CN108383954A - A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer - Google Patents
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer Download PDFInfo
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- CN108383954A CN108383954A CN201810294961.6A CN201810294961A CN108383954A CN 108383954 A CN108383954 A CN 108383954A CN 201810294961 A CN201810294961 A CN 201810294961A CN 108383954 A CN108383954 A CN 108383954A
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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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The present invention provides a kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer：A certain amount of high-temperature liquid state polyether macromonomer just synthesized and lubricant are added in reaction kettle, agitating and heating；Temperature is controlled at 100 105 DEG C, is initially added into a certain amount of initial initiator, organic peroxy class initiator, antifoaming agent, solubilizer, chain-transferring agent, initial initiator；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 and acrylic acid；After 10min is added dropwise in minor comonomer solution, a certain amount of organic peroxy class initiator is put 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 product of the present invention.Final solid sheet polycarboxylate water-reducer 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, and specifically a kind of solid sheet is poly-
The viscosity reduction of carboxylic acid water reducer increases profit preparation method.
Background technology
With the continuous propulsion of engineering construction, the use of polycarboxylate water-reducer and demand are all increasing, and common poly- carboxylic
Sour water-reducing agent mother liquor is solid containing usually 40% or so, because containing a large amount of moisture as solvent, causes in storage and transporter
Face expenditure is high.Especially farther out from water-reducing agent grown place, long-distance transportation is both uneconomical or is difficult to for many engineering projects now
Meet dosage requirement.Current solid polycarboxylic acid water reducing agent on the market is sprayed by being heated to liquid polycarboxylate water-reducer
It is obtained after dry, not only performance is declined, but also equipment is complicated, and cost is higher.
From the point of view of demand, develop having good prospects for solid sheet polycarboxylate water-reducer.The solid water-reducing agent must consider
The convenience of production and the efficiency of production, and excellent product performance, adaptability is good, is being used with common polycarboxylate water-reducer
There is no difference in performance, it is water-soluble good, it is conducive to construction.Using multiple lubrication defoaming means, mitigate significantly because of anhydrous high viscosity
Environment and caused by the not strong problem of reactivity.
Patent CN105017490A discloses a kind of method that anhydrous method prepares polycarboxylate water-reducer, which includes as follows
Synthesis step：1) at 70-85 DEG C, by 100 mole of monomer A fusings in reactor；2) it is slowly added to again into reactor
1.5-6 mole of monomer B and 1.15-2.6 mole initiators C forms mixing liquid；3) by 9-28.5 mole of monomer B and 2.3-
10.4 moles of chain-transferring agent T are mixed to form mixed liquor, then the mixed liquor is instilled in reactor；4) continue to be stirred to react 0h-1h
Afterwards, polycarboxylate water-reducer is obtained after discharging is cooling.
Patent CN105061689A discloses a kind of preparation method of powdery polycarboxylic acid high-performance water reducing agent, and the polycarboxylic acids is high
Performance water-reducing agent passes through free radical bulk polymerization by minor comonomer and unsaturated polyoxyethylene ether in the presence of no any solvent
Method obtains, the invention additionally provide it is prepared by polymerization product become can rapidly-soluble powder in water method.
Patent CN106279565A discloses a kind of two excitation system production solid polycarboxylic acid water reducing agent and preparation method thereof,
The invention produces the sincere aqua of solid polycarboxylic acids using two kinds of free radical polymerization process of redox excitation system and bulk polymerization,
Molecule is specifically carried out under initiator and chain-transferring agent effect with unsaturated carboxylic acid and unsaturated polyethenoxy ether class polymeric monomer
Polymerization, grafting and the solid polycarboxylic acids with combed molecular structure identical with conventional liq polycarboxylate water-reducer formed
Water-reducing agent.
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, lubricant, antifoaming agent carry out high temperature lubricating defoaming, increase reactivity, finally prepare
It has excellent performance, the good pure solid-state polycarboxylate water-reducer of adaptability.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of viscosity reduction increasing profit preparation of solid sheet polycarboxylate water-reducer
Method.
