CN108250447A - Polyether modified amino sulfonate high efficiency water reducing agent, preparation method and application - Google Patents
Polyether modified amino sulfonate high efficiency water reducing agent, preparation method and application Download PDFInfo
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- CN108250447A CN108250447A CN201611236905.4A CN201611236905A CN108250447A CN 108250447 A CN108250447 A CN 108250447A CN 201611236905 A CN201611236905 A CN 201611236905A CN 108250447 A CN108250447 A CN 108250447A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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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
Abstract
The present invention provides a kind of polyether modified amino sulfonate high efficiency water reducing agent, preparation method and applications, by the graft polyether side chain on sulfamate water reducer molecular backbone, increase the peptizaiton of Water-reducing Admixtures To Cements particle, improve slump retaining.The preparation method includes the following steps：(1) using the polyethers of the hydroxyl of specific structure as solvent, make amino phenyl sulfonyl hydrochlorate, phenolsulfonate, salicylic acid, phenolic compound, urea under acid condensation catalyst effect, condensation reaction occurs with aldehyde compound, obtains carboxylic sulfamate water reducer intermediate；(2) in the presence of water entrainer and esterification catalyst, the polyethers and carboxylic sulfamate water reducer intermediate for making the hydroxyl carry out esterification, remove water entrainer plus alkali neutralization, polyether-modified sulfamate water reducer is obtained, the molecular weight of the polyether-modified sulfamate water reducer is 24,000 38000.
Description
Technical field
The present invention relates to a kind of polyether modified amino sulfonate high efficiency water reducing agent, preparation method and applications, belong to coagulation
Native additive technical field.
Background technology
Concrete is widely used in various fields as a kind of construction material, with the development of concrete also promote it is mixed
Solidifying soil additive technology rapidly develops, and concrete admixture is one of essential component in modern concrete, is concrete
A kind of modified important method and technology.Common additive kind mainly has water-reducing agent, retarder, air entraining agent, early strength agent, prevents
Freeze agent, swelling agent etc., and water-reducing agent is wherein most important component part.The type of domestic high efficiency water reducing agent is main at present
Have：Sulfamate high-effective water-reducing agent, naphthalene sulfonate high efficiency water reducing agent, melamine sulfonate high efficiency water reducing agent etc..
Sulfamate high-effective water-reducing agent is a kind of non-bleed resin type efficient additive, and it is additional to belong to low alkaline concrete
Agent, be condensed under certain condition by mononuclear aromatics derivative, phenol compound, p-aminobenzene sulfonic acid and aldehyde compound and
Into.Hydroxyl (- OH), sulfonic group (- SO are introduced in the agent structure of sulfamate analog high efficiency water reducing agent3), amino (- NH2) etc.
Polar group, stronger interaction occurs by cement particle surface in they, including hydrogen bond, covalent bond, Acid-Base active force,
The effects that Van der Waals force, so as to generate absorption, the ionogen of macromolecular institute band adsorbed has very strong negative electrical charge, makes
Generate huge repulsion between cement granules, so as to overcome intergranular Van der Waals force, form a dispersion.Sulfamic acid
Salt based water reducer is because it is with simple production process, and to the good dispersion of cement particle, water-reducing rate is big, concrete strength obtained
High, the advantages that durability is good and as the domestic high efficiency water reducing agent with preferable future at present.But due to its own molecule knot
The limitation of structure and peptizaiton mechanism so that they are there are a series of as volume is big, damage of collapsing is big, shrinks big, concrete water bleeding
The problems such as serious.
For sulfamate analog high efficiency water reducing agent there are the problem of, many researchers to sulfamate water reducer carry out
Modification.Salicylic acid is introduced into sulfamate strand by patent document CN 104961375A, has been obtained one kind and has been contained carboxyl
The sulfamate high-effective water-reducing agent of adsorption group, volume is small, and water-reducing effect is good.Patent document CN 1970489A are by naphthalene sulphur
Hydrochlorate formaldehyde condensation products macromolecular is introduced into sulfamic acid molecules of salt, and obtained water-reducing agent workability is good, and concrete is enhanced
It is with obvious effects.Patent document CN 101824128A first by betanaphthol sulfonation, then contract with sulfamate water reducer molecule again
It closes, obtains beta-naphthol produced waste liquid modified sulfamate high-effective water-reducing agent, the workability of concrete is good, can reduce and subtract
Aqua production cost.It, can be to sulfamate high-effective although Many researchers are all modified sulfamate water reducer
The dispersion of water-reducing agent and slump retaining have some improvement, but it is mainly by introducing other adsorption groups on main chain,
Do not change the peptizaiton mechanism of water-reducing agent, rely primarily on electrostatic repulsion and disperseed, therefore cannot fundamentally solve it
The problems such as water-reducing rate is low, and volume is high, and damage of collapsing is big.
