By mixture made from 200.00g step (1), 2.00g 4- fluoro cinnamic acid methyl esters, 16.00
Maleic anhydride and the mixing of 6.00g hydroxyethyl methacrylate, and 100.00g water is added and makes its dissolution, it is mixed to obtain comonomer
Polymer 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) and aqueous sodium acetate solution (wherein sodium acetate 2.00g, water 20.00g) drop
Enter and reacted in 60.00g water, reaction temperature is 40 DEG C, and time for adding 4.0h keeps the temperature 2.0h after being added dropwise, and must be copolymerized
Product；
(4) neutralization reaction：The alkali of copolymerization product made from step (1) is adjusted into pH to 5~7 to get the anti-mud of water conservation
Type polycarboxylate water-reducer PCE-2.
Embodiment 3
(1) esterification：By 180.00g glucose, the amyl- 3- olefin(e) acid of 752.00g2- amino -4- methyl -5- phosphono,
Ethyoxyl polyethylene glycol, 22.00g hydroquinone and the 20.00g benzene sulfonic acid that 1440g molecular weight is 1200 are added in reaction kettle
Mixing reacts constant temperature 4.0h under nitrogen protection at 100 DEG C, during which removes water with vacuumizing or lead to method of the nitrogen with water,
It is down to room temperature after reaction to get to the mixed of esterification products and the amyl- 3- olefin(e) acid of unreacted 2- amino -4- methyl -5- phosphono
Close object；
(2) monomer blend：：By mixture made from 200.00g step (1), 2.10g 3- (2,4- difluorophenyl) propylene
Acetoacetic ester, 18.00g itaconic acid and the mixing of 10.00g hydroxypropyl acrylate, and 100.00g water is added and makes its dissolution, it is total to
Polycondensation monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein azo two
Cyanopentanoic acid 3.60g, water 40.00g) and trisodium phosphate aqueous solution (wherein tertiary sodium phosphate 1.80g, water 20.00g) instillation 60.00g
It is reacted in water, reaction temperature is 30 DEG C, and time for adding 3.0h keeps the temperature 2.0h after being added dropwise, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (1) is adjusted into pH to 5-7 to get the anti-chamotte mould of water conservation
Polycarboxylate water-reducer PCE-3.
Embodiment 4
(1) esterification：By 180.00g glucose, the amyl- 3- olefin(e) acid of 780.00g2- amino -5- phosphono, 1900.00g points
Son amount is added to reaction for 2400 ethyoxyl polyethylene glycol polypropylene glycol copolymers, 17.00g diphenylamines and 18.00g periodic acid
It is mixed in kettle, under nitrogen protection, constant temperature 3.0h is reacted at 105 DEG C, during which removed with the method for water with vacuumizing or lead to nitrogen
Water is removed, is down to room temperature after reaction to get mixing to esterification products and the amyl- 3- olefin(e) acid of unreactedization 2- amino -5- phosphono
Close object；
(2) monomer blend：：By mixture made from 200.00g step (1), 1.80g 4- amino -3- fluorine allyl benzene first
Acid esters, 20.00g acrylic acid and the mixing of 5.00g Isooctyl acrylate monomer, and 100.00g water is added and makes its dissolution, it is single to obtain copolymerization
Body mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 3.60g, water
20.00g), trisodium phosphate aqueous solution (wherein, tertiary sodium phosphate 3.00g, water 20.00g), aqueous ascorbic acid are (wherein, anti-bad
Hematic acid 0.90, water 20.00g) it instills in 60.00g water and is reacted, reaction temperature is 45 DEG C, and time for adding 2.0h is dripped
3.0h is kept the temperature after finishing, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (1) is adjusted into pH to 5~7 to get the anti-mud of water conservation
Type polycarboxylate water-reducer PCE-4.
