CN108503255A - A kind of preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization - Google Patents
A kind of preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization Download PDFInfo
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- CN108503255A CN108503255A CN201810275711.8A CN201810275711A CN108503255A CN 108503255 A CN108503255 A CN 108503255A CN 201810275711 A CN201810275711 A CN 201810275711A CN 108503255 A CN108503255 A CN 108503255A
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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
- C04B24/2682—Halogen containing polymers, e.g. PVC
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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
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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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Abstract
The present invention provides a kind of preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization：A certain amount of liquid polyether macromonomer is added in reaction kettle, agitating and heating；Temperature is controlled at 100 105 DEG C, is initially added into a certain amount of solubilizer, chain-transferring agent, organic peroxy class initiator, initial initiator, bleeding agent；After 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is 0.5 2h, and minor comonomer solution is made of a certain proportion of fluoro function monomer, alkyl acrylate and acrylic acid；After 10min is added dropwise in minor comonomer solution, a certain amount of organic peroxy class initiator is first put into for the first time into kettle, it is primary every 10min inputs later, put into last time before minor comonomer solution is added dropwise to complete；After completion of dropwise addition, temperature is raised at 110 115 DEG C, keeps temperature constant, cures 1 3h, postcooling slice encapsulation to get finished product of the present invention.Final solid sheet polycarboxylic acid slump retaining agent prepared by the present invention greatly reduces transportation cost convenient for storage.
Description
Technical field
The invention belongs to building material technical fields, are related to concrete admixture field, specifically a kind of ontology
The preparation method of the solid sheet polycarboxylic acid slump retaining agent of polymerization.
Background technology
In the production of premixing high performance concrete, slump retaining agent is indispensable important composition portion as water-reducing agent
Point.The same with common polycarboxylate water-reducer, the solid of common polycarboxylic acid slump retaining agent contains generally 40% or so, because containing a large amount of
Moisture as solvent, cause the cost in terms of storage and transport higher.With the continuous propulsion of engineering construction, polycarboxylic acids subtracts
The use of aqua and polycarboxylic acid slump retaining agent and demand are all increasing, and especially many engineering projects are produced from water-reducing agent now
Farther out, long-distance transportation is both uneconomical or is difficult to meet dosage requirement on ground.Current large arch dam polycarboxylic acid slump retaining agent on the market
It is by being obtained to liquid polycarboxylic acid slump retaining agent heating spray drying later, not only performance is declined, but also equipment is complicated,
Cost is higher.From the point of view of demand, solid polycarboxylic acid slump retaining agent has good prospects.
In the technique of bulk polymerization at this stage, it is faced with the high viscosity problem that a prodigious problem is exactly water-less environment,
Lead to the less efficient of crash response between molecule, therefore the viscosity for reducing reaction solution is in the weight for making reaction be smoothed out
Weight using suitable viscosity reduction means and coordinates the solid polycarboxylic acid slump retaining agent of rational technique preparation that can meet requirement.
Patent CN106749967A discloses a kind of preparation method of solid collapse protective poly-carboxylic acid water reducing agent, and specific steps are such as
Under：1) VPEG monomers are added in reaction kettle, are warming up to 20-30 DEG C, be at molten condition；2) be added dropwise by acrylic acid,
First mixed solution of unsaturated phosphate monomer and unsaturated silane composition and by initiator, chain-transferring agent and organic molten
Second mixed solution of agent composition, drips off in 0.5-1h, continues anti-0.8-1.2h；3) remover is vacuumized using mechanical pump
Organic solvent in material, later material by condense slicer be sliced to get the solid collapse protective poly-carboxylic acid diminishing
Agent.
Patent CN106749970A discloses a kind of sheet polycarboxylic acid slump retaining agent and its polymerization process for preparing admittedly, specific steps
It is as follows：805-845 parts of polyether macromonomers are placed in reaction kettle, heating stirring, until dissolving is complete；Equilibrium temperature is 65-75
DEG C, disposably put into 5-10 parts of weak chain-transferring agents, 2.0-4.5 parts of organic peroxy class initiators, 5.5-10.5 parts of unsaturated binary
Carboxylic acid and 5.0-11.5 parts of unsaturated sulfonic acid class minor comonomers；Then, the 5-10 parts of concentrated sulfuric acids, adjustment bottom liquid pH value to 5.0 is added；
Start the mixed solution that 35-65 parts of acrylic acid, 70-115 parts of acrylic acid hydroxy alkyl esters and 2.8-4.6 parts strong chain-transferring agent are added dropwise,
During dropwise addition, azo-initiator is put at twice；After being added dropwise, 12h is cured, 5.5-12.0 parts of neutralizers are added, stir
It mixes uniformly, is sliced to get finished product after cooling.