The polycarboxylate water-reducer of numerous document reports has the advantages of volume is small, and slip is high, and slump retaining is good, excellent
Water reducing ability comes from the combed molecular structure of polycarboxylate water-reducer, and the water-reducing agent of comb-type structure forms aquation in cement particle surface
Layer, generates larger steric hindrance, its absorption shape in cement particle surface is made to be different from the absorption shape of other water-reducing agents,
Cement particle keeps high granular state, does not reunite, therefore gradual loss is small.
The present invention intends being modified it from sulfamate water reducer molecular structure, in sulfamate water reducer point
Graft polyether side chain, provides steric hindrance on sub- main chain, changes its peptizaiton mechanism, improves dispersibility and slump retaining.
Invention content
Goal of the invention
It is an object of the present invention to provide a kind of preparation method of polyether modified amino sulfonate water reducer, by ammonia
Graft polyether side chain on base sulfonate water reducer molecular backbone increases the peptizaiton of Water-reducing Admixtures To Cements particle, carries high-thin arch dam
Property.
It is a further object to provide the polyether modified amino sulfonate water reducers obtained by above-mentioned preparation method.
It is a further object to provide the polyether modified amino sulfonate water reducer as cement-based material point
The application of powder.
Summary of the invention
According to the first aspect of the invention, a kind of preparation side of polyether modified amino sulfonate high efficiency water reducing agent is provided
Method includes the following steps：
(1) using the polyethers of hydroxyl as solvent, make amino phenyl sulfonyl hydrochlorate, phenolsulfonate, salicylic acid, phenols chemical combination
Object, urea occur condensation reaction with aldehyde compound, obtain carboxylic sulfamic acid under acid condensation catalyst effect
Salt water reducer midbody；
(2) in the presence of water entrainer and esterification catalyst, make the polyethers of the hydroxyl and carboxylic sulfamate
Water reducer midbody carries out esterification, removes water entrainer plus alkali neutralization, obtains polyether-modified sulfamate water reducer,
The polyether structure formula of the hydroxyl is such as shown in (I)
Wherein, wherein O-A represents at least one of oxyalkylene group of 2-4 carbon atom, x=5-100；
The amino phenyl sulfonyl hydrochlorate is 2- aminobenzenesulfonic acids, the sodium salt or potassium of 3- aminobenzenesulfonic acids, 4- amino phenyl sulfonyl hydrochlorates
At least one of salt；
The phenolsulfonate is 2- hydroxy benzene sulfonic acids, 3- hydroxy benzene sulfonic acids, the sodium salt of 4- phenolsulfonates, sylvite
Or at least one of calcium salt；
The phenolic compound is phenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol, right
At least one of benzenediol；
The aldehyde compound is at least one of formaldehyde, acetaldehyde, benzaldehyde；
The aldehyde compound and amino-aryl sulfonic acid salt+hydroxyaryisuffonic acids salt+salicylic acid+phenolic compound+urea
Molar ratio be 0.8-1.5；
The amino phenyl sulfonyl hydrochlorate, phenolsulfonate, salicylic acid, phenolic compound, urea molar ratio be 1:(0.1-
10):(0.5-5):(0.5-5):(0.1-5),
The molar ratio of the polyethers of the salicylic acid and hydroxyl is 1-10,
The molecular weight of the polyether-modified sulfamate water reducer is 24000-38000.
Molecular weight of the present invention is number-average molecular weight.
The polyethers of the hydroxyl is raw material commonly used in the art, and the structural parameters of wherein polyether segment are (such as molecular weight, random
Copolymerization, block copolymerization etc.) universal relation between water-reducing agent performance more has been reported that, it need not repeat herein.
Preferably, the condensation catalyst of the acidity for sulfuric acid, p-methyl benzenesulfonic acid, phosphoric acid at least one, addition
(pressing 100% content meter) is amino-aryl sulfonic acid salt+hydroxyaryisuffonic acids salt+salicylic acid+phenolic compound+urea+aldehydes
Close the 5wt%-20wt% of object (hereinafter referred to as monomer total amount).
Preferably, in step (1), aldehyde compound is added dropwise to amino phenyl sulfonyl hydrochlorate, phenolsulfonate, water in 1-3h
Poplar acid, phenolic compound, urea and acidity condensation catalyst mixed solution in, reaction temperature is 80-120 DEG C, during reaction
Between be 3-7h.As the usual way in this field, aldehyde compound is added dropwise at 80-100 DEG C.The reaction time is from aldehydes chemical combination
Start to count after object completion of dropwise addition.
