CN108503252A - A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent - Google Patents
A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent Download PDFInfo
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- CN108503252A CN108503252A CN201810275557.4A CN201810275557A CN108503252A CN 108503252 A CN108503252 A CN 108503252A CN 201810275557 A CN201810275557 A CN 201810275557A CN 108503252 A CN108503252 A CN 108503252A
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- 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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Abstract
The present invention provides a kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, and preparation method includes the following steps：1) a certain proportion of polyether macromonomer and water are added in reaction kettle, agitating and heating waits for its dissolving；2) control temperature is initially added into a certain amount of solubilizer, chain-transferring agent, organic peroxy class initiator at 70 75 DEG C；3) after 5min, start that solution B is added dropwise, 10min starts that solution A is added dropwise, and solution A time for adding is a hours, and solution B time for adding is a+0.5 hours；Solution A is made of a certain proportion of alkyl acrylate, acrylic acid and water, and solution B is made of azo-initiator, alcohol organic solvent and water；4) after completion of dropwise addition, temperature is raised to 95 98 DEG C, keeps temperature constant, is cured b hour, postcooling slice encapsulate and reach 92 98% high-adaptability large arch dam polycarboxylic acid slump retaining agents to get solid content.The method of the present invention products obtained therefrom has the characteristics that large arch dam, adaptability are good, function of slump protection is good, is suitble to industrial production.
Description
Technical field
The invention belongs to building material technical fields, are related to concrete admixture field, specifically a kind of Gao Shi
The preparation method of answering property large arch dam polycarboxylic acid slump retaining agent.
Background technology
For slump retaining agent as the indispensable raw material of ready-mixed concrete, dosage demand is very huge.With common polycarboxylic acids diminishing
Agent is the same, and the solid of common polycarboxylic acid slump retaining agent contains generally 40% or so, because containing a large amount of moisture as solvent, causes
Being spent in terms of storage and transport becomes the very important expenditure of enterprise.No matter manufacturing enterprise or engineering unit, it is poly- to large arch dam
Carboxylic acid slump retaining agent suffers from strong demand.Current large arch dam polycarboxylate water-reducer on the market is by the poly- carboxylic of liquid
It is obtained after sour water-reducing agent heating spray drying, not only performance is declined, but also device replication, and cost is higher.With engineering
Pace of construction moves forward steadily, a kind of large arch dam high-performance and good large arch dam polycarboxylic acid slump retaining agent of economy possesses very
Big development and application foreground.
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 CN103012694A discloses a kind of preparation method of the pure solid high-performance polycarboxylate water-reducer of polyester-type, should
Invention passes through esterification under the action of catalyst using (methyl) acrylic monomers and polyethylene glycols compound as reactant
Prepare polymerizable polymeric monomer, then with unsaturated carboxylic acid monomer, chain-transferring agent under the action of initiator in the ring without any solvent
It is made by free radical bulk polymerization under border.
Patent CN106893047A is disclosed a kind of preparing solid polycarboxylic acid water reducing agent using organic oxidation reduction system
Method, it is specific as follows：1) a certain amount of prenol polyglycol ether at a certain temperature, is added into reaction vessel and gathers
Ethylene glycol, stirring make its fusing；2) organic oxidizing agent and chain-transferring agent are sequentially added, is stirred evenly；3) acrylic acid is added dropwise and has
The mixture of machine reducing agent, is added dropwise, and isothermal reaction is for a period of time；4) be added sodium hydroxide powder adjust product PH to
5-7 while hot pours out product, is cooled to room temperature, by product grind into powder to get solid polycarboxylic acid water reducing agent.