Patent CN106749966A discloses a kind of preparation method of solid polycarboxylic acid slump retaining agent, includes the following steps：1)
Unsaturated polyoxyethylene ether, cumenyl polyoxyethylene ether are added in reaction kettle, heats up, is at molten condition, so
After be added at one time catalyst, and stir evenly；2) the first mixed solution is added dropwise respectively into material and the second mixing is molten
Liquid；3) it after reaction, is vacuumized using mechanical pump, the organic solvent in material, is then cut using condensation slicer
Piece is to get to the solid polycarboxylic acid slump retaining agent of white plates.
It is different from the above patent, the present invention uses the synthetic method of bulk polymerization, is directly docked with polyether macromonomer producer,
It is produced using the high-temperature liquid state polyethers just produced, and is selected by the technological design of optimization and raw material, introduce fluoro
The raw materials such as function monomer, solubilizer, thinner, lubricant carry out high temperature viscosity reduction, increase reactivity；Introducing bleeding agent, profit
With its excellent emulsification, dispersibility, each component raw material is made to be sufficiently mixed reaction, finally prepare have excellent performance, adaptability it is good
Good pure solid-state polycarboxylic acid slump retaining agent.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of system of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization
Preparation Method.
Solid polycarboxylic acid slump retaining agent is prepared by the way of bulk polymerization at present, can not all obtain water-reducing rate height, adaptability
Well, the superior product of function of slump protection, the viscosity for being primarily due to bulk polymerization is larger, can not finally obtain ideal
Slump retaining agent configuration and suitable molecular weight.The present invention use bulk polymerization synthetic method, directly with polyether macromonomer producer
Docking, is produced using the liquid polyethers of also non-cooling solidification, has good economy and operability.Into system
Fluoro function monomer is introduced, is non-polar group, there is defoaming foam control ability well, can significantly reduce the gas in system
Content is steeped, the contact probability between molecule and molecule is increased.
In terms of unclassified stores, solubilizer is introduced, it is ensured that each raw material can uniformly be mixed under low solvent condition；Draw
Enter thinner, reduces the viscosity of high-temperature anhydrous environment；Lubricant is introduced, makes entire reaction environment more sharp on the basis of viscosity reduction
It is graft-polymerized in molecule；The bleeding agent of introducing has hydrophilic lipophilic group, is aligned in the surface energy of solution, and can make table
Face tension is remarkably decreased, and obtains excellent emulsification, dispersibility, and each component raw material is enable to be sufficiently mixed reaction.In conjunction with entire anti-
Technological temperature is answered, selects medium temperature initiator that initial initiation, the slightly higher organic peroxy class of reselection half life temperature is driven to cause
Repeatedly input, acquisition smoothly cause effect in batches in the course of the polymerization process for agent.Later stage curing heat preservation for a long time, eliminates residual and draws
Sending out the unstability of agent water-reducing agent later stage performance influences, and promotes the reaction was complete to carry out.
Technical scheme is as follows：
A kind of preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylic acid slump retaining agent is mainly prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid alkyl
Ester, acrylic acid, initial initiator, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent,
Neutralizer；1000 parts of gross mass, preparation method includes the following steps：
1) 840-880 parts of liquid polyether macromonomers, 2-5 portions of thinners, 1-3 parts of lubricants are added in reaction kettle, are stirred
Mix heating；
2) temperature in the kettle is measured, control temperature is at 100-105 DEG C, after temperature is stablized, is added at one time 2.2-3.8 parts of solubilisings
Agent, 6-9 parts of chain-transferring agents, 0.5-1.5 parts of organic peroxy class initiators, 0.3-0.8 parts of initial initiators, 0.7-1 parts of infiltrations
Agent；
3) after 5min, start be added dropwise minor comonomer solution, minor comonomer solution time for adding be 0.5-2h, minor comonomer solution by
20-35 parts of fluoro function monomers, 45-70 parts of alkyl acrylates, 20-45 parts of acrylic acid compositions；Minor comonomer solution is added dropwise
After 10min, 0.3-0.7 parts of organic peroxy class initiators are first put into for the first time into kettle, it is primary every 10min inputs later, often
Secondary input amount is identical, and last time has been put into before minor comonomer solution is added dropwise to complete, and puts into 1.4-3.6 parts of organic mistakes in total
Oxygen class initiator；
4) after completion of dropwise addition, temperature is raised at 110-115 DEG C, keeps temperature constant, cures b hours, waits for reaction solution
When temperature is less than 30 DEG C, 6-10 parts of neutralizers are slowly added to, are protected to get the solid sheet polycarboxylic acids of bulk polymerization after cooling slice
It collapses agent.
