CN108484841A - A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization - Google Patents
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization Download PDFInfo
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- CN108484841A CN108484841A CN201810295664.3A CN201810295664A CN108484841A CN 108484841 A CN108484841 A CN 108484841A CN 201810295664 A CN201810295664 A CN 201810295664A CN 108484841 A CN108484841 A CN 108484841A
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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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
- C04B2103/302—Water reducers
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Abstract
The present invention provides a kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization：A certain amount of liquid polyether macromonomer just synthesized and thinner 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, solubilizer, chain-transferring agent, initial initiator；After 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is a hours, 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, is cured b hour, postcooling slice encapsulate to get product of the present invention.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, specifically a kind of bulk polymerization
Solid sheet polycarboxylate water-reducer 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 by dry to the heating spraying of 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 a kind of having good prospects for pure solid polycarboxylic acid water reducing agent of bulk polymerization.The solid diminishing
Agent must consider the convenience of production and the efficiency of production, and excellent product performance, and adaptability is good, with common polycarboxylic acids
Water-reducing agent does not have difference in performance, water-soluble good, is conducive to construction.
Patent CN102993387A discloses a kind of method that a step directly synthesizes pure solid high-performance polycarboxylate water-reducer,
The invention is added molecular weight regulator, is drawing using acrylic compounds and unsaturated polyoxyethylene ether as polymerization reaction monomer
Pure solid poly-carboxylic high-performance is made by free radical bulk polymerization in the environment of without any solvent under the action of hair agent
Water-reducing agent.
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 CN105061690A discloses a kind of preparation method of high water reducing type solid high-performance polycarboxylate water-reducer, tool
Steps are as follows for body：After the unsaturated polyoxyethylene ether combination polymeric monomer heating melting of two kinds of different molecular weights, make in initiator
It is basic by freedom with lower dropwise addition unsaturated carboxylic acid class minor comonomer, the mixed liquor of unsaturated acyl amine minor comonomer and chain-transferring agent
Body polymerisation be made, reaction after the completion of use neutralizer adjust pH for 5-6, cooling after by grinding be solid granular.
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 carry out high temperature viscosity reduction, increase reactivity, finally prepare and have excellent performance, adapt to
The good pure solid-state polycarboxylate water-reducer of property.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of system of the solid sheet polycarboxylate water-reducer of bulk polymerization
Preparation 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 not dropping also
The liquid polyethers of temperature 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.On this basis, it introduces and increases
Solvent further ensures that each raw material can uniformly be mixed under low solvent condition；Thinner is introduced, high-temperature anhydrous ring is reduced
The viscosity in border.In conjunction with entire reaction process temperature, the higher organic peroxy class initiator of half life temperature is selected, it is ensured that cause
Effect.
Technical scheme is as follows：
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylate water-reducer is mainly prepared from the following components：It is 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 packet
Include following steps：
1) 860-890 parts of liquid polyether macromonomers and 1-3 portions of thinners 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, 5-9 parts of chain-transferring agents, 2.5-5 parts of organic peroxy class initiators, 0.2-0.6 parts of initial initiators；
3) after 5min, start be added dropwise minor comonomer solution, minor comonomer solution time for adding be a hours, minor comonomer solution by
15-25 parts of fluoro function monomers, 70-100 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution, 0.4- is put into kettle
0.6 part of organic peroxy class initiator, it is primary every 10min inputs later, it has been put into most before minor comonomer solution is added dropwise to complete
It is primary afterwards；
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, cool down the solid sheet polycarboxylic acids diminishing to get bulk polymerization after being sliced
Agent.
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 polyoxyethylene
One or more of 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 1 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 temperatures
Close to the initiator of reaction temperature；It is preferred that the dibenzoyl peroxide that 1h half life temperatures are 92 DEG C.
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 half
Initiator of the phase temperature that declines 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 1:1 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 1:1 methylpropene sodium sulfonate and styrene sulfonic acid composition of sodium.
The thinner is 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 2 poly- methyl fluorosilicone and nonylphenol polyoxyethylene ether.
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；It is preferred that triisopropanolamine.
The minor comonomer solution time for adding a is 0.5-2h；Preferably 1h.
The curing time b is 1-3h；Preferably 1.5h.
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 growing
The too short problem of main chain caused by time high temperature, while shorter time for adding brings faster speed of production, production efficiency 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；On this basis, it introduces and increases
Solvent further ensures that each raw material can uniformly be mixed under low solvent condition；Thinner is introduced, high-temperature anhydrous ring is reduced
The viscosity in border.
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 used to
Limit the present invention.