At least one of preferably, in step (2), the esterification catalyst is sulfuric acid, p-methyl benzenesulfonic acid or phosphoric acid,
Esterification reaction temperature is 105-130 DEG C, reaction time 2-6h.The condensation catalyst added in step (1) can further be made
For esterification catalyst, but in order to promote the progress of esterification, the dosage of esterification catalyst is greater than the use of condensation catalyst
Amount, therefore, also needs to increase a part of catalyst in step (2).It is reacted when the dosage of esterification catalyst starts for esterification
The 8%-20% of system gross mass.Under the premise of step (1) is substantially lossless, the dosage of the esterification catalyst is urged for condensation
The summation of the catalytic amount newly added in agent and esterification；Reaction system gross mass is i.e. when the esterification starts：Institute
Have the quality of catalyst that is newly added in condensation monomer, the polyethers of hydroxyl, condensation catalyst, water entrainer and esterification it
With.
Benzene,toluene,xylene commonly used in the art, chloroform or carbon tetrachloride may be selected in the water entrainer.Water entrainer is usual
After the completion of reaction through being distilled off, the water entrainer distilled is recyclable.
Preferably, in step (2), add alkali neutralization to pH be 3-5.
As the Normal practice of this field, can also be by product dilution to mass percent concentration after neutralization procedure
30%-50%.
At least one, you can be the mixture of one of which or two or more arbitrary proportions.
According to the second aspect of the invention, it is high to additionally provide the polyether modified amino sulfonate that the preparation method obtains
Imitate water-reducing agent.
According to the third aspect of the present invention, the polyether modified amino sulfonate high efficiency water reducing agent is additionally provided as water
The application of cement-based material dispersant.
The obtained polyether modified amino sulfonate water reducer of the present invention is good as cement-based material dispersant water-reducing effect,
Its volume (the solid volume of folding) is the 1.5 ‰ -4 ‰ of cementitious material quality during use, and specific volume is determined according to actual requirement of engineering.
But when volume is less than 1.5 ‰, poor dispersion, it is impossible to meet engine request, when volume is more than 4 ‰, cost performance is not high, mistake
High additive there is also isolation bleeding.
The present invention increases sulfamate water reducer molecule by being grafted pfpe molecule side chain in sulfamate main chain
Steric hindrance, improve the dispersion performance of sulfamate high-effective water-reducing agent and dispersion holding performance (i.e. slump retaining).This is poly-
The sulfamate water reducer that ether is modified can be used alone, and can also be used in combination with other water-reducing agents on the market.
Specific embodiment
In order to better understand the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely in the following examples.Every equivalent change or modification made according to spirit of the invention, all
It should be included within the scope of the present invention.
In the embodiment of the present invention, the molecular weight of condensation product uses Wyatt technology corporation gel infiltrations
Chromatograph (GPC) measures.Experiment condition is as follows：
Gel column：Two root chromatogram columns of Shodex SB806+803 are connected；
Cleaning solution：0.1M NaNO3Solution；
Flow phase velocity：1.0mL/min；
Injection：20 μ L, 0.5% aqueous solutions；
Detector：Shodex RI-71 type differential refraction devices；
Reference substance：Polyethylene glycol GPC standard specimens (Sigma-Aldrich, molecular weight 1010000,478000,263000,
118000,44700,18600,6690,1960,826,232)。
Used cement is small open country II cement of field 525.5R.P. (Jiangnan little Ye Tian Cement Co., Ltds), and sand is thin
The middle sand of modulus Mx=2.6 is spent, cobble-stone diameter is the rubble of 5-20mm continuous gradings.Flowing degree of net paste of cement test is with reference to GB/
T8077-2000 standards carry out, amount of water 87g, and flowing degree of net paste of cement is measured on plate glass after stirring 3min.
Concrete slump, water-reducing rate, air content test are with reference to standard GB/T/T8076-2008《Concrete admixture》
Relevant regulations perform, and additive volume is the solid volume of folding.
As shown in table 1,2, the cement water reducing agent of synthesis is labeled as raw material used in the following example and polyether monomer
C.Wherein the synthesis of polyethers uses conventional method, using methanol as initiator, catalyst is added in, at a certain temperature, according to set
The polyether structure of meter is passed through ethylene oxide, propylene oxide, epoxy butane etc., carries out ring-opening polymerisation, can obtain after purification required
Polyethers, GPC test molecule amounts.Can be random or block copolymeric structure when being copolymerized there are many epoxy monomer, the present invention is right
This is not particularly limited.Specifically, copolymeric structure polyethers involved in following embodiment, is block structure.
1 raw material of table and specification
Polyethers list in 2 embodiment of table
Substantially lossless depending on step (1) in following embodiment, the dosage of the esterification catalyst is condensation catalyst and ester
Change the summation of catalytic amount newly added in reaction；Reaction system gross mass is single for all condensations when the esterification starts
The quality sum of catalyst newly added in body, the polyethers of hydroxyl, condensation catalyst, water entrainer and esterification.