Solid polycarboxylic acid water reducing agent is prepared by the way of bulk polymerization at present, can not all obtain water-reducing rate height, adaptability
Good product, the viscosity for being primarily due to bulk polymerization is larger, can not finally obtain ideal water-reducing agent configuration and
Suitable molecular weight.The present invention uses the synthetic method of bulk polymerization, is directly docked with polyether macromonomer producer, using also not
The liquid polyethers of cooling solidification is produced, and has good economy and operability.
In terms of raw material selection, fluoro function monomer is introduced, is non-polar group, there is defoaming foam control energy well
Power can significantly reduce the air bubble content in system, increase the contact probability between molecule and molecule；At the same time, defoaming is added
Agent is defoamed, and bubble removing is more comprehensively thoroughly removed.On this basis, solubilizer is introduced, further ensures that each raw material low molten
Can uniformly be mixed under the conditions of agent；Lubricant is introduced, cutting for solution in entire reaction environment is reduced on the basis of solubilising
Shearing stress, more conducively molecule are graft-polymerized.In conjunction with entire reaction process temperature, the higher organic peroxy of half life temperature is selected
Change class initiator, it is ensured that the effect of initiation.
Technical scheme is as follows：
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer, it is characterised in that：The solid sheet polycarboxylic acids
Water-reducing agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, lubricant, antifoaming agent, neutralizer；1000 parts of gross mass, preparation method includes following
Step：
1) 855-885 parts of liquid polyether macromonomers and 2-5 parts of lubricants are added in reaction kettle, agitating and 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, 2.5-5 parts of organic peroxy class initiators, 0.2-0.6 parts of initial initiators, 0.1-0.5 parts of defoamings
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
15-35 parts of fluoro function monomers, 60-90 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution, first thrown for the first time into kettle
Enter 0.2-0.5 parts of organic peroxy class initiators, primary every 10min inputs later, each input amount is identical, until minor comonomer
Solution has put into last time before being added dropwise to complete, and puts into 1-2.4 parts of organic peroxy class initiators in total；
4) after completion of dropwise addition, temperature is raised at 110-115 DEG C, keeps temperature constant, 1-3h is cured, waits for reaction solution temperature
When spending less than 30 DEG C, 6-10 parts of neutralizers are slowly added to, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylate water-reducer.
The liquid polyether macromonomer be polyethers producer produce offline also not solidified liquid polyether macromonomer, specifically by
Allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, vinyl butyl ether polyoxy second
One or more of alkene ether forms；It is preferred that isoamyl alcohol polyoxyethylene ether.
The fluoro function monomer is by one kind or two in acrylic acid trifluoro ethyl ester, methacrylic acid 2,2,2- trifluoro ethyl esters
Kind composition；Preferred mass ratio is 1:The composition of 2 acrylic acid trifluoro ethyl ester and methacrylic acid 2,2,2- trifluoro ethyl esters.
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；Preferred mass is than 1:2 sodium tripolyphosphate and lauryl sodium sulfate composition.
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；Preferred mass is than 1:2 methylpropene sodium sulfonate and styrene sulfonic acid composition of sodium.
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 1:1 stearic acid
The composition of amide and erucyl amide.
The antifoaming agent by silicone emulsion, the fatty acid ester compounded object of higher alcohols, polyoxyethylene polyoxypropylene pentaerythrite ether,
In polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene glycerin ether, dimethyl silicone polymer
One or more of compositions；It is preferred that the antifoaming agent of heat resisting type；It is preferred that the dimethyl silicone polymer that boiling point is 155 DEG C.
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；Preferably triethanolamine.
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, in terms of raw material selection, fluoro function monomer is introduced, is non-polar group, there is defoaming foam control energy well
Power can significantly reduce the air bubble content in system, increase the contact probability between molecule and molecule, and cooperation antifoaming agent disappears
Bubble, more comprehensively thoroughly removes bubble removing；On this basis, solubilizer is introduced, further ensures that each raw material under low solvent condition
Can uniformly be mixed；Lubricant is introduced, entire reaction environment is made to be more conducive to molecule graft polymerization on the basis of viscosity reduction.