Embodiment 5
(1) esterification：By 180.00g glucose, 788.00g1- amino -3- phosphono -2- cyclopentene -1- carboxylic acid,
Methoxy poly (ethylene glycol), 26.00g hydroquinone and the 30.00g concentrated sulfuric acid that 2800.00g molecular weight is 1600 are added to reaction kettle
Middle mixing reacts constant temperature 5.0h under nitrogen protection at 110 DEG C, is during which removed with vacuumizing or lead to method of the nitrogen with water
Water is down to room temperature after reaction to get to esterification products and unreacted 1- amino -3- phosphono -2- cyclopentene -1- carboxylic acid
Mixture；
(2) monomer blend：：By mixture made from 200.00g step (1), 1.50g 3- fluoro cinnamic acid methyl esters, 2.00g
Itaconic anhydride, 10.00g acrylic acid and the mixing of 10.00g hydroxyethyl methacrylate, and 100.00g water is added and makes its dissolution,
Obtain copolymerized monomer mixture solution；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, azo dicyano valeric acid aqueous solution (wherein, azo two
Cyanopentanoic acid 3.00g, water 40.00g), sodium hypophosphite aqueous solution (wherein, sodium hypophosphite 2.80g, water 20.00g) instill 60.00g
It is reacted in water, reaction temperature is 55 DEG C, and time for adding 2.0h keeps the temperature 1.0h after being added dropwise, obtains copolymerization product；
(4) neutralization reaction：The alkali of copolymerization product made from step (1) is adjusted into pH to 5~7 to get the anti-mud of water conservation
Type polycarboxylate water-reducer PCE-5.
To the anti-chamotte mould polycarboxylate water-reducer of water conservation and commercially available water-retaining type polycarboxylic acids obtained by embodiment 1 to embodiment 5
Water-reducing agent (PCE) carries out testing concrete performance according to solid volume 0.06% is rolled over, and adds 4.0% bentonite and 1.0% kaolin
(relative to cement consumption), test concrete initial slump, divergence, through when the slump and divergence, normal pressure bleeding rate, adopt
With 42.5 ordinary portland cement of China Resources P.O, concrete mix is：Cement 180kg/m3, flyash 60kg/m3, miberal powder
60kg/m3, sand 820kg/m3, stone 1055kg/m3, water 165kg/m3, acquired results are as shown in table 1.
The testing concrete performance result of the different additives of table 1
As shown in Table 1, using the anti-chamotte mould polycarboxylate water-reducer of water conservation prepared by the present invention than commercially available water-retaining type polycarboxylic acids
Water-reducing agent (PCE) has apparent anti-mud effect, higher water-reducing rate and function of slump protection, does not lose after 3h and also do not amplify, coagulation
Soil stabilization is good, and normal pressure bleeding rate is significantly lower than commercially available water-retaining type polycarboxylate water-reducer, illustrates that ethers prepared by the present invention is high
Water-retaining type polycarboxylate water-reducer has many advantages, such as that high-moisture-retention, anti-mud, high water reducing rate, high-thin arch dam and stability are good.
Those of ordinary skill in the art still are able to it is found that when technical solution of the present invention changes in following ranges
To same as the previously described embodiments or similar technical effect, protection scope of the present invention is still fallen within：
A kind of preparation method being retained anti-chamotte mould polycarboxylate water-reducer, includes the following steps：
(1) esterification：By glucose, the first compound, molecular weight be 400~5000 the poly- alkyl diol of alkoxy,
Polymerization inhibitor and catalyst, which are added in reaction kettle, to be mixed, and under nitrogen protection, 0.5~6h of constant temperature is reacted at 100~120 DEG C,
Period with vacuumizing or leading to method removing water of the nitrogen with water, is down to room temperature after reaction to get to esterification products and not anti-