Embodiment 1
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylate water-reducer is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiation
Agent, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method include with
Lower step：
1) by 860 parts of high-temperature liquid state isoamyl alcohol polyoxyethylene ethers and 1 part of mass ratio 1：2 poly- methyl fluorosilicone and nonyl
The composition of base phenol polyethenoxy ether 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 2.2 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 group
Close object, 2.5 parts of peroxidized t-butyl perbenzoates, 0.2 part of dibenzoyl peroxide；
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 18 parts of mass ratioes：1 acrylic acid trifluoro ethyl ester and the composition of methacrylic acid 2,2,2- trifluoro ethyl esters, 100 part third
Olefin(e) acid forms；After 10min is added dropwise in minor comonomer solution, 0.6 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 1.2 parts of peroxidized t-butyl perbenzoates；
4) after completion of dropwise addition, temperature is raised at 110 DEG C, keeps temperature constant, cures 1 hour, waits for reaction solution temperature
When less than 30 DEG C, 10 parts of sodium methoxides are slowly added to, cool down the solid sheet polycarboxylate water-reducer to get bulk polymerization after being sliced.
Embodiment 2
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylate water-reducer is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiation
Agent, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method include with
Lower step：
1) by 865 parts of high-temperature liquid state allyl polyethenoxy ethers and 1.2 parts of mass ratioes 1:1 octadecanol polyethers and dipropyl
The composition of glycol methyl ether 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；
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 21 parts of acrylic acid trifluoro ethyl esters, 91 parts of acrylic acid；After 10min is added dropwise in minor comonomer solution, first put into for the first time into kettle
0.5 part of cumyl peroxide, primary every 10min inputs later, each input amount is identical, until minor comonomer solution drips
Last time has been put at preceding, has put into 3 totally 1.5 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 degree is less than 30 DEG C, 9 parts of sodium ethoxides are slowly added to, cool down the solid sheet polycarboxylate water-reducer to get bulk polymerization after being sliced.
Embodiment 3
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylate water-reducer is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiation
Agent, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method include with
Lower step：
1) by 869 parts of high-temperature liquid state vinyl butyl ether polyoxyethylene ether and 1.4 parts of mass ratioes 1:1 aliphatic acid diethanol
The composition of amide and organosilicon sodium humate 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；
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 0.4 part of 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 5 totally 2 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 degree is less than 30 DEG C, 8 parts of triisopropanolamines are slowly added to, cool down the solid sheet polycarboxylic acids diminishing to get bulk polymerization after being sliced
Agent.
Embodiment 4
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylate water-reducer is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiation
Agent, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method include with
Lower step：
1) 880 parts of high-temperature liquid state methyl allyl polyoxyethylene ethers and 2 parts of organosilicon potassium humates are added to reaction kettle
In, agitating and heating；
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:The 1 tertiary fourth of perbenzoic acid
The composition of ester and cumyl peroxide, 0.6 part of peroxidating trimethylacetic acid tert-butyl ester；
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, 78 parts of propylene
Acid composition；After 10min is added dropwise in minor comonomer solution, 0.52 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 3.12 parts of mass ratioes 1 in total:The 1 tertiary fourth of perbenzoic acid
The composition of 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, cool down the solid sheet polycarboxylate water-reducer to get bulk polymerization after being sliced.
Embodiment 5
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylate water-reducer is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiation
Agent, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method include with
Lower step：
1) it is 1 by 890 parts of high-temperature liquid state mass ratioes：1 methyl allyl polyoxyethylene ether and prenol polyoxyethylene
The composition of ether, 2.5 parts of nonylphenol polyoxyethylene ether 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 2.3 parts of dodecyl sulphates at 104 DEG C
Magnesium, 7 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 two
The composition of isobutyronitrile；
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, 70 parts of propylene
Acid composition；After 10min is added dropwise in minor comonomer solution, 0.42 part of mass ratio 1 is first put into for the first time into kettle:1 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 3.36 parts of mass ratioes 1 in total:1 cumyl peroxide and peroxide
Change 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 degree is less than 30 DEG C, 6 parts of diethanol amine are slowly added to, cool down the solid sheet polycarboxylate water-reducer to get bulk polymerization after being sliced.
Embodiment 6
A kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization
Gu sheet polycarboxylate water-reducer is prepared from the following components：Polyether macromonomer, fluoro function monomer, acrylic acid, initial initiation
Agent, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method include with
Lower step：
1) 875 parts of high-temperature liquid state allyl polyethenoxy ethers and 3 parts of organosilicon potassium humates are added in reaction kettle, are stirred
Mix 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:The 1 tertiary fourth of perbenzoic acid
The composition of ester and di-t-butyl peroxide, 0.5 part of mass ratio 1:The combination of 1 dilauroyl peroxide and azodiisobutyronitrile
Object；
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, 0.4 part of mass ratio 1 is first put into for the first time into kettle:The 1 tertiary fourth of perbenzoic acid
The composition of ester 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 11 totally 4.4 parts of mass ratioes 1 in total:1 peroxidized t-butyl perbenzoate and
The composition of 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, cool down the solid sheet polycarboxylate water-reducer to get bulk polymerization after being sliced.