The polyether macromonomer is that polyethers producer produces offline also not solidified liquid polyether macromonomer, specifically by allyl
Base polyoxyethylene ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether
One or more of composition；Preferably isoamyl alcohol polyoxyethylene ether.
The fluoro function monomer, specifically by acrylic acid trifluoro ethyl ester, methacrylic acid 2,2,2- trifluoro ethyl esters) in one
Kind or two kinds of compositions；Preferably mass ratio 2:The combination of 1 acrylic acid trifluoro ethyl ester and methacrylic acid 2,2,2- trifluoro ethyl esters
Object.
The alkyl acrylate is by hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, metering system
One or more of sour hydroxypropyl acrylate forms；Preferably mass ratio is 1:1 hydroxy-ethyl acrylate and the group of hydroxypropyl acrylate
Close object.
The initial initiator is initiator of the 1h half life temperatures at 70-95 DEG C, specifically by dibenzoyl peroxide, mistake
Aoxidize one or more of lauroyl, azodiisobutyronitrile, peroxidating trimethylacetic acid tert-butyl ester composition；It is preferred that 1h half-life period temperature
Spend the initiator close to reaction temperature；It is preferred that the dibenzoyl peroxide of 92 DEG C of 1h half life temperatures.
The organic peroxy class initiator is organic peroxy class initiator of the 1h half life temperatures at 120-140 DEG C, specifically
It is made of one or more of peroxidized t-butyl perbenzoate, cumyl peroxide, di-t-butyl peroxide；It is preferred that 1h
Initiator of the half life temperature close to reaction temperature；It is preferred that the peroxidized t-butyl perbenzoate that 1h half life temperatures are 122 DEG C.
The solubilizer is by one or more of sodium tripolyphosphate, lauryl sodium sulfate, Stepanol MG group
At；Preferably mass ratio 1:2 sodium tripolyphosphate and the composition of lauryl sodium sulfate.
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 is than 2:1 is the combination of 2- acrylamide-2-methyl propane sulfonics and sodium hypophosphite
Object.
The thinner is by poly- methyl fluorosilicone, nonylphenol polyoxyethylene ether, octadecanol polyethers, dipropylene glycol first
One or more of ether, fatty diglycollic amide, organosilicon sodium humate, organosilicon potassium humate form；It is preferred that resistance to height
Warm type thinner；Preferred mass is than 1:The composition of 1 poly- methyl fluorosilicone and nonylphenol polyoxyethylene ether.
The lubricant is by calcium stearate, magnesium stearate, zinc stearate, stearic amide, erucyl amide, oleamide
One or more of compositions；It is preferred that high temperature resistant type lubricant；It is preferred that mass ratio of the melting range not higher than 100 DEG C is 1:2 erucic acid acyl
The composition of amine and oleamide.
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；Preferably anionic bleeding agent；Preferably with the sodium alkyl benzene sulfonate of phenyl.
The neutralizer is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, second
One or more of compositions of hydramine, diethanol amine, triethanolamine, triisopropanolamine；Preferably sodium methoxide.
The beneficial effects of the invention are as follows：
1, it using the synthetic method of bulk polymerization, is directly docked with polyether macromonomer producer, uses also non-cooling solidification
Liquid polyethers is produced, and has good economy and operability, and the solid sheet for finally obtaining water-free pure solid is poly-
Carboxylic acid water reducer greatly reduces the cost of transport and storage；Using the shorter time for adding of faster rate of addition, avoid
The too short problem of main chain caused by long-time high temperature, while shorter time for adding brings faster speed of production, production efficiency
It is high.
