CN108373525A - A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent - Google Patents
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent Download PDFInfo
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- CN108373525A CN108373525A CN201810275878.4A CN201810275878A CN108373525A CN 108373525 A CN108373525 A CN 108373525A CN 201810275878 A CN201810275878 A CN 201810275878A CN 108373525 A CN108373525 A CN 108373525A
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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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
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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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/30—Inorganic compounds
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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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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- Engineering & Computer Science (AREA)
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Abstract
The present invention provides a kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent：A certain proportion of polyether macromonomer and water are added in reaction kettle, agitating and heating waits for its dissolving；Temperature is controlled at 52 60 DEG C, is initially added into a certain amount of hydrogen peroxide, bleeding agent, chain-transferring agent；After 5min, start that solution B is added dropwise, starts that solution A is added dropwise after solution B is added dropwise, in 10min, solution A time for adding is a hours, and solution B time for adding is a+0.5 hours；Solution A is made of a certain proportion of alkyl acrylate, acrylic acid and water, and solution B is made of medium temperature initiator, alcohol organic solvent and water；It after completion of dropwise addition, heats to 66 72 DEG C and keeps temperature constant, cure b hours, moisturizing is to 1000 parts to get product of the present invention.The present invention is selected by rational technological design and raw material, and the polycarboxylic acid slump retaining agent adaptability of preparation is good, and performance is stablized, and the anti-anti- adsorption capacity of mud is strong, has excellent slump holding capacity.
Description
Technical field
The invention belongs to building material technical fields, are related to concrete admixture field, and specifically a kind of double initiations are high
The preparation method of stability polycarboxylic acid slump retaining agent.
Background technology
With the rapid development of technology of high performance concrete, requirement of the engineer application for water-reducing agent performance also constantly carries
Height, while there has also been requirements at the higher level to slump retaining agent performance.It is various trans-regional, cross-region with the continuous propulsion of engineering construction
The case where engineering project continues to bring out, and polycarboxylic acid slump retaining agent often will appear " not acclimatized " in use；Along with sand
The influence for the problems such as stone material is limited by regions and multifarious, and quality sand and stone resources are again increasingly in short supply, market are steady to performance
The polycarboxylic acid slump retaining agent fixed, adaptability is good, function of slump protection is excellent is in great demand.
It takes suitable technique and raw material to select, prepares molecular weight stabilizers distribution, the good polycarboxylic acids diminishing of adaptability
Agent, one of key are the selections of initiator, must allow the steady controllable of initiation system；Moreover, double initiation systems are conducive to selectivity
Prepare specific molecular configuration.
Patent CN105949404A discloses a kind of preparation method of release controllable type polycarboxylic acid slump retaining agent, which includes
Following steps：1) mass fraction is pressed by unsaturated polyoxyethylene ether monomer 144-180 parts, and 144-180 parts of deionized water is added three
In mouth flask, during which stirring is heated to 45-60 DEG C of heat preservation to dissolving；2) mass fraction is pressed by 1.0-2.0 parts of chain-transferring agent
It is dissolved in 30-60 parts of deionized water with 0.5-1.5 parts of initiator and is configured to A liquid；3) mass fraction is pressed by unsaturated acids 2-20
Part, 20-30 parts of beta-unsaturated esters, which are dissolved in 10-20 parts of deionized water, is configured to B liquid；4) A, B while into three-necked flask is added dropwise
Liquid, time for adding are respectively 180-210min, 150-180min, are terminated after the reaction was continued 60-80min, and deionized water is added
It is diluted to theoretical solid containing being got product for 40%.
Patent CN105601836A discloses a kind of preparation method of polycarboxylate water-reducer, which includes following step
Suddenly：1) unsaturated carboxylic acid or acid anhydrides, 1-hydroxy ethylidene-1,1-diphosphonic acid or 2- hydroxyphosphonoacetic acid, polymerization inhibitor are mixed, is protected in nitrogen
Under shield, it is warming up to 40-60 DEG C, adds catalyst, is warming up to 100-140 DEG C, 0.5~3h of insulation reaction, during which removes water, instead
It is down to room temperature after answering, obtains the first mixture；2) the first mixture, unsaturated carboxylic acid hydroxy ester, ether type monomer are mixed,
And water is added and makes its dissolving, obtain copolymerized monomer mixture solution；3) 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 copolymerization product is obtained；4) copolymerization product alkali is adjusted into pH
To 5-7 to get finished product.