It is different from the above patent, the present invention does not prepare large arch dam polycarboxylic acid slump retaining agent using the method for bulk polymerization completely,
Suitable water is added in bottom material, and is selected by the technological design of optimization and raw material, prepares functional large arch dam production
Product avoid properties of product caused by pursuing anhydrous bulk polymerization simply and cannot be satisfied the problem of market needs.Using single initiation
The way of distillation afterwards removes extra initiator, obtains the diminishing agent molecule of more reasonable structure.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of preparation of high-adaptability large arch dam polycarboxylic acid slump retaining agent
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 can not obtain the polycarboxylic acid slump retaining agent that function of slump protection is good, adaptability is excellent, be primarily due to bulk polymerization
The viscosity of reaction is larger, can not finally obtain ideal water-reducing agent molecular configuration and suitable molecular weight.The present invention by
A small amount of water is introduced in bottom material, constructs the environment that viscosity is smaller, is carried out suitable for synthetic reaction.On this basis, solubilising is introduced
Agent further ensures that each raw material can uniformly be mixed under low solvent condition.
The invention selects the azo-initiator of suitable half-life period for the technological temperature of reaction.Specifically, temperature is selected
It selects too low, the half-life period of initiator can be caused long, initiator residual quantity is big, and the conversion ratio of monomer is the bottom of with regard to；And temperature is excessively high,
Then half-life period is too short, just there is a large amount of decomposition in early days, and the initiator of no sufficient amount is kept to polymerization speed appropriate to the polymerization later stage
Rate, the molecular structure for ultimately causing polymerizate are uneven.Under the temperature condition of this technique, other initiators such as over cure
Sour ammonium etc. easy tos produce induction and decomposes, i.e., consumes an initiator molecule in rain, is reduced so as to cause the efficiency of initiator, together
When the phenomenon that also degree of polymerization being made to reduce；And azo-initiator does not occur induction and decomposes, and is easy to form the polymerization of high molecule mass
Object.Selection is suitble to that half-life period the is suitble to and compound initiation of azo-initiator that half life temperature is slightly higher, allows entire primosome
System is steady excessive.Finally using the heating curing of the rear way of distillation, remaining initiator can be not only removed, it is suitable that control obtains comparison
Suitable molecular weight will further can also carry out reaction completely, obtaining product of good performance.
Technical scheme is as follows：
A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, it is characterised in that：The high-adaptability Gao Gu
It is mainly prepared from the following components containing polycarboxylic acid slump retaining agent：Polyether macromonomer, azo releaser, alcohol organic solvent, third
Olefin(e) acid Arrcostab, acrylic acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；1000 parts of gross mass, system
Preparation Method includes the following steps：
1) 570-605 parts of polyether macromonomers and 180-200 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) measure temperature in the kettle, control temperature is at 70-75 DEG C, after temperature is stablized, be added at one time 2.5-4 parts of solubilizer,
6-10 parts of chain-transferring agents, 2-4 parts of organic peroxy class initiators；
3) after 5min, start that solution B, solution A is added dropwise successively, after initiator is added, start that solution A is added dropwise in 10min,
Solution A time for adding is a hours, and solution B time for adding is a+0.5 hours；Solution B by 2.2-3.8 parts of azo-initiators,
10-15 parts of alcohol organic solvents, 50-60 parts of water composition, solution A by 45-72 parts of alkyl acrylates, 20-44 parts of acrylic acid and
50-60 parts of water compositions；
4) after completion of dropwise addition, temperature is risen to 95-98 DEG C, keeps temperature constant, cures b hours, waits for reaction solution temperature
When less than 40 DEG C, 6-10 parts of neutralizers are slowly added to, the high-adaptability for reaching 92-98% after cooling slice to get solid content is high
Admittedly finished product containing polycarboxylic acid slump retaining agent.
The polyether macromonomer is by allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, prenol polyoxy second
One or more of alkene ether, vinyl butyl ether polyoxyethylene ether form；It is preferred that isoamyl alcohol polyoxyethylene ether.
The alkyl acrylate is by hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, metering system
One or more of sour hydroxypropyl acrylate forms；Preferred mass ratio is 2:The combination of 1 hydroxy-ethyl acrylate and hydroxypropyl acrylate
Object.