Embodiment 1
0.08mol 4- Sodium p-aminobenzene sulfonats are weighed, 0.02mol 4- sodium hydroxybenzenesulfonate is placed in equipped with agitating paddle, reflux
In the 500mL three-necked flasks of condenser pipe, 0.1mol polyethers PH-1,0.1mol salicylic acid, 0.1mol urea and 0.12mol benzene are added in
Phenol, being warming up to 80 DEG C makes it all dissolve, and adds in the 20.6g concentrated sulfuric acids (10wt% of monomer total amount) while stirring, is dripped in 20min
After adding 0.52mol formaldehyde, 5h is reacted at 90 DEG C of steady temperature, you can obtain sulfamate water reducer molecular backbone.Then
Dimethylbenzene 60g is added in flask, is slowly added to concentrated sulfuric acid 10g, water knockout drum is installed, increases the temperature to 130 DEG C, esterification
4h after no water steams, turns off stirring and heating, stops reaction, recycles the water entrainer dimethylbenzene in water knockout drum.Reaction finishes
It is neutralized with 30%NaOH solution, adds in 250g water to get to polyether-modified sulfamate high-effective water-reducing agent, count equal molecule
It is 32800 to measure, and is named as C-1.(11.5wt% of reaction system gross mass when esterification catalyst dosage starts for esterification)
Embodiment 2
0.09mol4- Sodium p-aminobenzene sulfonats are weighed, 0.01mol4- sodium hydroxybenzenesulfonate is placed in equipped with agitating paddle, returned cold
In the 500mL three-necked flasks of solidifying pipe, addition 0.08mol polyethers PH-2,0.1mol salicylic acid, 0.01mol urea and 0.19mol pairs
Benzenediol, being warming up to 85 DEG C makes it all dissolve, and adds in concentrated sulfuric acid 11.73g (5wt% of monomer total amount), 20min while stirring
After 0.504mol formaldehyde is inside slowly added dropwise, 4h is reacted at 90 DEG C of steady temperature, you can obtain sulfamate water reducer molecule
Main chain.Then toluene 60g is added in flask, is slowly added to p-methyl benzenesulfonic acid 20g, water knockout drum is installed, increases the temperature to 120
DEG C, esterification 5h after no water steams, stops reaction, recycles water entrainer toluene.Reaction is finished in 30%NaOH solution
With add in 250g water to get to polyether-modified sulfamate high-effective water-reducing agent, number-average molecular weight 31650 is named as
C-2.(10.76wt% of reaction system gross mass when esterification catalyst dosage starts for esterification)
Embodiment 3
Weigh 0.048mol 4- Sodium p-aminobenzene sulfonats, 0.032mol 2- Sodium p-aminobenzene sulfonats, 0.04mol 4- hydroxy benzenes
Sodium sulfonate, be placed in equipped with agitating paddle, reflux condensing tube 500mL three-necked flasks in, add in 0.05mol polyethers PH-3,0.1mol
Salicylic acid, 0.1mol urea and 0.1mol phenol, being warming up to 100 DEG C makes it all dissolve, and adds in 28.4g while stirring to methyl
Benzene sulfonic acid (15wt% of monomer total amount) after 0.52mol formaldehyde is slowly added dropwise in 20min, reacts at 110 DEG C of steady temperature
5h, you can obtain sulfamate water reducer molecular backbone.Then benzene 50g is added in flask, is slowly added to phosphatase 11 0g (matter
It measures score to be more than 85%), water knockout drum is installed, increases the temperature to 120 DEG C, esterification 4h, after no water steams, stop anti-
Should, recycle water liquid benzene.Reaction is finished and is neutralized with NaOH solution, adds in 250g water to get to polyether-modified sulfamate
High efficiency water reducing agent, number-average molecular weight 36710, is named as C-3.(esterification catalyst dosage is reacted when starting for esterification
The 17.6wt% of system gross mass)
Embodiment 4
Weigh 0.1mol 4- Sodium p-aminobenzene sulfonats, 0.04mol 3- Sodium p-aminobenzene sulfonats, 0.05mol 3- hydroxy benzene sulfonic acids
Sodium be placed in equipped with agitating paddle, reflux condensing tube 500mL three-necked flasks in, add in 0.07mol polyethers PH-4,0.1mol bigcatkin willows
Acid, 0.1mol urea and 0.1mol m-methyl phenols, being warming up to 90 DEG C makes it all dissolve, and adds in concentrated sulfuric acid 20g while stirring
(9.34wt% of monomer total amount), after 0.735mol formaldehyde is slowly added dropwise in phosphatase 11 0g, 20min, at 120 DEG C of steady temperature
React 3h, you can obtain sulfamate water reducer molecular backbone.Then chloroform 50g is added in flask, is slowly added to dense sulphur
Sour 10g, phosphoric acid 5g install water knockout drum, increase the temperature to 130 DEG C, esterification 5h, after no water steams, stop reaction, return