2, in conjunction with entire reaction process temperature, 1h half life temperatures is selected to drive initial initiation in 70-95 DEG C of initiator,
Reselection 1h half life temperatures are repeatedly put into batches in the course of the polymerization process in 120-140 DEG C of organic peroxy class initiator, are obtained
Smoothly cause effect, enables reaction to continue to carry out under high temperature environment, the water-reducing agent molecular weight finally obtained is more suitable.
3, fluoro function monomer is introduced into system, is non-polar group, and there is defoaming foam control ability well, can show
The air bubble content in reduction system is write, the contact probability between molecule and molecule is increased；On this basis, solubilizer is introduced, into
One step ensures each raw material can uniformly be mixed under low solvent condition；Thinner is introduced, the viscous of high-temperature anhydrous environment is reduced
Degree；Lubricant is introduced, entire reaction environment is made to be more conducive to molecule graft polymerization on the basis of viscosity reduction；The bleeding agent of introducing has
Have hydrophilic lipophilic group, aligned in the surface energy of solution, and surface tension can be made to be remarkably decreased, obtain excellent emulsification,
Dispersibility enables each component raw material to be sufficiently mixed reaction.
4, using the rear way of distillation, maturation stage long-time heat preservation partly declines remaining especially 1h in composite initiation system
Phase temperature is eliminated in 120-140 DEG C of organic peroxy class initiator in distillation process, prevents residual initiator to water-reducing agent
The unstability of later stage performance influences, moreover it is possible to promote the reaction was complete to carry out, finally obtain ideal molecular weight and molecular configuration.
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 had to
It is of the invention in limiting.
Embodiment 1
The solid sheet polycarboxylic acids guarantor of the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, the bulk polymerization is collapsed
Agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, alkyl acrylate, acrylic acid, initial initiator,
Organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent, neutralizer；1000 parts of gross mass, system
Preparation Method includes the following steps：
1) by 840 parts of liquid isoamyl alcohol polyoxyethylene ethers, 2 parts of mass ratioes 1：2 poly- methyl fluorosilicone and nonyl phenol
The composition of polyoxyethylene ether, 1 part of mass ratio are 1:2 erucyl amide and the composition of oleamide are added in reaction kettle,
Agitating and heating；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 2.2 parts of mass ratioes 1 at 100 DEG C:2
Sodium tripolyphosphate and lauryl sodium sulfate composition, 9 parts of mass ratioes 2:1 be 2- acrylamide-2-methyl propane sulfonics and time
Sodium phosphite, 0.5 part of mass ratio 1:1 peroxidized t-butyl perbenzoate and the composition of cumyl peroxide, 0.8 part of mistake
Aoxidize dibenzoyl, 0.7 part of sodium alkyl benzene sulfonate；
3) after 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is 0.5 hour, minor comonomer solution
It is 2 by 20 parts of mass ratioes:1 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 70 parts of quality
Than being 1:1 hydroxy-ethyl acrylate and the composition of hydroxypropyl acrylate, 45 parts of acrylic acid compositions；Minor comonomer solution is added dropwise
After 10min, 0.7 part of mass ratio 1 is first put into for the first time into kettle:1 isopropyl benzene hydroperoxide and the group of cumyl peroxide
Object is closed, primary every 10min inputs later, each input amount is identical, has been put into before minor comonomer solution is added dropwise to complete last
2 totally 1.4 parts of mass ratioes 1 are once put into total:1 isopropyl benzene hydroperoxide and the composition of cumyl peroxide；
4) after completion of dropwise addition, temperature is raised at 115 DEG C, keeps temperature constant, cures 3 hours, waits for reaction solution temperature
When less than 30 DEG C, 8 parts of sodium methoxides are slowly added to, cool down the solid sheet polycarboxylic acid slump retaining agent to get bulk polymerization after being sliced.