Using multiple lubrication defoaming means, mitigate the not strong problem of reactivity caused by due to anhydrous high viscosity environment significantly.
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
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer, it is characterised in that：The solid sheet polycarboxylic acids
Water-reducing agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method includes the following steps：
1) it is 1 by 875 parts of liquid allyl polyethenoxy ethers and 5 parts of mass ratioes:1 stearic amide and erucyl amide
Composition is 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 1 at 105 DEG C:2
Sodium tripolyphosphate and lauryl sodium sulfate composition, 9 parts of sodium hypophosphites, 5 parts of mass ratioes 1:1 perbenzoic acid uncle
The composition of butyl ester and di-t-butyl peroxide, 0.6 part of mass ratio 1:1 dilauroyl peroxide and the group of azodiisobutyronitrile
Close object, 0.1 part of dimethyl silicone polymer；
3) after 5min, start be added dropwise minor comonomer solution, minor comonomer solution time for adding be 2 hours, minor comonomer solution by
18 parts of mass ratioes are 1：1 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 75 parts of acrylic acid
Composition；After 10min is added dropwise in minor comonomer solution, 0.2 part of mass ratio 1 is first put into for the first time into kettle:1 perbenzoic acid uncle
The composition of butyl ester and di-t-butyl peroxide, primary every 10min inputs later, each input amount is identical, until minor comonomer
Solution has put into last time before being added dropwise to complete, and puts into 11 totally 2.2 parts of mass ratioes 1 in total:The 1 tertiary fourth of perbenzoic acid
The composition of ester and di-t-butyl 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, 7 parts of ethanol amines are slowly added to, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylate water-reducer.
Embodiment 2
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer, it is characterised in that：The solid sheet polycarboxylic acids
Water-reducing agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method includes the following steps：
1) 878 parts of liquid isoamyl alcohol polyoxyethylene ethers and 2 parts of stearic amides are added in reaction kettle, stirring adds
Heat；
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:1
Sodium tripolyphosphate and lauryl sodium sulfate composition, 5 parts of mass ratioes 1:1 methylpropene sodium sulfonate and sodium styrene sulfonate
Composition, 2.5 parts of peroxidized t-butyl perbenzoates, 0.2 part of dibenzoyl peroxide, 0.2 part of silicone emulsion；
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 1 by 20 parts of mass ratioes：1 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 80 parts of propylene
Acid composition；After 10min is added dropwise in minor comonomer solution, 0.5 part of peroxidized t-butyl perbenzoate is first put into for the first time into kettle, later
Primary every 10min inputs, each input amount is identical, has put into last time before minor comonomer solution is added dropwise to complete, in total
Put into 2 totally 1 part of peroxidized t-butyl perbenzoates；
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 spending less than 30 DEG C, 10 parts of sodium methoxides are slowly added to, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylate water-reducer.
Embodiment 3
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer, it is characterised in that：The solid sheet polycarboxylic acids
Water-reducing agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method includes the following steps：
1) it is 1 by 885 parts of liquid mass ratioes：1 methyl allyl polyoxyethylene ether and isoamyl alcohol polyoxyethylene ether
Composition, 2.5 parts of erucyl amides 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 3.5 parts of dodecyl sulphates at 104 DEG C
Magnesium, 8 parts of mass ratioes 1:1 2- acrylamide-2-methyl propane sulfonics and the composition of sodium hypophosphite, 4 parts of mass ratioes 1:1
The composition of cumyl peroxide and di-t-butyl peroxide, 0.6 part of mass ratio 1:1 dibenzoyl peroxide and azo
The composition of bis-isobutyronitrile, 0.45 part of mass ratio 1:The composition of the 1 fatty acid ester compounded object of silicone emulsion and higher alcohols；
3) after 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is 1.5 hours, minor comonomer solution
It is 1 by 15 parts of mass ratioes:2 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 73 parts of propylene
Acid composition；After 10min is added dropwise in minor comonomer solution, 0.25 part of mass ratio 1 is first put into for the first time into kettle:2 peroxidating diisopropyl
The composition of benzene and di-t-butyl peroxide, primary every 10min inputs later, each input amount is identical, until minor comonomer is molten
Liquid has put into last time before being added dropwise to complete, and puts into 8 totally 2 parts of mass ratioes 1 in total:2 cumyl peroxide and peroxidating
The composition of di-t-butyl；
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 spending less than 30 DEG C, 6 parts of diethanol amine are slowly added to, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylate water-reducer.