Take-up aqua chloroform.Reaction is finished and is neutralized with NaOH solution, adds in 250g water to get to polyether-modified sulfamate high-effective
Water-reducing agent, number-average molecular weight 34450, is named as C-4.(reaction system when esterification catalyst dosage starts for esterification
The 11.65wt% of gross mass)
Embodiment 5
Weigh 0.03mol4- Sodium p-aminobenzene sulfonats, 0.07mol3- sodium hydroxybenzenesulfonate, 0.06mol4- hydroxy benzene sulfonic acids
Sodium, be placed in equipped with agitating paddle, reflux condensing tube 500mL three-necked flasks in, add in 0.073mol polyethers PH-5,0.15mol water
Poplar acid, 1.5mol urea and 0.1mol phenol, being warming up to 80 DEG C makes it all dissolve, and it is (single to add in 43.05g phosphoric acid while stirring
The 13.05wt% of body total amount), after formaldehyde 54.5g is slowly added dropwise in 20min, react 7h at 80 DEG C of steady temperature, you can obtain
Sulfamate water reducer molecular backbone.Then dimethylbenzene 60g is added in flask, is slowly added to p-methyl benzenesulfonic acid 20g,
Water knockout drum is installed, increases the temperature to 105 DEG C, esterification 4h, after no water steams, stops reaction, recycles water entrainer diformazan
Benzene.Reaction is finished and is neutralized with NaOH solution, adds in 250g water to get to polyether-modified sulfamate high-effective water-reducing agent,
Number-average molecular weight is 28760, is named as C-5.(reaction system gross mass when esterification catalyst dosage starts for esterification
15.38wt%)
Embodiment 6
0.12mol4- Sodium p-aminobenzene sulfonats are weighed, 0.05mol 2- sodium hydroxybenzenesulfonate is placed in equipped with agitating paddle, reflux
In the 500mL three-necked flasks of condenser pipe, 0.04mol polyethers PH-3,0.1mol salicylic acid, 0.14mol urea and 0.6mol are added in
Phenol, being warming up to 85 DEG C makes it all dissolve, while stirring addition concentrated sulfuric acid 20g (11.4wt% of monomer total amount), in 20min
After 0.4mol formaldehyde is slowly added dropwise, 5h is reacted at 90 DEG C of steady temperature, you can obtain sulfamate water reducer molecular backbone.
Then toluene 60g is added in flask, is slowly added to concentrated sulfuric acid 10g, water knockout drum is installed, increases the temperature to 130 DEG C, esterification
2h after no water steams, stops reaction, recycles water entrainer toluene.Reaction is finished to be neutralized with NaOH solution, adds in 250g water,
Polyether-modified sulfamate high-effective water-reducing agent is obtained, number-average molecular weight 37230 is named as C-6.(catalyzing esterification
The 12.2wt% of reaction system gross mass when agent dosage starts for esterification)
Embodiment 7
Weigh 0.05mol4- Sodium p-aminobenzene sulfonats, 0.05mol 2- Sodium p-aminobenzene sulfonats, 0.05mol4- hydroxy benzene sulfonic acids
Sodium, 0.05mol2- sodium hydroxybenzenesulfonate, be placed in equipped with agitating paddle, reflux condensing tube 500mL three-necked flasks in, add in
0.02mol polyethers PH-7,0.2mol salicylic acid, 0.01mol urea and 0.14mol phenol, being warming up to 95 DEG C makes it all dissolve,
15g phosphoric acid (6.6wt% of monomer total amount) is added in while stirring, after 0.55mol benzaldehydes are slowly added dropwise in 20min, constant
5h is reacted at 100 DEG C of temperature, you can obtains sulfamate water reducer molecular backbone.Then carbon tetrachloride is added in flask
60g is slowly added to phosphatase 11 0g, installs water knockout drum, increases the temperature to 120 DEG C, esterification 5h, after no water steams, stops
Water entrainer carbon tetrachloride is recycled in reaction.Reaction is finished and is neutralized with NaOH solution, adds in 250g water to get to polyether-modified ammonia
Base sulfonate high efficiency water reducing agent, number-average molecular weight 24680 are named as C-7.(esterification catalyst dosage is opened for esterification
The 8.1wt% of reaction system gross mass during the beginning)
Embodiment 8
Weigh 0.08mol4- Sodium p-aminobenzene sulfonats, 0.05mol3- Sodium p-aminobenzene sulfonats, 0.02mol 4- hydroxy benzene sulfonic acids
Sodium, be placed in equipped with agitating paddle, reflux condensing tube 500mL three-necked flasks in, add in 0.08mol polyethers PH-1,0.1mol bigcatkin willows
Acid, 0.1mol urea and 0.1mol phenol, being warming up to 80 DEG C makes it all dissolve, and adding in the 25g concentrated sulfuric acids while stirring, (monomer is total