Patent CN105859979A discloses a kind of anti-chamotte mould polycarboxylic acid slump retaining agent and preparation method thereof, the slump retaining agent by with
Lower raw material is calculated in percentage by weight to be made：Unsaturated polyoxyethylene ether monomer is 50-75%, acrylic acid 4-8%, Malaysia
Acid anhydrides is 6-12%, and hydroxy-ethyl acrylate or hydroxypropyl acrylate are 11-20%, chain-transferring agent 0.5-3.0%, initiator use
Amount is 0.1-5%, and initiation auxiliary agent is 0.01-2%；Specifically preparation method is：Acrylic acid, hydroxy-ethyl acrylate and third is added dropwise in double dropwise additions
Olefin(e) acid hydroxypropyl ester solution and initiation auxiliary agent 2-3.5h, it is 6-7 to keep the temperature 1-1.5 hours back end hydrogenation sodium hydroxide solutions and adjust pH value, is obtained
Solid content is the anti-chamotte mould polycarboxylic acid slump retaining agent of 40-45%.
It is different from the above patent, the present invention is used using the method for heating residual initiator after double initiations-and caused effect
Stable initiator, and selected by the technological design of optimization and raw material, it is cured for a long time using rear temperature raising method, removal is extra to draw
Agent is sent out, the diminishing agent molecule of more reasonable structure is obtained.It is final to prepare that adaptability is good, and the anti-anti- adsorption capacity of mud is strong, have excellent
The polycarboxylic acid slump retaining agent of slump holding capacity.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of double preparations for causing high stability polycarboxylic acid slump retaining agent
Method.
Polycarboxylic acid slump retaining agent is in use, however it remains some problems, it is more perfect that performance is developed in an urgent demand
High-performance slump retaining agent, meet the needs of different engineerings, varying environment use.The present invention is first made using double methods caused
Make initially to cause with hydrogen peroxide, reaction is driven to carry out, reuses the initiation stable medium temperature initiator of effect and carry out continuing to be added dropwise drawing
Hair obtains the initiation system excessively steady, progress is controllable.
The invention selects the medium temperature initiator of suitable half-life period for the technological temperature of reaction, it is not easy to induction point occur
Solution, is easy to form the polymer of high molecule mass；The bleeding agent of introducing has hydrophilic radical, and row is oriented in the surface energy of solution
Row, and surface tension can be made to be remarkably decreased, excellent emulsification, dispersibility are obtained, each component raw material is enable to be sufficiently mixed reaction,
Greatly improve reaction efficiency and monomer conversion.It is cured for a long time using rear temperature raising method, removes extra initiator, eliminated residual and draw
Sending out agent influences the unstability of slump retaining agent later stage performance, and promotes the reaction was complete to carry out, and obtains the diminishing of more reasonable structure
Agent molecule.Final to prepare that adaptability is good, and the anti-anti- adsorption capacity of mud is strong, the polycarboxylic acids guarantor with excellent slump holding capacity is collapsed
Agent.
Technical scheme is as follows：
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, double initiation high stability polycarboxylic acids guarantors are collapsed
Agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohol organic solvent, hydrogen peroxide,
Acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, preparation method includes the following steps：
1) 395-425 parts of polyether macromonomers and 150-200 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 0.1-0.3 parts of infiltrations at 52-60 DEG C
Agent, 3-7 parts of chain-transferring agents, 0.2-0.5 parts of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start to be added dropwise after solution B is added dropwise, in 10min molten
Liquid A, solution A time for adding are a hours, and solution B time for adding is a+0.5 hours；Solution B by 2.6-4.8 parts of medium temperature initiators,
10-15 parts of alcohol organic solvents and 80-90 parts of water compositions, solution A is by 30-45 parts of alkyl acrylates, 20-28 parts of acrylic acid
It is formed with 50-60 parts of water；
4) after completion of dropwise addition, 66-72 DEG C is heated, keeps temperature constant, cures b hours, waits for that reaction solution temperature is less than
At 30 DEG C, 6-12 parts of neutralizers are slowly added to, moisturizing gathers to double initiation high stabilities that 1000 parts are 50% to get mass fraction
Carboxylic acid slump retaining agent.
The polyether macromonomer is by allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, prenol polyoxy second
One or more of alkene ether, vinyl butyl ether polyoxyethylene ether form；Preferably isoamyl alcohol polyoxyethylene ether.