Embodiment 4
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer, it is characterised in that：The solid sheet polycarboxylic acids
Water-reducing agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method includes the following steps：
1) by 855 parts of liquid allyl polyethenoxy ethers and 3 parts of mass ratioes 1:The combination of 1 erucyl amide and oleamide
Object is 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 2.5 parts of sodium tripolyphosphates, 6 at 101 DEG C
Part mass ratio 1:1 sodium vinyl sulfonate and the composition of acrylic sodium sulfonate, 2.8 parts of cumyl peroxides, 0.25 part of mistake
Aoxidize lauroyl, 0.5 mass ratio 1:1 part polyoxyethylene polyoxypropylene glycerin ether and the composition of dimethyl silicone polymer；
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 made of 30 parts of acrylic acid trifluoro ethyl esters, 90 parts of acrylic acid；After 10min is added dropwise in minor comonomer solution, first put into for the first time into kettle
0.45 part of cumyl peroxide, primary every 10min inputs later, each input amount is identical, until minor comonomer solution is added dropwise
Last time has been put into before completing, has put into 3 totally 1.35 parts of cumyl peroxides in total；
4) after completion of dropwise addition, temperature is raised at 111 DEG C, keeps temperature constant, cures 1.5 hours, waits for reaction solution temperature
When spending less than 30 DEG C, 9 parts of sodium ethoxides are slowly added to, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylate water-reducer.
Embodiment 5
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer, it is characterised in that：The solid sheet polycarboxylic acids
Water-reducing agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method includes the following steps：
1) 869 parts of liquid methyl allyl polyoxyethylene ethers and 4 parts of calcium stearates are added in reaction kettle, stirring adds
Heat；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 3 parts of mass ratioes 1 at 103 DEG C:The three of 1
Polyphosphate sodium and Stepanol MG composition, 8 parts of sodium hypophosphites, 3.3 parts of mass ratioes 1:1 perbenzoic acid uncle
The composition of butyl ester and cumyl peroxide, 0.6 part of peroxidating trimethylacetic acid tert-butyl ester, 0.4 part of mass ratio 1:1 polyoxy third
The composition of alkene glycerin ether and polyoxyethylene polyoxypropylene glycerin ether；
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 2 by 15 parts of mass ratioes：1 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 88 parts of propylene
Acid composition；After 10min is added dropwise in minor comonomer solution, 0.32 part of mass ratio 1 is first put into for the first time into kettle:1 perbenzoic acid
The composition of the tert-butyl ester and cumyl peroxide, primary every 10min inputs later, each input amount is identical, until small list
Liquid solution has put into last time before being added dropwise to complete, and puts into 6 totally 1.92 parts of mass ratioes 1 in total:1 perbenzoic acid uncle
The composition of butyl ester and cumyl peroxide；
4) after completion of dropwise addition, temperature is raised at 115 DEG C, keeps temperature constant, cures 2 hours, waits for reaction solution temperature
When less than 30 DEG C, 7 parts of triethanolamines are slowly added to, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylate water-reducer.