The azo-initiator is azo-initiator of the 1h half life temperatures at 70-90 DEG C, specifically different by azo two
Butyronitrile, azobisisovaleronitrile, azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo dicyclohexyl formonitrile HCN salt
One or both of hydrochlorate forms；Preferred mass ratio is 2:1 azodiisobutyronitrile and the group of azo-bis-iso-dimethyl
Close object.
The alcohol organic solvent is by one or more of methanol, ethyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, glycerine
Composition；It is preferred that the alcohol with certain chain transfer ability；Preferred mass is than 1:2 ethyl alcohol and the composition of ethylene glycol.
The solubilizer is one or more of sodium tripolyphosphate, lauryl sodium sulfate, Stepanol MG group
At；Preferred mass is than 2:1 lauryl sodium sulfate and the composition of Stepanol MG.
The chain-transferring agent is by thioacetic acid, mercaptopropionic acid, mercaptoethanol, sodium vinyl sulfonate, acrylic sodium sulfonate, first
One or more of base sodium allylsulfonate, sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonics, sodium hypophosphite group
At；It is preferred that weak chain-transferring agent；Preferred mass ratio is 1:The group of 1 sodium vinyl sulfonate and 2- acrylamide-2-methyl propane sulfonics
Close object.
The organic peroxy class initiator be organic peroxy class initiator of the 1h half life temperatures at 60-72 DEG C, specifically by
One or more of the peroxidating trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate group
At；Preferred mass is than 2:The 1 peroxidating trimethylacetic acid tert-butyl ester and the composition of di-isopropyl peroxydicarbonate.
The neutralizer is by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, second
One or more of hydramine, diethanol amine, triethanolamine, triisopropanolamine form；Preferred mass ratio is 2:1 sodium methoxide
With the composition of ethanol amine.
The solution A time for adding a is 2-3.5h；Preferably 2h.
The curing time b is 2-6h；Preferably 2h.
The beneficial effects of the invention are as follows：
1, polymerisation is significantly reduced by introducing a certain amount of bottom water and solubilizer using suitable synthesis technology
When viscosity, provide preferable reaction environment for system, the spies such as products obtained therefrom has large arch dam, adaptability is good, function of slump protection is good
Point is suitble to industrial production.
2, using compound initiation, 1h half life temperatures is selected to drive initial cause in 60-72 DEG C of initial initiator；It selects again
1h half life temperatures are selected in 70-90 DEG C of azo-initiator；Meanwhile azo-initiator does not occur induction and decomposes, and causes effect
Compare steady；Entire initiation system transition is steady, stablizes suitable molecular weight conducive to formation.
3, not soluble in water for azo-initiator and the characteristics of be dissolved in alcohol, coordinate the alcohols with certain chain tra nsfer function
Azo-initiator is dissolved in after alcohols and is re-dissolved in water by organic solvent, using the method being at the uniform velocity added dropwise, rationally control reaction
Rate is conducive to industrial production.
4, using the rear way of distillation, two-part temperature heats up in maturation stage, is especially remaining in composite initiation system
The slightly higher initiator of half life temperature eliminates in distillation process, prevents residual initiator to water-reducing agent later stage performance not
Stability influence, moreover it is possible to promote the reaction was complete to carry out；Azo-initiator keeps molecular weight distribution more stable, and heating distillation can
Slightly to expand the distribution of molecular weight, molecular weight distribution is allowed to be optimized, while extra moisture evaporation can be excluded, obtained
Gu containing the polycarboxylate water-reducer for reaching 92-98%.