The alkyl acrylate is by hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, metering system
One or more of sour hydroxypropyl acrylate forms；Preferred mass ratio is 1:1 hydroxyethyl methacrylate and hydroxypropyl acrylate
Composition.
The medium temperature initiator is initiator of the 1h half life temperatures at 50-75 DEG C, specifically by azobisisoheptonitrile, azo
One or more of dicyano valeric acid, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate form；It is preferred that matter
Amount is than being 1:1 is the composition of azobisisoheptonitrile and di-cyclohexylperoxy di-carbonate.
The alcohol organic solvent is the alcohol with certain chain transfer ability, specifically by methanol, ethyl alcohol, benzyl alcohol, second two
One or more of alcohol, propylene glycol, glycerine form；Preferred mass ratio is 2:1 ethyl alcohol and the composition of propylene glycol.
The bleeding agent is by sulfated castor oil, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, alkyl sulfate sodium, secondary alkyl
Sodium sulfonate, secondary alkyl sulphate sodium, Negel, succinic acid alkyl ester sulfonate sodium, one kind in sulfamic acid sodium or several
Kind composition；Preferred anionic type bleeding agent；Preferred mass ratio is 1:The composition of 1 sodium alkyl benzene sulfonate and sulfamic acid sodium.
The chain-transferring agent is by thioacetic acid, mercaptopropionic acid, mercaptoethanol, sodium vinyl sulfonate, acrylic sodium sulfonate, first
One or more of base sodium allylsulfonate, sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonics, sodium hypophosphite group
At；It is preferred that weak chain-transferring agent；Preferred mass ratio is 1:The group of 1 acrylic sodium sulfonate and 2- acrylamide-2-methyl propane sulfonics
Close object.
The neutralizer is by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, second
One or more of hydramine, diethanol amine, triethanolamine, triisopropanolamine form；Preferred mass ratio is 1:1 potassium carbonate and
The composition of sodium methoxide.
The hydrogen peroxide is that mass percent is 27.5% industrial grade hydrogen peroxide.
The solution A time for adding a is 2-4h；Preferably 2h.
The curing time b is 1-3h；Preferably 1.5h.The beneficial effects of the invention are as follows：
1, it using the method for double initiations, first uses hydrogen peroxide to make initial initiation, drives reaction to carry out, reuse initiation effect
Stable medium temperature initiator carries out continuing to be added dropwise causing, and obtains the initiation system excessively steady, progress is controllable；Medium temperature initiator is not
It is easy to happen induction to decompose, is easy to form the polymer of high molecule mass；In conjunction with entire reaction process temperature, half-life period temperature is selected
Slightly lower medium temperature initiator is spent, coordinates the alcohol organic solvent with certain chain tra nsfer function, medium temperature initiator is dissolved in alcohols
It is re-dissolved in water later, some medium temperature initiators not soluble in water, which are dissolved in alcohol, facilitates dropwise addition, then uses the method being at the uniform velocity added dropwise,
Rationally control reaction rate is conducive to industrial production.
2, the bleeding agent introduced has hydrophilic radical, is aligned in the surface energy of solution, and surface tension can be made notable
Decline, obtains excellent emulsification, dispersibility, each component raw material is enable to be sufficiently mixed reaction, greatly improve reaction efficiency and list
Transformation rate；And the bleeding agent introduced belongs to anion surfactant, even if final residue also contributes to pair in the product
The peptizaiton of cement slurry.
3, using rear temperature raising method, two-part temperature, the later stage carries out long-time heat preservation curing, will be remained in composite initiation system
Initiator eliminated in heating maturing process, preventing residual initiator influences the unstability of water-reducing agent later stage performance,
It can also promote the reaction was complete to carry out, water-reducing agent molecular weight can be allowed more optimized, obtain ideal molecular weight and molecular configuration.
4, it is selected by rational technological design and raw material, the polycarboxylic acid slump retaining agent adaptability of preparation is good, and performance is stablized, and resists
The anti-adsorption capacity of mud is strong, has excellent slump holding capacity.
Specific implementation mode
For the ease of those of ordinary skill in the art understand and implement the present invention, with reference to embodiment to the present invention make into
The detailed description of one step, it should be appreciated that embodiment described herein is merely to illustrate and explain the present invention, and is not used to
Limit the present invention.