The mixture for the first compound answered；Above-mentioned first compound is 2- amino -4- methyl -5- phosphorus -3- penetenoic acid, 2- amino -4-
Methyl -5- phosphorus -3- pentenoic acid ethyl ester, 2- amino -4- methyl -5- phosphorus -3- amylene-4 acid methyl ester, 2- amino -4- methyl -5- phosphorus -3-
Amylene propyl propionate, 2- amino -4- ethyl -5- phosphorus -3- pentenoic acid ethyl ester, 2- amino -4- ethyl -5- phosphorus -3- amylene propyl propionate, 2-
Amino -4- ethyl -5- phosphorus -3- amylene-4 acid methyl ester, the amyl- 3- olefin(e) acid of 2- amino -4- methyl -5- phosphono, 2- amino -5- phosphono are amyl-
3- olefin(e) acid, 1- amino -3- phosphono -2- cyclopentene -1- carboxylic acid, at least one in 1- amino -3- phosphono -3- cyclopentene -1- carboxylic acid
Kind；The above-mentioned poly- alkyl diol of alkoxy is methoxy poly (ethylene glycol), methoxy poly (ethylene glycol) polypropylene glycol copolymers, ethyoxyl are poly-
At least one of ethylene glycol and ethyoxyl polyethylene glycol polypropylene glycol copolymers；
(2) monomer blend：By mixture made from step (1), unsaturated fluorine-containing minor comonomer, unsaturated carboxylic acid or unsaturation
Carboxylic acid anhydrides and esters of unsaturated carboxylic acids mixing, and water is added and makes its dissolution, obtain copolymerized monomer mixture solution；Above-mentioned unsaturation
Fluorine-containing minor comonomer is 3- fluoro cinnamic acid methyl esters, 4- fluoro cinnamic acid methyl esters, 3- (2- fluorophenyl) propyl- 2- olefin(e) acid ethyl ester, 3- (4- fluorobenzene
Base)-ethyl acrylate, 3- (3- fluorophenyl) ethyl acrylate, 3- (3- fluorophenyl) ethyl acrylate, 4- amino -3- fluorine allyl
Yl benzoic acid ester, 5- (4- fluoro-phenyl) -2- amylene-4 acid methyl ester, the fluoro- 4- p-Methoxymethylcinnamate of 2-, 2,3- cinnamic acid difluoride
Ethyl ester, 3- (2,4- difluorophenyl) ethyl acrylate, 3- (3,5- difluorophenyl) ethyl acrylate, 3- (2- ethyl -4- fluorobenzene
At least one of base) ethyl acrylate；Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides be acrylic acid, methacrylic acid, fumaric acid,
At least one of itaconic acid, maleic anhydride, itaconic anhydride；Above-mentioned esters of unsaturated carboxylic acids is hydroxy-ethyl acrylate, metering system
Sour hydroxyl ethyl ester, hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, Isooctyl acrylate monomer, methacrylic acid are different
At least one of monooctyl ester and methyl methacrylate；
(3) copolyreaction：By above-mentioned copolymerized monomer mixture solution, initiator solution and molecular weight regulator aqueous solution
Instill water in reacted, reaction temperature be 10~60 DEG C, time for adding be 0.8~5.0h, after being added dropwise keep the temperature 0~
4.2h obtains copolymerization product；The total amount of water used in the step and step (2) make the copolymerization product mass concentration be 20~
80%；
(4) neutralization reaction：The alkali of copolymerization product made from step (3) is adjusted into pH to 5~7 to get the anti-mud of water conservation
Type polycarboxylate water-reducer.
In the step (1), glucose, the first compound and molecular weight be 400~5000 the poly- alkyl diol of alkoxy
Molar ratio be 1: 3~10: 0.5~5, catalyst amount be the first compound, glucose and the total matter of the poly- alkyl diol of alkoxy
The 0.6~5.0% of amount, polymerization inhibitor dosage be the first compound, glucose and the poly- alkyl diol gross mass of alkoxy 0.5~
4.0%.In the step (2), mixture made from step (1), unsaturated fluorine-containing minor comonomer, unsaturated carboxylic acid or unsaturated carboxylic
The mass ratio of acid anhydrides and esters of unsaturated carboxylic acids is 200: 1.0~2.6: 6.5~30: 2.5~15.In the step (3), initiator
Dosage be 0.5~4.0% of the gross mass of solute in copolymerized monomer mixture solution, the dosage of molecular weight regulator is copolymerization
The 0.3~3.0% of the gross mass of solute in monomer mixture solution.