Embodiment 2
The preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, the solid sheet polycarboxylic acids diminishing of the bulk polymerization
Agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, alkyl acrylate, acrylic acid, initial initiator,
Organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent, neutralizer；1000 parts of gross mass, system
Preparation Method includes the following steps：
1) it is 1 by 880 parts of liquid mass ratioes:1 isoamyl alcohol polyoxyethylene ether and vinyl butyl ether polyoxyethylene ether
Composition, 5 parts of mass ratioes 1:1 poly- methyl fluorosilicone and the composition of nonylphenol polyoxyethylene ether, 3 parts of mass ratioes are
1:2 calcium stearate and the composition of oleamide are added in reaction kettle, agitating and heating；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 3.8 parts of mass ratioes 2 at 105 DEG C:1
Sodium tripolyphosphate and lauryl sodium sulfate composition, 6 parts of mass ratioes 1:2 be 2- acrylamide-2-methyl propane sulfonics and time
Sodium phosphite, 1.5 parts of peroxidized t-butyl perbenzoates, 0.3 part of dilauroyl peroxide, 1 part of sodium alkyl sulfonate；
3) after 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is 0.7 hour, minor comonomer solution
It is 1 by 27 parts of mass ratioes:1 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 45 parts of quality
Than being 1:1 hydroxyethyl methacrylate and the composition of hydroxy propyl methacrylate, 20 parts of acrylic acid compositions；Minor comonomer is molten
After drop adds 10min, 0.65 part of isopropyl benzene hydroperoxide is first put into for the first time into kettle, it is primary every 10min inputs later,
Each input amount is identical, and last time put into before minor comonomer solution is added dropwise to complete, in total input 3 times totally 1.95 parts it is different
Cumene hydroperoxide；
4) after completion of dropwise addition, temperature is raised at 110 DEG C, keeps temperature constant, cures 2.5 hours, waits for reaction solution temperature
When degree is less than 30 DEG C, 6 parts of sodium ethoxides are slowly added to, cool down the solid sheet polycarboxylic acid slump retaining agent to get bulk polymerization after being sliced.
Embodiment 3
The preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, the solid sheet polycarboxylic acids diminishing of the bulk polymerization
Agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, alkyl acrylate, acrylic acid, initial initiator,
Organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent, neutralizer；1000 parts of gross mass, system
Preparation Method includes the following steps：
1) 863 parts of liquid methyl allyl polyoxyethylene ethers, 3 parts of nonylphenol polyoxyethylene ether, 2 parts of stearic amides are added
Enter into reaction kettle, agitating and heating；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 2.5 parts of sodium tripolyphosphates, 7 at 101 DEG C
Part 2- acrylamide-2-methyl propane sulfonics, 0.8 part of cumyl peroxide, 0.5 part of azodiisobutyronitrile, 0.75 part of secondary alkyl
Sodium sulfovinate；
3) after 5min, start be added dropwise minor comonomer solution, minor comonomer solution time for adding be 1 hour, minor comonomer solution by
35 parts of acrylic acid trifluoro ethyl esters, 50 parts of hydroxy-ethyl acrylates, 25 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution, to
0.4 part of cumyl peroxide is first put into kettle for the first time, primary every 10min inputs later, each input amount is identical, directly
Last time has been put into before being added dropwise to complete to minor comonomer solution, has put into 5 totally 2 parts of cumyl peroxides in total；
4) after completion of dropwise addition, temperature is raised at 114 DEG C, keeps temperature constant, cures 2 hours, waits for reaction solution temperature
When less than 30 DEG C, 9 parts of ethanol amines are slowly added to, cool down the solid sheet polycarboxylic acid slump retaining agent to get bulk polymerization after being sliced.