Embodiment 1
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, it is characterised in that：Double initiation high stables
Property polycarboxylic acid slump retaining agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohols are organic
Solvent, hydrogen peroxide, acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, final product quality score after preparation
It is 50%, preparation method includes the following steps：
1) 395 parts of allyl polyethenoxy ethers and 200 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) temperature in the kettle is measured, control temperature is at 60 DEG C, and after temperature is stablized, it is 1 to be added at one time 0.3 part of mass ratio:1
The composition of sodium alkyl benzene sulfonate and sulfamic acid sodium, 7 parts of mass ratioes are 1:1 acrylic sodium sulfonate and 2- acrylamides -2-
The composition of methyl propane sulfonic acid, 0.5 part of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start to be added dropwise after solution B is added dropwise, in 10min molten
Liquid A, solution A time for adding are 2 hours, and solution B time for adding is 2.5 hours；Solution B is 1 by 4.8 parts of mass ratioes:1 is
The composition of azobisisoheptonitrile and di-cyclohexylperoxy di-carbonate, 15 parts of mass ratioes are 2:1 ethyl alcohol and the group of propylene glycol
Object and 80 parts of water compositions are closed, solution A is 1 by 45 parts of mass ratioes:The combination of 1 hydroxyethyl methacrylate and hydroxypropyl acrylate
Object, 28 parts of acrylic acid and 50 parts of water compositions；
4) it after completion of dropwise addition, heats to 66 DEG C, keeps temperature constant, cure 1 hour, wait for that reaction solution temperature is less than 30 DEG C
When, it is 1 to be slowly added to 12 parts of mass ratioes:1 potassium carbonate and the composition of sodium methoxide, moisturizing is to 1000 parts to get mass fraction
For 50% double initiation high stability polycarboxylic acid slump retaining agents.
Embodiment 2
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, it is characterised in that：Double initiation high stables
Property polycarboxylic acid slump retaining agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohols are organic
Solvent, hydrogen peroxide, acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, final product quality score after preparation
It is 50%, preparation method includes the following steps：
1) 400 parts of methyl allyl polyoxyethylene ethers and 160 parts of water are added in reaction kettle, agitating and heating waits for that its is molten
Solution；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 0.2 part of sodium alkyl benzene sulfonate at 58 DEG C
Composition, 6 parts of acrylic sodium sulfonates, 0.4 part of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start to be added dropwise after solution B is added dropwise, in 10min molten
Liquid A, solution A time for adding are 2.5 hours, and solution B time for adding is 3 hours；Solution B is 1 by 4.5 parts of mass ratioes:2 are
The composition of azobisisoheptonitrile and di-cyclohexylperoxy di-carbonate, 10 parts of mass ratioes are 1:1 ethyl alcohol and the group of propylene glycol
Object and 90 parts of water compositions are closed, solution A is made of 44 parts of hydroxyethyl methacrylates, 25 parts of acrylic acid and 50 parts of water；
4) it after completion of dropwise addition, heats to 67 DEG C, keeps temperature constant, cure 1.5 hours, wait for that reaction solution temperature is less than 30
DEG C when, be slowly added to 10 parts of sodium ethoxides, moisturizing to 1000 parts be 50% to get mass fraction double initiation high stability polycarboxylic acids
Slump retaining agent.
Embodiment 3
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, it is characterised in that：Double initiation high stables
Property polycarboxylic acid slump retaining agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohols are organic
Solvent, hydrogen peroxide, acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, final product quality score after preparation
It is 50%, preparation method includes the following steps：
1) 425 parts of isoamyl alcohol polyoxyethylene ethers and 200 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) measure temperature in the kettle, control temperature is at 56 DEG C, after temperature is stablized, be added at one time 0.25 part of sulfamic acid sodium,
3.2 parts of methylpropenyl sodium sulfonates, 0.25 part of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start to be added dropwise after solution B is added dropwise, in 10min molten
Liquid A, solution A time for adding are 3 hours, and solution B time for adding is 3.5 hours；Solution B by 2.6 parts of azobisisoheptonitrile, 11 parts
Ethyl alcohol and 85 parts of water compositions, solution A are 1 by 30 parts of mass ratioes:The combination of 2 hydroxyethyl methacrylate and hydroxypropyl acrylate
Object, 21 parts of acrylic acid and 55 parts of water compositions；
4) it after completion of dropwise addition, heats to 68 DEG C, keeps temperature constant, cure 2 hours, wait for that reaction solution temperature is less than 30 DEG C
When, 8 parts of sodium methoxides are slowly added to, moisturizing is protected to double initiation high stability polycarboxylic acids that 1000 parts are 50% to get mass fraction
It collapses agent.