The 11.3wt% of amount), after 0.564mol formaldehyde is slowly added dropwise in 20min, react 4h at 110 DEG C of steady temperature, you can obtain
Sulfamate water reducer molecular backbone.Then benzene 60g is added in flask, is slowly added to phosphatase 11 5g, water knockout drum is installed, is risen
High-temperature is to 125 DEG C, esterification 6h, after no water steams, stops reaction, recycles water liquid benzene.Reaction, which finishes, uses NaOH
Solution neutralizes, and adds in 250g water to get to polyether-modified sulfamate high-effective water-reducing agent, number-average molecular weight 36580,
It is named as C-8.(13.7wt% of reaction system gross mass when esterification catalyst dosage starts for esterification)
Embodiment 9
Weigh 0.06mol4- Sodium p-aminobenzene sulfonats, 0.03mol3- Sodium p-aminobenzene sulfonats, 0.02mol 4- aminobenzenesulfonic acids
Sodium, be placed in equipped with agitating paddle, reflux condensing tube 500mL three-necked flasks in, add in 0.1mol polyethers PH-6,0.16mol bigcatkin willows
Acid, 0.1mol urea and 0.1mol phenol, being warming up to 80 DEG C makes it all dissolve, and adding in 26.5g phosphoric acid while stirring, (monomer is total
The 15.9wt% of amount), after 0.49mol acetaldehyde is slowly added dropwise in 20min, react 4h at 100 DEG C of steady temperature, you can obtain ammonia
Base sulfonate water reducer molecular backbone.Then dimethylbenzene 60g is added in flask, is slowly added to phosphoric acid 5g, p-methyl benzenesulfonic acid
10g installs water knockout drum, increases the temperature to 110 DEG C, esterification 5h, after no water steams, stops reaction, recycles water entrainer
Dimethylbenzene.Reaction is finished and is neutralized with NaOH solution, adds in 250g water to get to polyether-modified sulfamate high-effective diminishing
Agent, number-average molecular weight 36750, is named as C-9.(reaction system total matter when esterification catalyst dosage starts for esterification
The 18.3wt% of amount)
Comparative example
0.06mol 4- Sodium p-aminobenzene sulfonats are weighed, 0.05mol 4- Sodium p-aminobenzene sulfonats are placed in equipped with agitating paddle, reflux
In the 500mL three-necked flasks of condenser pipe, 0.1mol salicylic acids, 0.1mol urea, 0.1mol phenol and 20g water are warming up to 80 DEG C
It is made all to dissolve, the 10g concentrated sulfuric acids (9.3wt% of monomer total amount) is added in while stirring, 0.43mol is slowly added dropwise in 20min
After formaldehyde, 5h is reacted at 90 DEG C of steady temperature, reaction is finished to be neutralized with NaOH solution, is added in 100g water, be can obtain amino sulphur
Hydrochlorate high efficiency water reducing agent, number-average molecular weight 14600, is named as C-10.
Application Example 1
In order to evaluate dispersion of the polyether modified amino benzene sulfonate high efficiency water reducing agent to cement paste prepared by the present invention
Performance, with reference to standard GB/T/T8077-2000《Concrete admixture homogenieity test method》Relevant regulations take 300g water
Mud, 87g water, comparative example C-10 volumes are cement 0.3%, and the volume of other additives is 0.25%, in order to investigate water-reducing agent pair
The sensitivity of volume, C-1 and C-10 have chosen the contrast test of different addition quantity, are starched only on stirring 3min test plate glass
Fluidity, and test the paste flowing degree after 1h.Result of the test is as shown in Table 3 and Table 4.
As can be seen from Table 3, the dispersibility of polyether modified amino sulfonate high efficiency water reducing agent produced by the present invention does not change
Property sulfamate high-effective water-reducing agent (C-10) greatly improve, and its fluidity does not lose substantially after 1 hour, it is main former
Because being after pfpe molecule being grafted to the side chain of sulfamic acid molecules of salt, to form steric hindrance, the work of cement dispersion is changed
With mechanism, so as to inherently be improved to the dispersibility of sulfamate water reducer and slump retaining.Pass through as can be seen from Table 4
Polyether-modified sulfamate high-effective water-reducing agent (C-1) is respectively provided with preferable flowing in the range of volume 0.2%-0.35%
Property, it is insensitive to volume, but continue to improve volume and will appear and take off bottom excreting water phenomenon.Without modified sulfamate diminishing
Agent (C-10) is to volume sensitivity, and fluidity loss is fast.