Embodiment 6
A kind of viscosity reduction increasing profit preparation method of solid sheet polycarboxylate water-reducer, it is characterised in that：The solid sheet polycarboxylic acids
Water-reducing agent is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method includes the following steps：
1) it is 2 by 865 parts of liquid ethylene base butyl ether polyoxyethylene ether and 5 parts of mass ratioes:1 stearic amide and erucic acid
The composition of amide is 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 2.8 parts of dodecyl sulphates at 102 DEG C
Sodium, 7 parts of 2- acrylamide-2-methyl propane sulfonics, 3 parts of di-t-butyl peroxides, 0.3 part of azodiisobutyronitrile, 0.3 part of polyoxy
Ethylene polyoxy propyl alcohol amidogen ether；
3) after 5min, start be added dropwise minor comonomer solution, minor comonomer solution time for adding be 1 hour, minor comonomer solution by
25 parts of methacrylic acid 2,2,2- trifluoro ethyl esters, 82 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution, into kettle first
Secondary first to put into 0.48 part of di-t-butyl peroxide, primary every 10min inputs later, each input amount is identical, until minor comonomer
Solution has put into last time before being added dropwise to complete, and puts into 5 totally 2.4 parts of di-t-butyl peroxides in total；
4) after completion of dropwise addition, temperature is raised at 112 DEG C, keeps temperature constant, cures 1.7 hours, waits for reaction solution temperature
When spending less than 30 DEG C, 8 parts of triisopropanolamines are slowly added to, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylic acids diminishing
Agent.
The solid sheet polycarboxylate water-reducer and water of bulk polymerization prepared by embodiment 1,2,3,4,5,6 press 4：6 ratio
It is dissolved in water, determines that it is water-soluble preferably.
The solid sheet polycarboxylate water-reducer of the bulk polymerization of test above-described embodiment 1,2,3,4,5,6 and common poly- carboxylic respectively
Net slurry initial fluidity, 1h mobility under sour slump retaining agent mother liquor comparable sodium and concrete initial slump/divergence
With through when the slump/divergence.Experiment cement used is that new 42.5 ordinary portland cement of China refers to GB/8076-2008《Outside concrete
Add agent》Testing standard.
The different Water-reducing Admixtures To Cements net slurry flow effects of table 1
The different water-reducing 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, bulk polymerization
Gu the net slurry initial fluidity religion as ordinary water-reducing agent of sheet polycarboxylate water-reducer embodiment 1,2,3,4,5,6 is consistent, 1h streams
Dynamic property is also consistent compared with ordinary water-reducing agent mother liquor；Concrete flowability data comparison, the function of slump protection of embodiment 1,2,3,4,5,6
It can reach unanimity with ordinary water-reducing agent concrete flowability, overall data illustrates the solid sheet polycarboxylate water-reducer formula and preparation
Technical maturity is reliable, and in high viscosity reaction environment, high conversion rate tends to one with 40% water-reducing agent mother liquor performance of liquid at this stage
It causes, water-reducing rate is high.
Claims (10)
1. a kind of viscosity reduction of solid sheet polycarboxylate water-reducer increases profit preparation method, it is characterised in that：The solid sheet polycarboxylic acids subtracts
Aqua is mainly prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiator, organic peroxy
Class initiator, solubilizer, chain-transferring agent, lubricant, antifoaming agent, neutralizer；1000 parts of gross mass, preparation method include following step
Suddenly：
1) 855-885 parts of liquid polyether macromonomers and 2-5 parts of lubricants are added in reaction kettle, agitating and heating；
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, 2.5-5 parts of organic peroxy class initiators, 0.2-0.6 parts of initial initiators, 0.1-0.5 parts of antifoaming agent；
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 15-
35 parts of fluoro function monomers, 60-90 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution, first put into for the first time into kettle
0.2-0.5 parts of organic peroxy class initiators, primary every 10min inputs later, each input amount is identical, until minor comonomer solution
Last time has been put into before being added dropwise to complete, has put into 1-2.4 parts of organic peroxy class initiators in total；
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, increases to get solid sheet viscosity reduction after cooling slice and moistens polycarboxylate water-reducer.
2. preparation method according to claim 1, it is characterised in that：The polyether macromonomer by allyl polyethenoxy ether,
One or more of methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether
Composition.
3. preparation method according to claim 1, it is characterised in that：The fluoro function monomer by acrylic acid trifluoro ethyl ester,
One or both of methacrylic acid 2,2,2- trifluoro ethyl esters form.