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 preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, the high-adaptability large arch dam polycarboxylic acids guarantor are collapsed
Agent is prepared from the following components：Polyether macromonomer, azo releaser, alcohol organic solvent, alkyl acrylate, propylene
Acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；1000 parts of gross mass, preparation method includes following
Step：
1) 580 parts of vinyl butyl ether polyoxyethylene ether and 180 parts of water are added in reaction kettle, agitating and heating waits for that its is molten
Solution；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 4 parts of mass ratioes 2 at 75 DEG C:The 12 of 1
The composition of sodium alkyl sulfate and Stepanol MG, 10 parts of mass ratioes are 1:1 sodium vinyl sulfonate and 2- acryloyls
The composition of amine -2- methyl propane sulfonic acids, 2 parts of mass ratioes 2:The 1 peroxidating trimethylacetic acid tert-butyl ester and dicetyl peroxydicarbonate diisopropyl
The composition of ester；
3) after 5min, start that solution B, solution A is added dropwise successively, after initiator is added, start that solution A is added dropwise in 10min,
Solution A time for adding is 2 hours, and solution B time for adding is 2.5 hours；Solution B is 2 by 3.6 parts of mass ratioes:1 azo two
The composition of isobutyronitrile and azo-bis-iso-dimethyl, 15 parts of mass ratioes 1:2 ethyl alcohol and the composition of ethylene glycol, 60 parts
Water forms, and solution A is 2 by 48 parts of mass ratioes:1 hydroxy-ethyl acrylate and the composition of hydroxypropyl acrylate, 31 parts of acrylic acid
It is formed with 60 parts of water；
4) after completion of dropwise addition, temperature is risen to 95 DEG C, keeps temperature constant, cures 6 hours, waits for that reaction solution temperature is less than
At 40 DEG C, it is 2 to be slowly added to 7 parts of mass ratioes:1 sodium methoxide and the composition of ethanol amine cool down after being sliced to get solid content
The 98% high-adaptability large arch dam polycarboxylic acid slump retaining agent.
Embodiment 2
A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, the high-adaptability large arch dam polycarboxylic acids guarantor are collapsed
Agent is prepared from the following components：Polyether macromonomer, azo releaser, alcohol organic solvent, alkyl acrylate, propylene
Acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；1000 parts of gross mass, preparation method includes following
Step：
1) 605 parts of isoamyl alcohol polyoxyethylene ethers and 200 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 2.5 parts of mass ratioes 2 at 74 DEG C:The three of 1
The composition of polyphosphate sodium and Stepanol MG, 6 parts of mass ratioes are 1:1 sodium vinyl sulfonate and 2- acrylamides -2-
The composition of methyl propane sulfonic acid, 2 parts of peroxidating trimethylacetic acid tert-butyl esters；
3) after 5min, start that solution B, solution A is added dropwise successively, after initiator is added, start that solution A is added dropwise in 10min,
Solution A time for adding is 2.2 hours, and solution B time for adding is 2.7 hours；Solution B by 2.2 parts of azodiisobutyronitriles, 10 parts
Ethyl alcohol, 50 parts of water compositions, solution A are made of 47 parts of hydroxy-ethyl acrylates, 20 parts of acrylic acid and 50 parts of water；
4) after completion of dropwise addition, temperature is risen to 96 DEG C, keeps temperature constant, cures 5.5 hours, waits for that reaction solution temperature is low
When 40 DEG C, 6 parts of sodium methoxides are slowly added to, cool down the poly- carboxylic of high-adaptability large arch dam to get solid content 97% after being sliced
Sour slump retaining agent.