3 flowing degree of net paste of cement evaluation table of table
The paste flowing degree contrast table of 4 different addition quantity of table
Application Example 2
With reference to standard GB/T 8076-2008《Concrete admixture》The test request of high-performance water reducing agent in standard, institute
The cement of use is small open country II cement of field 525.5R.P., and sand is the middle sand of fineness modulus Mx=2.6, and stone is 5-10mm
Diameter handstone and the big stone continuous grading rubble of 10-20mm grain sizes are material, according to proportioning test condensation polymer diminishing as defined in table 5
Indexs, the test results such as water-reducing rate, air content, the slump holding capacity of agent are shown in Table 6.The volume of embodiment is 0.25%,
Comparative example C-10 volumes are the 0.3% of cement consumption.
5 test concrete mix of table
The performance evaluation table of 6 concrete of table
6 concrete flowability of table statistics indicate that, due to the introducing of polyether lateral chain, provide larger space steric hindrance, be in volume
Under 0.25%, polyether-modified sulfamate high-effective water-reducing agent can show dispersibility and slump retaining well.
Claims (8)
1. a kind of preparation method of polyether modified amino sulfonate high efficiency water reducing agent, which is characterized in that include the following steps：
(1) using the polyethers of hydroxyl as solvent, make amino phenyl sulfonyl hydrochlorate, phenolsulfonate, salicylic acid, phenolic compound, urine
Element occurs condensation reaction with aldehyde compound, obtains carboxylic sulfamate and subtract under acid condensation catalyst effect
Aqua intermediate；
(2) in the presence of water entrainer and esterification catalyst, make the polyethers of the hydroxyl and carboxylic sulfamate diminishing
Agent intermediate carries out esterification, removes water entrainer plus alkali neutralization, obtains polyether-modified sulfamate water reducer,
The polyether structure formula of the hydroxyl is such as shown in (I)
Wherein, wherein O-A represents at least one of oxyalkylene group of 2-4 carbon atom, x=5-100；
The amino phenyl sulfonyl hydrochlorate is 2- aminobenzenesulfonic acids, in the sodium salt or sylvite of 3- aminobenzenesulfonic acids, 4- amino phenyl sulfonyl hydrochlorates
At least one；
The phenolsulfonate is 2- hydroxy benzene sulfonic acids, 3- hydroxy benzene sulfonic acids, the sodium salt of 4- phenolsulfonates, sylvite or calcium
At least one of salt；
The phenolic compound for phenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol, to benzene two
At least one of phenol；
The aldehyde compound is at least one of formaldehyde, acetaldehyde, benzaldehyde；
The aldehyde compound rubs with amino-aryl sulfonic acid salt+hydroxyaryisuffonic acids salt+salicylic acid+phenolic compound+urea
You are than being 0.8-1.5；
The amino phenyl sulfonyl hydrochlorate, phenolsulfonate, salicylic acid, phenolic compound, urea molar ratio be 1:(0.1-10):
(0.5-5):(0.5-5):(0.1-5),
The molar ratio of the polyethers of the salicylic acid and hydroxyl is 1-10,
The molecular weight of the polyether-modified sulfamate water reducer is 24000-38000.
2. the preparation method of polyether modified amino sulfonate high efficiency water reducing agent as described in claim 1, which is characterized in that described
Acid condensation catalyst is sulfuric acid, at least one of p-methyl benzenesulfonic acid, phosphoric acid, and addition is amino-aryl sulfonic acid salt+hydroxyl
The 5wt%-20wt% of base arylsulphonate+salicylic acid+phenolic compound+urea+aldehyde compound.
3. the preparation method of polyether modified amino sulfonate high efficiency water reducing agent as described in claim 1, which is characterized in that step
(1) in, aldehyde compound is added dropwise to amino phenyl sulfonyl hydrochlorate, phenolsulfonate, salicylic acid, phenolic compound, urine in 1-3h
In the mixed solution of element and acid condensation catalyst, reaction temperature is 80-120 DEG C, reaction time 3-7h.
4. the preparation method of polyether modified amino sulfonate high efficiency water reducing agent as described in claim 1, which is characterized in that step
(2) in, the esterification catalyst is sulfuric acid, p-methyl benzenesulfonic acid or phosphoric acid, and esterification reaction temperature is 105-130 DEG C, and is esterified
Reaction temperature is at least 10 DEG C higher than setting-up point, reaction time 2-6h.
5. the preparation method of polyether modified amino sulfonate high efficiency water reducing agent as described in claim 1, which is characterized in that described
Water entrainer is benzene,toluene,xylene, chloroform or carbon tetrachloride.