4. preparation method according to claim 1, it is characterised in that：The initial initiator is 1h half life temperatures in 70-
95 DEG C of initiator, specifically by dibenzoyl peroxide, dilauroyl peroxide, azodiisobutyronitrile, the tertiary fourth of peroxidating trimethylacetic acid
One or more of ester forms.
5. preparation method according to claim 1, it is characterised in that：The organic peroxy class initiator is 1h half life temperatures
In 120-140 DEG C of organic peroxy class initiator, specifically by peroxidized t-butyl perbenzoate, cumyl peroxide, peroxidating
One or more of di-t-butyl forms.
6. preparation method according to claim 1, it is characterised in that：The solubilizer is by sodium tripolyphosphate, dodecyl sulphur
One or more of sour sodium, Stepanol MG form.
7. preparation method according to claim 1, it is characterised in that：The chain-transferring agent is by thioacetic acid, mercaptopropionic acid, mercapto
Base ethyl alcohol, sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate, sodium styrene sulfonate, 2- acrylamide -2- first
One or more of base propane sulfonic acid, sodium hypophosphite form.
8. preparation method according to claim 1, it is characterised in that：The lubricant is by calcium stearate, magnesium stearate, tristearin
One or more of sour zinc, stearic amide, erucyl amide, oleamide form.
9. preparation method according to claim 1, it is characterised in that：The antifoaming agent is by silicone emulsion, high-carbon polyol fatty acid
Ester complexes, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxy
One or more of propylene polyoxyethylene glycerol ether, dimethyl silicone polymer form.
10. preparation method according to claim 1, it is characterised in that：The neutralizer is by sodium hydroxide, potassium hydroxide, carbon
One in sour sodium, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanol amine, diethanol amine, triethanolamine, triisopropanolamine
Kind or several compositions.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109928661A (en) * | 2019-04-15 | 2019-06-25 | 山西格瑞特建筑科技股份有限公司 | A kind of viscosity reduction type solid polycarboxylic acid water reducing agent 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 |
| CN113416283A (en) * | 2021-08-12 | 2021-09-21 | 福建钟山化工有限公司 | High-dispersibility solid polycarboxylate superplasticizer, and preparation method and application method thereof |
| CN113912787A (en) * | 2021-11-09 | 2022-01-11 | 高速铁路建造技术国家工程实验室 | Preparation method and equipment of soap-free emulsion for concrete protective coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496445A (en) * | 2016-11-15 | 2017-03-15 | 湖北工业大学 | A kind of hydrophobic minor comonomer modification viscosity reduction type polycarboxylate water-reducer masterbatch |
| CN106543382A (en) * | 2016-12-07 | 2017-03-29 | 湖北工业大学 | A kind of solid lamellar polycarboxylate water-reducer and its polymerization process for preparing |
-
2018
- 2018-03-30 CN CN201810294961.6A patent/CN108383954A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496445A (en) * | 2016-11-15 | 2017-03-15 | 湖北工业大学 | A kind of hydrophobic minor comonomer modification viscosity reduction type polycarboxylate water-reducer masterbatch |
| CN106543382A (en) * | 2016-12-07 | 2017-03-29 | 湖北工业大学 | A kind of solid lamellar polycarboxylate water-reducer and its polymerization process for preparing |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109928661A (en) * | 2019-04-15 | 2019-06-25 | 山西格瑞特建筑科技股份有限公司 | A kind of viscosity reduction type solid polycarboxylic acid water reducing agent and preparation method thereof |
| CN113416283A (en) * | 2021-08-12 | 2021-09-21 | 福建钟山化工有限公司 | High-dispersibility solid polycarboxylate superplasticizer, and preparation method and application method thereof |
| CN113912787A (en) * | 2021-11-09 | 2022-01-11 | 高速铁路建造技术国家工程实验室 | Preparation method and equipment of soap-free emulsion for concrete protective coating |
| CN113912787B (en) * | 2021-11-09 | 2023-09-15 | 高速铁路建造技术国家工程实验室 | Preparation method and equipment of soap-free emulsion for concrete protective coating |
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Application publication date: 20180810 |