Embodiment 3
A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, the high-adaptability large arch dam polycarboxylic acids guarantor are collapsed
Agent is prepared from the following components：Polyether macromonomer, azo releaser, alcohol organic solvent, alkyl acrylate, propylene
Acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；1000 parts of gross mass, preparation method includes following
Step：
1) 570 parts of methyl allyl polyoxyethylene ethers and 185 parts of water are added in reaction kettle, agitating and heating waits for that its is molten
Solution；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 2.8 parts of sodium tripolyphosphates, 7 at 73 DEG C
Part 2- acrylamide-2-methyl propane sulfonics, 3 portions of di-isopropyl peroxydicarbonates；
3) after 5min, start that solution B, solution A is added dropwise successively, after solution B is added, start that solution A is added dropwise in 10min,
Solution A time for adding is 2.5 hours, and solution B time for adding is 3 hours；Solution B by 2.5 parts of azo-bis-iso-dimethyls,
12 parts of ethylene glycol, 55 parts of water compositions, solution A are made of 72 parts of hydroxypropyl acrylates, 23 parts of acrylic acid and 60 parts of water；
4) after completion of dropwise addition, temperature is risen to 96 DEG C, keeps temperature constant, cures 5 hours, waits for that reaction solution temperature is less than
At 40 DEG C, 8 parts of ethanol amines are slowly added to, cool down the high-adaptability large arch dam polycarboxylic acids to get solid content 96% after being sliced
Slump retaining agent.
Embodiment 4
A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, the high-adaptability large arch dam polycarboxylic acids guarantor are collapsed
Agent is prepared from the following components：Polyether macromonomer, azo releaser, alcohol organic solvent, alkyl acrylate, propylene
Acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；1000 parts of gross mass, preparation method includes following
Step：
1) 572 parts of allyl polyethenoxy ethers and 190 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 3 parts of mass ratioes 2 at 72 DEG C:The 12 of 1
The composition of sodium alkyl sulfate and Stepanol MG, 8 parts of mass ratioes are 1:1 sodium vinyl sulfonate and acrylic sulfonic acid
The composition of sodium, 3.5 parts of mass ratioes 1:The 1 peroxidating trimethylacetic acid tert-butyl ester and the composition of di-isopropyl peroxydicarbonate；
3) after 5min, start that solution B, solution A is added dropwise successively, after solution B is added, start that solution A is added dropwise in 10min,
Solution A time for adding is 2.7 hours, and solution B time for adding is 3.2 hours；Solution B is 1 by 3.2 parts of mass ratioes:1 azo
The composition of two isobutyl dimethyl phthalates and azo-bis-isobutyrate hydrochloride, 13 parts of methanol, 60 parts of water compositions, solution A is by 45 parts of matter
Amount is than being 2:The 1 hydroxy-ethyl acrylate and composition of hydroxy propyl methacrylate, 44 parts of acrylic acid and 50 parts of water compositions；
4) after completion of dropwise addition, temperature is risen to 97 DEG C, keeps temperature constant, cures 4 hours, waits for that reaction solution temperature is less than
At 40 DEG C, it is 1 to be slowly added to 9 parts of mass ratioes:1 sodium hydroxide and the composition of sodium methoxide, to get containing admittedly after cooling slice
The high-adaptability large arch dam polycarboxylic acid slump retaining agent of amount 92%.
Embodiment 5
A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, the high-adaptability large arch dam polycarboxylic acids guarantor are collapsed
Agent is prepared from the following components：Polyether macromonomer, azo releaser, alcohol organic solvent, alkyl acrylate, propylene
Acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；1000 parts of gross mass, preparation method includes following
Step：
1) 577 parts of vinyl butyl ether polyoxyethylene ether and 195 parts of water are added in reaction kettle, agitating and heating waits for that its is molten
Solution；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 3.5 parts of mass ratioes 1 at 71 DEG C:The three of 1
Polyphosphate sodium and the composition of lauryl sodium sulfate, 6.5 parts of mass ratioes are 2:1 sodium vinyl sulfonate and acrylic sulfonic acid
The composition of sodium, 3.5 parts of di-cyclohexylperoxy di-carbonates；
3) after 5min, start that solution B, solution A is added dropwise successively, after solution B is added, start that solution A is added dropwise in 10min,
Solution A time for adding is 3 hours, and solution B time for adding is 3.5 hours；Solution B by 3.5 parts of azo-bis-isobutyrate hydrochlorides,
10 parts of glycerine, 50 parts of water compositions, solution A are made of 60 parts of alkyl acrylates, 30 parts of acrylic acid and 55 parts of water；
4) after completion of dropwise addition, temperature is risen to 98 DEG C, keeps temperature constant, cures 4.5 hours, waits for that reaction solution temperature is low
When 40 DEG C, it is 1 to be slowly added to 6 parts of mass ratioes:1 sodium ethoxide and the composition of triethanolamine cool down after being sliced to get institute
State high-adaptability large arch dam polycarboxylic acid slump retaining agent.