Embodiment 4
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, it is characterised in that：Double initiation high stables
Property polycarboxylic acid slump retaining agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohols are organic
Solvent, hydrogen peroxide, acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, final product quality score after preparation
It is 50%, preparation method includes the following steps：
1) 410 parts of vinyl butyl ether polyoxyethylene ether and 180 parts of water are added in reaction kettle, agitating and heating waits for that its is molten
Solution；
2) temperature in the kettle is measured, control temperature is at 60 DEG C, and after temperature is stablized, it is 1 to be added at one time 0.28 part of mass ratio:1
Sodium alkyl sulfonate and sodium alkyl benzene sulfonate composition, 3 parts of sodium styrene sulfonate, 0.3 part of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start to be added dropwise after solution B is added dropwise, in 10min molten
Liquid A, solution A time for adding are 3.5 hours, and solution B time for adding is 4 hours；Solution B is by 3.3 parts of two rings of dicetyl peroxydicarbonate
Own ester, 12 parts of ethylene glycol and 88 parts of water compositions, solution A are 2 by 38 parts of mass ratioes:1 hydroxyethyl methacrylate and methyl-prop
The composition of olefin(e) acid hydroxypropyl acrylate, 25 parts of acrylic acid and 56 parts of water compositions；
4) it after completion of dropwise addition, heats to 69 DEG C, keeps temperature constant, cure 2.5 hours, wait for that reaction solution temperature is less than 30
DEG C when, be slowly added to 9 parts of ethanol amines, moisturizing to 1000 parts be 50% to get mass fraction double initiation high stability polycarboxylic acids
Slump retaining agent.
Embodiment 5
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, it is characterised in that：Double initiation high stables
Property polycarboxylic acid slump retaining agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohols are organic
Solvent, hydrogen peroxide, acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, final product quality score after preparation
It is 50%, preparation method includes the following steps：
1) 418 parts of isoamyl alcohol polyoxyethylene ethers and 180 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) measure temperature in the kettle, control temperature is at 60 DEG C, after temperature is stablized, be added at one time 0.3 part of sodium alkyl benzene sulfonate,
3 parts of mass ratioes 1:1 sodium vinyl sulfonate and the composition of acrylic sodium sulfonate, 0.33 part of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start to be added dropwise after solution B is added dropwise, in 10min molten
Liquid A, solution A time for adding are 3.5 hours, and solution B time for adding is 4 hours；Solution B is by 4.2 parts of two rings of dicetyl peroxydicarbonate
Own ester, 12 parts of methanol and 84 parts of water compositions, solution A are made of 31 parts of hydroxy propyl methacrylates, 25 parts of acrylic acid and 56 parts of water；
4) it after completion of dropwise addition, heats to 70 DEG C, keeps temperature constant, cure 3 hours, wait for that reaction solution temperature is less than 30 DEG C
When, be slowly added to 10 parts of triethanolamines, moisturizing to 1000 parts be 50% to get mass fraction double initiation high stability polycarboxylic acids
Slump retaining agent.
Embodiment 6
A kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, it is characterised in that：Double initiation high stables
Property polycarboxylic acid slump retaining agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohols are organic
Solvent, hydrogen peroxide, acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, final product quality score after preparation
It is 50%, preparation method includes the following steps：
1) 402 parts of allyl polyethenoxy ethers and 190 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) measure temperature in the kettle, control temperature is at 55 DEG C, after temperature is stablized, be added at one time 0.18 part of sodium alkyl sulfonate,
4.8 parts of mass ratioes are 1:1 methylpropene sodium sulfonate and the composition of sodium styrene sulfonate, 0.44 part of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start to be added dropwise after solution B is added dropwise, in 10min molten
Liquid A, solution A time for adding are 2.7 hours, and solution B time for adding is 3.2 hours；Solution B is by 3.7 parts of mass ratioes 1:1 idol
The composition of two different heptonitrile of nitrogen and azo dicyano valeric acid, 14 parts of ethylene glycol and 86 parts of water compositions, solution A is by 40 parts of acrylic acid
Hydroxypropyl acrylate, 24 parts of acrylic acid and 52 parts of water compositions；
4) it after completion of dropwise addition, heats to 72 DEG C, keeps temperature constant, cure 3 hours, wait for that reaction solution temperature is less than 30 DEG C
When, be slowly added to 11 parts of triisopropanolamines, moisturizing to 1000 parts be 50% to get mass fraction double poly- carboxylics of initiation high stability
Sour slump retaining agent.