Embodiment 4
The preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, the solid sheet polycarboxylic acids diminishing of the bulk polymerization
Agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, alkyl acrylate, acrylic acid, initial initiator,
Organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent, neutralizer；1000 parts of gross mass, system
Preparation Method includes the following steps：
1) 860 parts of liquid allyl polyethenoxy ethers, 4 parts of poly- methyl fluorosilicones, 1.5 parts of erucyl amides are added to instead
It answers in kettle, agitating and heating；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 2.8 parts of dodecyl sulphates at 103 DEG C
Sodium, 8 parts of sodium hypophosphites, 1 part of di-t-butyl peroxide, 0.5 part of peroxidating trimethylacetic acid tert-butyl ester, 0.8 part of amber acid alkyl ester
Sodium sulfonate；
3) after 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is 1.2 hours, minor comonomer solution
It is made of 21 parts of methacrylic acid 2,2,2- trifluoro ethyl esters, 51 parts of hydroxypropyl acrylates, 39 parts of acrylic acid；Minor comonomer solution drips
After adding 10min, 0.6 part of di-t-butyl peroxide is first put into for the first time into kettle, it is primary every 10min inputs later, it throws every time
It is identical to enter amount, last time has been put into before minor comonomer solution is added dropwise to complete, puts into 6 totally 3.6 parts of two uncles of peroxidating in total
Butyl；
4) after completion of dropwise addition, temperature is raised at 111 DEG C, keeps temperature constant, cures 1.8 hours, waits for reaction solution temperature
When degree is less than 30 DEG C, 7 parts of sodium bicarbonates are slowly added to, are collapsed to get the solid sheet polycarboxylic acids guarantor of bulk polymerization after cooling slice
Agent.
Embodiment 5
The preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, the solid sheet polycarboxylic acids diminishing of the bulk polymerization
Agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, alkyl acrylate, acrylic acid, initial initiator,
Organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent, neutralizer；1000 parts of gross mass, system
Preparation Method includes the following steps：
1) it is 1 by 867 parts of liquid mass ratioes:1 methyl allyl polyoxyethylene ether and isoamyl alcohol polyoxyethylene ether
Composition, 4.5 parts of dipropylene glycol methyl ethers, 2.5 parts of oleamides are added in reaction kettle, agitating and heating；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 3 parts of dodecyl sulphates at 103 DEG C
Magnesium, 8.5 parts of methylpropene sodium sulfonates, 1.2 parts of mass ratioes 1:The combination of 1 cumyl peroxide and di-t-butyl peroxide
Object, 0.6 part of mass ratio 1:1 dibenzoyl peroxide and the composition of azodiisobutyronitrile, 0.85 part of sulfamic acid sodium；
3) after 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is 1.7 hours, minor comonomer solution
It is 1 by 24 parts of mass ratioes:2 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 45 parts of methyl
Hydroxy-ethyl acrylate, 30 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution, 0.35 part of matter is first put into for the first time into kettle
Measure ratio 1:1 cumyl peroxide and the composition of di-t-butyl peroxide, it is primary every 10min inputs later, it throws every time
It is identical to enter amount, last time has been put into before minor comonomer solution is added dropwise to complete, puts into 9 totally 3.15 parts of mass ratioes 1 in total:1
Cumyl peroxide and di-t-butyl peroxide composition；
4) after completion of dropwise addition, temperature is raised at 114 DEG C, keeps temperature constant, cures 1.5 hours, waits for reaction solution temperature
When degree is less than 30 DEG C, 10 parts of sodium carbonate are slowly added to, cool down the solid sheet polycarboxylic acid slump retaining agent to get bulk polymerization after being sliced.
Embodiment 6
The preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, the solid sheet polycarboxylic acids diminishing of the bulk polymerization
Agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, alkyl acrylate, acrylic acid, initial initiator,
Organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent, neutralizer；1000 parts of gross mass, system
Preparation Method includes the following steps：
1) it is by 854 parts of liquid ethylene base butyl ether polyoxyethylene ether, 3.5 parts of organosilicon sodium humates, 1.5 parts of mass ratioes
1:1 zinc stearate and the composition of stearic amide are added in reaction kettle, agitating and heating；
2) temperature in the kettle is measured, control temperature is at 104 DEG C, and after temperature is stablized, it is 1 to be added at one time 3.6 parts of mass ratioes:1
Sodium tripolyphosphate and the composition of Stepanol MG, 7.5 parts of acrylic sodium sulfonates, 1.3 parts of tertiary fourths of perbenzoic acid
Ester, 0.7 part of mass ratio 1:1 dilauroyl peroxide and the composition of azodiisobutyronitrile, 0.9 part of Negel；
3) after 5min, start be added dropwise minor comonomer solution, minor comonomer solution time for adding be 2 hours, minor comonomer solution by
30 parts of fluoro function monomers, 65 parts of hydroxy propyl methacrylates, 20 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution,
First put into 0.3 part of peroxidized t-butyl perbenzoate for the first time into kettle, primary every 10min inputs later, each input amount phase
Together, last time has been put into before minor comonomer solution is added dropwise to complete, has put into 11 totally 3.3 parts of perbenzoic acid uncles in total
Butyl ester；
4) after completion of dropwise addition, temperature is raised at 113 DEG C, keeps temperature constant, cures 1 hour, waits for reaction solution temperature
When less than 30 DEG C, 8.8 parts of diethanol amine are slowly added to, are collapsed to get the solid sheet polycarboxylic acids guarantor of bulk polymerization after cooling slice
Agent.