6. the preparation method of polyether modified amino sulfonate high efficiency water reducing agent as described in claim 1, which is characterized in that step
(2) in, add alkali neutralization to pH be 3-5.
7. the polyether modified amino sulfonate high efficiency water reducing agent that any one of the claim 1-6 preparation methods obtain.
8. application of the polyether modified amino sulfonate high efficiency water reducing agent as cement-based material dispersant described in claim 7.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911559A (en) * | 2018-07-27 | 2018-11-30 | 科之杰新材料集团有限公司 | A kind of preparation method of modified sulfamate water reducer |
| CN111378109A (en) * | 2018-12-31 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Aniline polyether, preparation method thereof and application of aniline polyether in modified aliphatic superplasticizer |
| CN111471171A (en) * | 2019-01-24 | 2020-07-31 | 江苏苏博特新材料股份有限公司 | Aryl sulfonic acid intermediate, preparation method thereof and application thereof in synthesizing low-temperature-sensitivity additive for concrete |
| CN112321784A (en) * | 2019-12-26 | 2021-02-05 | 联泓(江苏)新材料研究院有限公司 | Bulk polymer and preparation method and application thereof |
| CN113105153A (en) * | 2021-04-08 | 2021-07-13 | 金陵科技学院 | Synthetic method of anti-mud slump-retaining type high-efficiency water reducing agent containing silicon base and amino |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0672750A (en) * | 1992-07-17 | 1994-03-15 | Nippon Paper Ind Co Ltd | Cement water reducing agent, cement composition containing the agent and its hardened material |
| CN101050081A (en) * | 2006-04-07 | 2007-10-10 | 武汉市保立化学品有限责任公司 | High performance water reducing agent in new type comb shaped molecular structure |
| CN104961375A (en) * | 2015-06-26 | 2015-10-07 | 金陵科技学院 | Carboxyl group-containing modified amino sulfonate high efficiency water reducer preparation method |
| CN106188455A (en) * | 2016-07-25 | 2016-12-07 | 抚顺东科精细化工有限公司 | A kind of synthetic method of bisphenol A polyethenoxy ether modified sulfamate water reducer |
-
2016
- 2016-12-28 CN CN201611236905.4A patent/CN108250447B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0672750A (en) * | 1992-07-17 | 1994-03-15 | Nippon Paper Ind Co Ltd | Cement water reducing agent, cement composition containing the agent and its hardened material |
| CN101050081A (en) * | 2006-04-07 | 2007-10-10 | 武汉市保立化学品有限责任公司 | High performance water reducing agent in new type comb shaped molecular structure |
| CN104961375A (en) * | 2015-06-26 | 2015-10-07 | 金陵科技学院 | Carboxyl group-containing modified amino sulfonate high efficiency water reducer preparation method |
| CN106188455A (en) * | 2016-07-25 | 2016-12-07 | 抚顺东科精细化工有限公司 | A kind of synthetic method of bisphenol A polyethenoxy ether modified sulfamate water reducer |
Non-Patent Citations (2)
| Title |
|---|
| 王国建等: "后酯化法制备聚羧酸盐系高效减水剂的研究", 《新型建筑材料》 * |
| 王子明等: "《混凝土高效减水剂》", 31 August 2011 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108911559A (en) * | 2018-07-27 | 2018-11-30 | 科之杰新材料集团有限公司 | A kind of preparation method of modified sulfamate water reducer |
| CN111378109A (en) * | 2018-12-31 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Aniline polyether, preparation method thereof and application of aniline polyether in modified aliphatic superplasticizer |
| CN111471171A (en) * | 2019-01-24 | 2020-07-31 | 江苏苏博特新材料股份有限公司 | Aryl sulfonic acid intermediate, preparation method thereof and application thereof in synthesizing low-temperature-sensitivity additive for concrete |
| CN111471171B (en) * | 2019-01-24 | 2023-07-18 | 江苏苏博特新材料股份有限公司 | Arylsulfonic acid intermediate, preparation method thereof and application of aryl sulfonic acid intermediate in synthesizing low-temperature-sensitivity additive for concrete |
| CN112321784A (en) * | 2019-12-26 | 2021-02-05 | 联泓(江苏)新材料研究院有限公司 | Bulk polymer and preparation method and application thereof |
| CN112321784B (en) * | 2019-12-26 | 2023-08-11 | 联泓(江苏)新材料研究院有限公司 | Bulk polymer and preparation method and application thereof |
| CN113105153A (en) * | 2021-04-08 | 2021-07-13 | 金陵科技学院 | Synthetic method of anti-mud slump-retaining type high-efficiency water reducing agent containing silicon base and amino |
| CN113105153B (en) * | 2021-04-08 | 2022-08-12 | 金陵科技学院 | Synthetic method of anti-mud slump-retaining type high-efficiency water reducing agent containing silicon base and amino |
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