The catalyst is at least one of the concentrated sulfuric acid, periodic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and ethylsulfonic acid.Institute
Stating polymerization inhibitor is at least one of phenthazine, hydroquinone and diphenylamines.The initiator is water soluble, redox initiation
System or water-soluble azo initiator.The molecular weight regulator is thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, secondary
At least one of sodium phosphate, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (8)
1. a kind of preparation method for being retained anti-chamotte mould polycarboxylate water-reducer, it is characterised in that：Include the following steps：
(1) esterification：By glucose, the first compound, the poly- alkyl diol of alkoxy that molecular weight is 400~5000, polymerization inhibitor
Agent and catalyst, which are added in reaction kettle, to be mixed, and under nitrogen protection, 0.5~6h of constant temperature is reacted at 100~120 DEG C, during which
Water is removed with vacuumizing or leading to method of the nitrogen with water, is down to room temperature after reaction to get to esterification products and unreacted
The mixture of first compound；Above-mentioned first compound is 2- amino -4- methyl -5- phosphorus -3- penetenoic acid, 2- amino -4- methyl -
5- phosphorus -3- pentenoic acid ethyl ester, 2- amino -4- methyl -5- phosphorus -3- amylene-4 acid methyl ester, 2- amino -4- methyl -5- phosphorus -3- penetenoic acid
Propyl ester, 2- amino -4- ethyl -5- phosphorus -3- pentenoic acid ethyl ester, 2- amino -4- ethyl -5- phosphorus -3- amylene propyl propionate, 2- amino -
4- ethyl -5- phosphorus -3- amylene-4 acid methyl ester, the amyl- 3- olefin(e) acid of 2- amino -4- methyl -5- phosphono, the amyl- 3- alkene of 2- amino -5- phosphono
At least one of acid, 1- amino -3- phosphono -2- cyclopentene -1- carboxylic acid, 1- amino -3- phosphono -3- cyclopentene -1- carboxylic acid；On
Stating the poly- alkyl diol of alkoxy is methoxy poly (ethylene glycol), methoxy poly (ethylene glycol) polypropylene glycol copolymers, the poly- second two of ethyoxyl
At least one of pure and mild ethyoxyl polyethylene glycol polypropylene glycol copolymers；
(2) monomer blend：By mixture made from step (1), unsaturated fluorine-containing minor comonomer, unsaturated carboxylic acid or unsaturated carboxylic acid
Acid anhydride and esters of unsaturated carboxylic acids mixing, and water is added and makes its dissolution, obtain copolymerized monomer mixture solution；Above-mentioned unsaturation is fluorine-containing
Minor comonomer is 3- fluoro cinnamic acid methyl esters, 4- fluoro cinnamic acid methyl esters, 3- (2- fluorophenyl) propyl- 2- olefin(e) acid ethyl ester, 3- (4- fluorophenyl)-
Ethyl acrylate, 3- (3- fluorophenyl) ethyl acrylate, 3- (3- fluorophenyl) ethyl acrylate, 4- amino -3- fluorine allyl benzene
Formic acid esters, 5- (4- fluoro-phenyl) -2- amylene-4 acid methyl ester, the fluoro- 4- p-Methoxymethylcinnamate of 2-, 2,3- cinnamic acid difluoride ethyl ester,
3- (2,4- difluorophenyl) ethyl acrylate, 3- (3,5- difluorophenyl) ethyl acrylate, 3- (2- ethyl -4- fluorophenyl) propylene
At least one of acetoacetic ester；Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides be acrylic acid, methacrylic acid, fumaric acid, itaconic acid,
At least one of maleic anhydride, itaconic anhydride；Above-mentioned esters of unsaturated carboxylic acids is hydroxy-ethyl acrylate, hydroxyethyl methacrylate second
Ester, hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, Isooctyl acrylate monomer, isooctyl methacrylate and
At least one of methyl methacrylate；
(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 10~60 DEG C, and time for adding is 0.8~5.0h, and 0~4.2h is kept the temperature after being added dropwise, is obtained
Copolymerization product；The total amount of water used in the step and step (2) makes the mass concentration of the copolymerization product be 20~80%；
(4) neutralization reaction：It is poly- to get the anti-chamotte mould of water conservation that the alkali of copolymerization product made from step (3) is adjusted into pH to 5~7
Carboxylic acid water reducer.
2. preparation method as described in claim 1, it is characterised in that：In the step (1), glucose, the first compound and
The molar ratio of the poly- alkyl diol of the alkoxy that molecular weight is 400~5000 is 1: 3~10: 0.5~5, catalyst amount first
The 0.6~5.0% of compound, glucose and the poly- alkyl diol gross mass of alkoxy, polymerization inhibitor dosage are the first compound, grape
The 0.5~4.0% of sugar and the poly- alkyl diol gross mass of alkoxy.
3. preparation method as described in claim 1, it is characterised in that：In the step (2), mixture made from step (1),
The mass ratio of unsaturated fluorine-containing minor comonomer, unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides and esters of unsaturated carboxylic acids is 200: 1.0~2.6
: 6.5~30: 2.5~15.
4. preparation method as described in claim 1, it is characterised in that：In the step (3), the dosage of initiator is that copolymerization is single
The 0.5~4.0% of the gross mass of solute in body mixture solution, the dosage of molecular weight regulator are copolymerized monomer mixture solution
The 0.3~3.0% of the gross mass of middle solute.
5. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The catalyst is dense sulphur
At least one of acid, periodic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid and ethylsulfonic acid.
6. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The polymerization inhibitor is pheno thiophene
At least one of piperazine, hydroquinone and diphenylamines.
7. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The initiator is water-soluble
Property redox initiation system or water-soluble azo initiator.
8. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The molecular weight regulator
For thioacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, tertiary sodium phosphate, sodium formate, sodium acetate and lauryl mercaptan
At least one of.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272458A (en) * | 2019-06-25 | 2019-09-24 | 北京金隅水泥节能科技有限公司 | Function monomer and preparation method thereof, water-reducing agent and its preparation method and application and concrete |
| CN110894284A (en) * | 2019-12-23 | 2020-03-20 | 湖北荆州华邦化学有限公司 | Polyester polyol for refrigerator heat insulation polyurethane foam composite material and preparation method thereof |
| CN111154048A (en) * | 2020-01-07 | 2020-05-15 | 湖北凯祥新技术有限公司 | Long-branch-chain-end hydroxyl-grafted sugar molecule mud-resistant polycarboxylate superplasticizer and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2541218B2 (en) * | 1987-05-15 | 1996-10-09 | 日本油脂株式会社 | Additive for cement |
| CN101172805A (en) * | 2007-10-29 | 2008-05-07 | 武汉理工大学 | Monosaccharide inarch polycarboxylic acids high efficiency water reducing agent and preparation method thereof |
| CN106279559A (en) * | 2016-07-26 | 2017-01-04 | 上海台界化工有限公司 | A kind of saccharide carboxylate modified polycarboxylic acid water reducer and preparation method thereof |
| CN107501482A (en) * | 2017-09-20 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of low responsive type polycarboxylate water-reducer |
| CN108047393A (en) * | 2017-12-28 | 2018-05-18 | 科之杰新材料集团有限公司 | A kind of preparation method for enhancing viscosity reduction type polycarboxylic acids plasticiser |
-
2018
- 2018-06-01 CN CN201810560901.4A patent/CN108864375B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2541218B2 (en) * | 1987-05-15 | 1996-10-09 | 日本油脂株式会社 | Additive for cement |
| CN101172805A (en) * | 2007-10-29 | 2008-05-07 | 武汉理工大学 | Monosaccharide inarch polycarboxylic acids high efficiency water reducing agent and preparation method thereof |
| CN106279559A (en) * | 2016-07-26 | 2017-01-04 | 上海台界化工有限公司 | A kind of saccharide carboxylate modified polycarboxylic acid water reducer and preparation method thereof |
| CN107501482A (en) * | 2017-09-20 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of low responsive type polycarboxylate water-reducer |
| CN108047393A (en) * | 2017-12-28 | 2018-05-18 | 科之杰新材料集团有限公司 | A kind of preparation method for enhancing viscosity reduction type polycarboxylic acids plasticiser |
Cited By (8)
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|---|---|---|---|---|
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| CN110894284A (en) * | 2019-12-23 | 2020-03-20 | 湖北荆州华邦化学有限公司 | Polyester polyol for refrigerator heat insulation polyurethane foam composite material and preparation method thereof |
| CN111154048A (en) * | 2020-01-07 | 2020-05-15 | 湖北凯祥新技术有限公司 | Long-branch-chain-end hydroxyl-grafted sugar molecule mud-resistant polycarboxylate superplasticizer and application thereof |
| CN112708052A (en) * | 2020-10-30 | 2021-04-27 | 科之杰新材料集团(贵州)有限公司 | Ether viscosity-reducing hydration regulator and preparation method thereof |
| CN112708052B (en) * | 2020-10-30 | 2022-10-25 | 科之杰新材料集团(贵州)有限公司 | Ether viscosity-reducing hydration regulator and preparation method thereof |
| CN113980198A (en) * | 2021-11-01 | 2022-01-28 | 科之杰新材料集团有限公司 | Slow-release controllable polycarboxylic slump retaining agent and preparation method thereof |
| CN113980198B (en) * | 2021-11-01 | 2023-07-25 | 科之杰新材料集团有限公司 | Sustained-release controllable polycarboxylic acid slump retaining agent and preparation method thereof |
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