Solid sheet polycarboxylic acid slump retaining agent and water prepared by embodiment 1,2,3,4,5,6 presses 4：6 ratio is dissolved in water, really
Its fixed water solubility is preferably.
The solid sheet polycarboxylic acid slump retaining agent of test above-described embodiment 1,2,3,4,5,6 and common polycarboxylic acid slump retaining agent are female respectively
Cement paste initial fluidity, 1,2h mobility and concrete initial slump/divergence under liquid comparable sodium and through when collapse
Degree of falling/divergence.Experiment cement used is new 42.5 ordinary portland cement of China, with reference to GB/8076-2008《Concrete admixture》It surveys
Test-object is accurate.
The different slump retaining agents of table 1 influence pulp flowage
| Slump retaining agent type | Initial fluidity mm | 1h mobility mm | 2h mobility mm |
| Common slump retaining agent | \ | 245 | 215 |
| Embodiment 1 | \ | 240 | 220 |
| Embodiment 2 | \ | 235 | 230 |
| Embodiment 3 | \ | 240 | 210 |
| Embodiment 4 | \ | 250 | 240 |
| Embodiment 5 | \ | 240 | 245 |
| Embodiment 6 | \ | 235 | 240 |
The different slump retaining agents of table 2 influence concrete flowability
According to above-mentioned initial fluidity, 1,2h mobility and concrete it is initial and through when mobility compare, Gu the poly- carboxylic of sheet
Sour slump retaining agent embodiment 1,2,3,4,5,6 without net slurry initial fluidity as common slump retaining agent, more commonly protect by 1h mobility
The agent mother liquor that collapses is slightly aobvious to be not so good as, but slump retaining is preferable, and 2h flowing sex expressions are better than common slump retaining agent；Concrete flowability data pair
It can reach unanimity with common slump retaining agent concrete flowability than, the function of slump protection of embodiment 1,2,3,4,5,6 or slightly better, it is whole
Volume data illustrates that the solid sheet polycarboxylic acid slump retaining agent formula and mature preparation process are reliable, in high viscosity reaction environment, conversion ratio
Height reaches unanimity with 40% slump retaining agent mother liquor performance of liquid at this stage, and slump retaining is slightly good.
Claims (10)
1. a kind of preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization, it is characterised in that：The bulk polymerization is consolidated
Sheet polycarboxylic acid slump retaining agent is mainly prepared from the following components：Polyether macromonomer, fluoro function monomer, alkyl acrylate,
Acrylic acid, initial initiator, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, lubricant, bleeding agent, neutralization
Agent；1000 parts of gross mass, preparation method includes the following steps：
1) 840-880 parts of liquid polyether macromonomers, 2-5 portions of thinners, 1-3 parts of lubricants are added in reaction kettle, stirring adds
Heat；
2) measure temperature in the kettle, control temperature is at 100-105 DEG C, after temperature is stablized, be added at one time 2.2-3.8 parts of solubilizer,
6-9 parts of chain-transferring agents, 0.5-1.5 parts of organic peroxy class initiators, 0.3-0.8 parts of initial initiators, 0.7-1 parts of bleeding agents；
3) after 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is 0.5-2h, and minor comonomer solution is by 20-
35 parts of fluoro function monomers, 45-70 parts of alkyl acrylates, 20-45 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution,
First put into 0.3-0.7 parts of organic peroxy class initiators for the first time into kettle, primary every 10min inputs later, each input amount
It is identical, last time has been put into before minor comonomer solution is added dropwise to complete, 1.4-3.6 parts of organic peroxy classes has been put into total and causes
Agent；
4) after completion of dropwise addition, temperature is raised at 110-115 DEG C, keeps temperature constant, 1-3h is cured, waits for that reaction solution temperature is low
When 30 DEG C, 6-10 parts of neutralizers are slowly added to, cool down the solid sheet polycarboxylic acid slump retaining agent to get bulk polymerization after being sliced.