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 and concrete initial slump/divergence under sour slump retaining agent mother liquor comparable sodium and
Through when the slump/divergence.Experiment cement used is that new 42.5 ordinary portland cement of China refers to GB/8076-2008《Concrete is additional
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, 1h mobility and concrete it is initial and through when mobility compare, bulk polymerization is consolidated
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 flowings
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 with it is general
Logical water-reducing agent concrete flowability can reach unanimity, and overall data illustrates the solid sheet polycarboxylate water-reducer formula and preparation process
Mature and reliable, in high viscosity reaction environment, high conversion rate reaches unanimity with 40% water-reducing agent mother liquor performance of liquid at this stage, subtracts
Water rate is high.
Claims (10)
1. a kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, it is characterised in that：The bulk polymerization is consolidated
Sheet polycarboxylate water-reducer is mainly prepared from the following components：Polyether macromonomer, acrylic acid, initially draws fluoro function monomer
Send out agent, organic peroxy class initiator, solubilizer, chain-transferring agent, thinner, neutralizer；1000 parts of gross mass, preparation method include
Following steps：
1) 860-890 parts of liquid polyether macromonomers and 1-3 portions of thinners 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,
5-9 parts of chain-transferring agents, 2.5-5 parts of organic peroxy class initiators, 0.2-0.6 parts of initial initiators；
3) after 5min, start that minor comonomer solution is added dropwise, minor comonomer solution time for adding is a hours, and minor comonomer solution is by 15-25
Part fluoro function monomer, 70-100 parts of acrylic acid compositions；After 10min is added dropwise in minor comonomer solution, first put into for the first time into kettle
0.4-0.6 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 1.4-3.6 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, cures b hours, waits for reaction solution temperature
When less than 30 DEG C, 6-10 parts of neutralizers are slowly added to, cool down the solid sheet polycarboxylate water-reducer to get bulk polymerization after being sliced.
2. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The polyether macromonomer is by allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, ethylene
One or more of base butyl ether polyoxyethylene ether forms.
3. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The fluoro function monomer is made of one or both of acrylic acid trifluoro ethyl ester, methacrylic acid 2,2,2- trifluoro ethyl esters.
4. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The initial initiator is initiator of the 1h half life temperatures at 70-95 DEG C, specifically by dibenzoyl peroxide, peroxidating 12
One or more of acyl, azodiisobutyronitrile, peroxidating trimethylacetic acid tert-butyl ester form.
5. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The organic peroxy class initiator is organic peroxy class initiator of the 1h half life temperatures at 120-140 DEG C, specifically by peroxidating
One or more of t-butyl perbenzoate, cumyl peroxide, di-t-butyl peroxide form.
6. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The solubilizer is made of one or more of sodium tripolyphosphate, lauryl sodium sulfate, Stepanol MG.
7. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The chain-transferring agent is by thioacetic acid, mercaptopropionic acid, mercaptoethanol, sodium vinyl sulfonate, acrylic sodium sulfonate, metering system sulphur
One or more of sour sodium, sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonics, sodium hypophosphite form.
8. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The thinner is by poly- methyl fluorosilicone, nonylphenol polyoxyethylene ether, octadecanol polyethers, dipropylene glycol methyl ether, aliphatic acid
One or more of diglycollic amide, organosilicon sodium humate, organosilicon potassium humate form.
9. the preparation method of the solid sheet polycarboxylate water-reducer of a kind of bulk polymerization according to claim 1, it is characterised in that：
The neutralizer is by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanol amine, two
One or more of ethanol amine, triethanolamine, triisopropanolamine form.
10. a kind of preparation method of the solid sheet polycarboxylate water-reducer of bulk polymerization, feature exist according to claim 1
In：The minor comonomer solution time for adding a is 0.5-2h；The curing time b is 1-3h.
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| 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 |
| CN111533852A (en) * | 2020-05-14 | 2020-08-14 | 中建材料技术研究成都有限公司 | Solid polycarboxylic acid water reducing agent and preparation method thereof |
| CN112608421A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
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| 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 |
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| 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 |
| CN112608421A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN112708042A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN112708042B (en) * | 2019-11-25 | 2021-11-19 | 科之杰新材料集团有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN112608421B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| CN112608420B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| WO2021226869A1 (en) * | 2020-05-13 | 2021-11-18 | 辽宁奥克化学股份有限公司 | Solid polycarboxylic acid water reducing agent and preparation method therefor |
| DE112020007177T5 (en) | 2020-05-13 | 2023-02-23 | Liaoning Oxiranchem Inc. | Solid polycarboxylic acid superplasticizer and method of making same |
| CN111533852A (en) * | 2020-05-14 | 2020-08-14 | 中建材料技术研究成都有限公司 | Solid polycarboxylic acid water reducing agent and preparation method thereof |
| CN113416017A (en) * | 2021-07-27 | 2021-09-21 | 山西桑穆斯建材化工有限公司 | Polycarboxylate superplasticizer for reducing concrete viscosity and preparation method thereof |
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Application publication date: 20180904 |