Embodiment 6
A kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, the high-adaptability large arch dam polycarboxylic acids guarantor are collapsed
Agent is prepared from the following components：Polyether macromonomer, azo releaser, alcohol organic solvent, alkyl acrylate, propylene
Acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；1000 parts of gross mass, original is solid containing about 70%, passes through
Final product quality score is 92-98% after afterwards prepared by distillation, and preparation method includes the following steps：
1) it is 1 by 593 parts of mass ratioes:1 methyl allyl polyoxyethylene ether and the combination of isoamyl alcohol polyoxyethylene ether
Object and 180 parts of water are added in reaction kettle, and agitating and heating waits for its dissolving；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 4 parts of Stepanol MGs at 75 DEG C
Composition, 10 parts of acrylic sodium sulfonates, 4 parts of mass ratioes 1:The 2 peroxidating trimethylacetic acid tert-butyl ester and dicetyl peroxydicarbonate two is different
The composition of propyl ester；
3) after 5min, start that solution B, solution A is added dropwise successively, after solution B is added, start that solution A is added dropwise in 10min,
Solution A time for adding is 2.5 hours, and solution B time for adding is 3 hours；Solution B is two NSC 18620 of azo by 3.8 parts of mass ratioes
The composition of hydrochloride and azo dicyclohexyl formonitrile HCN hydrochloride, 10 parts of benzyl alcohols, 60 parts of water compositions, solution A is by 48 parts of matter
Amount is than being 1:The 1 hydroxy-ethyl acrylate and composition of hydroxy propyl methacrylate, 22 parts of acrylic acid and 60 parts of water compositions；
4) after completion of dropwise addition, temperature is risen to 95 DEG C, keeps temperature constant, cures 5.2 hours, waits for that reaction solution temperature is low
When 40 DEG C, 6 parts of triethanolamines are slowly added to, are cooled down after being sliced to get the high-adaptability large arch dam polycarboxylic acid slump retaining agent.
High-adaptability large arch dam polycarboxylic acid slump retaining agent and water prepared by embodiment 1,2,3,4,5,6 presses 4：6 ratio is molten
Yu Shui determines that it is water-soluble preferably.
The high-adaptability large arch dam polycarboxylic acid slump retaining agent of test above-described embodiment 1,2,3,4,5,6 and common polycarboxylic acids respectively
The net slurry initial fluidity in different cement, 1,2h mobility and concrete under slump retaining agent mother liquor comparable sodium is initial
The slump/divergence and through when the slump/divergence.Experiment cement used is new 42.5 ordinary portland cement of China, 42.5 general silicon of conch
Cement, 42.5 ordinary portland cement of Yadong, with reference to GB/8076-2008《Concrete admixture》Testing standard.