2. the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization according to claim 1, it is characterised in that：It is described
Liquid polyether macromonomer is that polyethers producer produces offline also not solidified liquid polyether macromonomer, specifically by allyl polyoxy second
Alkene ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, one kind in vinyl butyl ether polyoxyethylene ether or
Several compositions.
3. the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization according to claim 1, it is characterised in that：It is described
Fluoro function monomer, specifically by acrylic acid trifluoro ethyl ester, methacrylic acid 2,2, one or both of 2- trifluoro ethyl esters composition.
4. the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization according to claim 1, it is characterised in that：It is described
Alkyl acrylate is by hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate
One or more composition.
5. the preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization according to claim 1, it is characterised in that：It is described
Initial initiator be initiator of the 1h half life temperatures at 70-95 DEG C, specifically by dibenzoyl peroxide, dilauroyl peroxide,
One or more of azodiisobutyronitrile, peroxidating trimethylacetic acid tert-butyl ester form.
6. the preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization according to claim 1, it is characterised in that：It is described
Organic peroxy class initiator is organic peroxy class initiator of the 1h half life temperatures at 120-140 DEG C, specifically by benzoyl peroxide first
One or more of tert-butyl acrylate, cumyl peroxide, di-t-butyl peroxide form.
7. the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization according to claim 1, it is characterised in that：It is described
Solubilizer is made of one or more of sodium tripolyphosphate, lauryl sodium sulfate, Stepanol MG.
8. the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization according to claim 1, it is characterised in that：It is described
Chain-transferring agent is by thioacetic acid, mercaptopropionic acid, mercaptoethanol, sodium vinyl sulfonate, acrylic sodium sulfonate, methacrylic sulfonic acid
One or more of sodium, sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonics, sodium hypophosphite form.
9. the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization according to claim 1, it is characterised in that：It is described
Thinner is by poly- methyl fluorosilicone, nonylphenol polyoxyethylene ether, octadecanol polyethers, dipropylene glycol methyl ether, aliphatic acid diethyl
One or more of alkylolamides, organosilicon sodium humate, organosilicon potassium humate form.
10. the preparation method of the solid sheet polycarboxylic acid slump retaining agent of bulk polymerization according to claim 1, it is characterised in that：Institute
Lubricant is stated by one kind in calcium stearate, magnesium stearate, zinc stearate, stearic amide, erucyl amide, oleamide or several
Kind composition；
The bleeding agent is by sulfated castor oil, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, alkyl sulfate sodium, secondary alkyl sulfonic acid
One or more of sodium, secondary alkyl sulphate sodium, Negel, succinic acid alkyl ester sulfonate sodium, sulfamic acid sodium group
At；
The neutralizer is by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethyl alcohol
One or more of amine, diethanol amine, triethanolamine, triisopropanolamine form.
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| CN110092876A (en) * | 2019-05-27 | 2019-08-06 | 四川琪汇新材料有限责任公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN110240676A (en) * | 2019-04-10 | 2019-09-17 | 武汉理工大学 | A kind of preparation method of solid polycarboxylic acid water reducing agent |
| CN110938177A (en) * | 2019-11-19 | 2020-03-31 | 湖北工业大学 | Solid sheet-shaped polycarboxylic acid slump retaining agent prepared by core-shell emulsion method and method |
| CN110951010A (en) * | 2019-11-19 | 2020-04-03 | 湖北工业大学 | Solid sheet-shaped polycarboxylic slump retaining agent and method for preparing same by using ultra-concentrated emulsion method |
| CN111825373A (en) * | 2020-08-11 | 2020-10-27 | 贵州石博士科技有限公司 | Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether |
| CN114790261A (en) * | 2022-03-25 | 2022-07-26 | 武汉源锦建材科技有限公司 | Preparation method of viscosity-reduction type polycarboxylate superplasticizer |
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| CN111825373A (en) * | 2020-08-11 | 2020-10-27 | 贵州石博士科技有限公司 | Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether |
| CN114790261A (en) * | 2022-03-25 | 2022-07-26 | 武汉源锦建材科技有限公司 | Preparation method of viscosity-reduction type polycarboxylate superplasticizer |
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