Double initiation high stability polycarboxylic acid slump retaining agents of test above-described embodiment 1,2,3,4,5,6 and common polycarboxylic acids respectively
The net slurry initial fluidity in different cement, 1,2h mobility and concrete under slump retaining agent mother liquor comparable sodium is initial
The slump/divergence and through when the slump/divergence.Experiment cement used is new 42.5 ordinary portland cement of China, 42.5 general silicon of conch
Cement, 42.5 ordinary portland cement of Yadong, with reference to GB/8076-2008《Concrete admixture》Testing standard.
The different slump retaining agents of table 1 influence (new 42.5 ordinary portland cement of China) pulp flowage
The different slump retaining agents of table 2 influence (425 ordinary portland cement of conch) to pulp flowage
| Slump retaining agent type | Initial fluidity mm | 1h mobility mm | 2h mobility mm |
| Common slump retaining agent | \ | 190 | 170 |
| Embodiment 1 | \ | 225 | 215 |
| Embodiment 2 | \ | 220 | 215 |
| Embodiment 3 | \ | 235 | 225 |
| Embodiment 4 | \ | 230 | 220 |
| Embodiment 5 | \ | 230 | 225 |
| Embodiment 6 | \ | 225 | 215 |
The different slump retaining agents of table 3 influence (42.5 ordinary portland cement of Yadong) to pulp flowage
| Slump retaining agent type | Initial fluidity mm | 1h mobility mm | 2h mobility mm |
| Common slump retaining agent | \ | 240 | 230 |
| Embodiment 1 | \ | 235 | 220 |
| Embodiment 2 | \ | 230 | 215 |
| Embodiment 3 | \ | 225 | 215 |
| Embodiment 4 | \ | 235 | 230 |
| Embodiment 5 | \ | 225 | 220 |
| Embodiment 6 | \ | 240 | 225 |
The different slump retaining agents of table 4 influence (new 42.5 ordinary portland cement of China) concrete flowability
The different slump retaining agents of table 5 influence (42.5 ordinary portland cement of conch) to concrete flowability
The different slump retaining agents of table 6 influence (42.5 ordinary portland cement of Yadong) to concrete flowability
According to above-mentioned initial fluidity, 1,2h mobility and concrete it is initial and through when mobility compare, high-adaptability is high
Admittedly embodiment containing polycarboxylic acid slump retaining agent 1,2,3,4,5,6, without net slurry initial fluidity, uses difference as common slump retaining agent
When cement experiment, 1h, 2h flow the more common slump retaining agent mother liquor performance of sex expression mobility and stablize, and slump retaining is preferable；Concrete stream
Dynamic property data comparison, the concrete flowability of the function of slump protection of embodiment 1,2,3,4,5,6 in different brands cement can tend to
Stablize, overall data illustrates that the high-adaptability large arch dam polycarboxylic acid slump retaining agent formula and mature preparation process are reliable, and at this stage
Common slump retaining agent mother liquor is compared, and function of slump protection is stablized, adaptable.
Claims (10)
1. a kind of double preparation methods for causing high stability polycarboxylic acid slump retaining agent, it is characterised in that：Double initiation high stabilities
Polycarboxylic acid slump retaining agent is prepared from the following components：Polyether macromonomer, alkyl acrylate, medium temperature initiator, alcohols are organic molten
Agent, hydrogen peroxide, acrylic acid, chain-transferring agent, bleeding agent, neutralizer, water；1000 parts of gross mass, preparation method includes the following steps：
1) 395-425 parts of polyether macromonomers and 150-200 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 0.1-0.3 parts of bleeding agents, 3-7 at 52-60 DEG C
Part chain-transferring agent, 0.2-0.5 parts of hydrogen peroxide；
3) after 5min, start that solution B, solution A is added dropwise successively, start that solution A is added dropwise after solution B is added dropwise, in 10min,
Solution A time for adding is a hours, and solution B time for adding is a+0.5 hours；Solution B is by 2.6-4.8 parts of medium temperature initiators, 10-
15 parts of alcohol organic solvents and 80-90 parts of water compositions, solution A is by 30-45 parts of alkyl acrylates, 20-28 parts of acrylic acid and 50-
60 parts of water compositions；
4) after completion of dropwise addition, 66-72 DEG C is heated, keeps temperature constant, is cured b hours, waits for that reaction solution temperature is less than 30 DEG C
When, be slowly added to 6-12 parts of neutralizers, moisturizing to 1000 parts be 50% to get mass fraction double initiation high stability polycarboxylic acids
Slump retaining agent finished product.
2. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：It is described poly-
Ether polymeric monomer is by allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, vinyl butyl
One or more of ether polyoxyethylene ether forms.
3. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：Described third
Olefin(e) acid Arrcostab is by one in hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate
Kind or several compositions.
4. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：In described
Warm initiator is initiator of the 1h half life temperatures at 50-75 DEG C, specifically by azobisisoheptonitrile, azo dicyano valeric acid, mistake
Aoxidize one or more of two diisopropyl carbonates, di-cyclohexylperoxy di-carbonate composition.
5. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：The alcohol
Class organic solvent is made of one or more of methanol, ethyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, glycerine.
6. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：It is described to ooze
Saturating agent is by sulfated castor oil, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, alkyl sulfate sodium, sodium secondary alkyl sulfonate, secondary alkyl sulphur
One or more of acid esters sodium, Negel, succinic acid alkyl ester sulfonate sodium, sulfamic acid sodium form.
7. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：The chain
Transfer agent by thioacetic acid, mercaptopropionic acid, mercaptoethanol, sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate,
One or more of sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonics, sodium hypophosphite form.
8. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：In described
With agent by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanol amine, diethanol amine,
One or more of triethanolamine, triisopropanolamine form.
9. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：It is described double
Oxygen water is that mass percent is 27.5% industrial grade hydrogen peroxide.
10. double preparation methods for causing high stability polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：It is described
Solution A time for adding a is 2-4h；The curing time b is 1-3h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713573A (en) * | 2019-09-18 | 2020-01-21 | 山东申鑫建材科技有限公司 | Method for synthesizing polycarboxylate superplasticizer slump-retaining mother liquor |
| CN112876168A (en) * | 2021-02-09 | 2021-06-01 | 武汉理工大学 | Thin-wall high-pier concrete and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2020422A1 (en) * | 2007-07-31 | 2009-02-04 | Sika Technology AG | Emulgating polymers and their use |
| US20100197853A1 (en) * | 2007-07-10 | 2010-08-05 | The Nippon Synthetic Chemical Industry Co., Ltd. | Aqueous synthetic resin emulsion for cement mortar admixture, re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture, and cement mortar admixture employing the same |
| CN103408706A (en) * | 2013-08-19 | 2013-11-27 | 科之杰新材料集团有限公司 | High-performance polycarboxylic acid water reducing agent and preparation method thereof |
| CN105254822A (en) * | 2015-11-20 | 2016-01-20 | 科之杰新材料集团有限公司 | Preparation method of polycarboxylate superplasticizer |
-
2018
- 2018-03-30 CN CN201810275878.4A patent/CN108373525A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100197853A1 (en) * | 2007-07-10 | 2010-08-05 | The Nippon Synthetic Chemical Industry Co., Ltd. | Aqueous synthetic resin emulsion for cement mortar admixture, re-emulsifiable aqueous synthetic resin emulsion powder for cement mortar admixture, and cement mortar admixture employing the same |
| EP2020422A1 (en) * | 2007-07-31 | 2009-02-04 | Sika Technology AG | Emulgating polymers and their use |
| CN103408706A (en) * | 2013-08-19 | 2013-11-27 | 科之杰新材料集团有限公司 | High-performance polycarboxylic acid water reducing agent and preparation method thereof |
| CN105254822A (en) * | 2015-11-20 | 2016-01-20 | 科之杰新材料集团有限公司 | Preparation method of polycarboxylate superplasticizer |
Non-Patent Citations (2)
| Title |
|---|
| 姚志光: "《高分子化学》", 31 January 2013, 北京理工大学出版社 * |
| 韦军: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713573A (en) * | 2019-09-18 | 2020-01-21 | 山东申鑫建材科技有限公司 | Method for synthesizing polycarboxylate superplasticizer slump-retaining mother liquor |
| CN112876168A (en) * | 2021-02-09 | 2021-06-01 | 武汉理工大学 | Thin-wall high-pier concrete and preparation method thereof |
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