The different slump retaining agents of table 1 influence (new 42.5 ordinary portland cement of China) pulp flowage
The different slump retaining agents of table 2 influence (42.5 ordinary portland cement of conch) to pulp flowage
| Slump retaining agent type | Initial fluidity mm | 1h mobility mm | 2h mobility mm |
| Common slump retaining agent | \ | 200 | 180 |
| Embodiment 1 | \ | 225 | 215 |
| Embodiment 2 | \ | 220 | 210 |
| Embodiment 3 | \ | 215 | 205 |
| Embodiment 4 | \ | 230 | 215 |
| Embodiment 5 | \ | 220 | 215 |
| Embodiment 6 | \ | 225 | 210 |
The different slump retaining agents of table 3 influence (42.5 ordinary portland cement of Yadong) to pulp flowage
| Slump retaining agent type | Initial fluidity mm | 1h mobility mm | 2h mobility mm |
| Common slump retaining agent | \ | 220 | 195 |
| Embodiment 1 | \ | 245 | 225 |
| Embodiment 2 | \ | 225 | 215 |
| Embodiment 3 | \ | 220 | 210 |
| Embodiment 4 | \ | 230 | 220 |
| Embodiment 5 | \ | 215 | 210 |
| Embodiment 6 | \ | 235 | 225 |
The different slump retaining agents of table 4 influence (new 42.5 ordinary portland cement of China) concrete flowability
The different slump retaining agents of table 5 influence (42.5 ordinary portland cement of conch) to concrete flowability
The different slump retaining agents of table 6 influence (42.5 ordinary portland cement of Yadong) to concrete flowability
According to above-mentioned initial fluidity, 1,2h mobility and concrete it is initial and through when mobility compare, high-adaptability is high
Admittedly embodiment containing polycarboxylic acid slump retaining agent 1,2,3,4,5,6, without net slurry initial fluidity, uses difference as common slump retaining agent
When cement experiment, the more common slump retaining agent mother liquor performance of 1h mobility is more consistent or even exceeds, and slump retaining is preferable, 2h mobility tables
Now it is better than common slump retaining agent；Concrete flowability data comparison, the function of slump protection of embodiment 1,2,3,4,5,6 is in different product
Concrete flowability in board cement can tend towards stability, and overall data illustrates that the high-adaptability large arch dam polycarboxylic acid slump retaining agent is matched
Side and mature preparation process are reliable, in high viscosity reaction environment, high conversion rate, with 40% slump retaining agent mother liquor phase of liquid at this stage
Than slump retaining is slightly good, adaptable.
Claims (10)
1. a kind of preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent, it is characterised in that：The high-adaptability large arch dam
Polycarboxylic acid slump retaining agent is mainly prepared from the following components：Polyether macromonomer, azo releaser, alcohol organic solvent, propylene
Acid alkyl ester, acrylic acid, organic peroxy class initiator, solubilizer, chain-transferring agent, neutralizer, water；It is prepared by 1000 parts of gross mass
Method includes the following steps：
1) 570-605 parts of polyether macromonomers and 180-200 parts of water are added in reaction kettle, agitating and heating waits for its dissolving；
2) temperature in the kettle is measured, control temperature after temperature is stablized, is added at one time 2.5-4 parts of solubilizer, 6-10 at 70-75 DEG C
Part chain-transferring agent, 2-4 parts of organic peroxy class initiators；
3) after 5min, start that solution B, solution A is added dropwise successively, after solution B is added, start that solution A, solution A is added dropwise in 10min
Time for adding is a hours, and solution B time for adding is a+0.5 hours；Solution B by 2.2-3.8 parts of azo-initiators, 10-15 parts
Alcohol organic solvent, 50-60 parts of water compositions, solution A is by 45-72 parts of alkyl acrylates, 20-44 parts of acrylic acid and 50-60 parts
Water forms；
4) after completion of dropwise addition, temperature is risen to 95-98 DEG C, keeps temperature constant, cures b hours, waits for that reaction solution temperature is less than
At 40 DEG C, 6-10 parts of neutralizers are slowly added to, reach the high-adaptability large arch dam of 92-98% after cooling slice to get solid content
Polycarboxylic acid slump retaining agent finished product.
2. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：It is described poly-
Ether polymeric monomer is by allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, vinyl butyl
One or more of ether polyoxyethylene ether forms.
3. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：Described third
Olefin(e) acid Arrcostab is by one in hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate
Kind or several compositions.
4. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：The idol
Nitrogen class initiator is azo-initiator of the 1h half life temperatures at 70-90 DEG C, specifically by azodiisobutyronitrile, azo diisoamyl
Nitrile, azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, one kind in azo dicyclohexyl formonitrile HCN hydrochloride or two
Kind composition.
5. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：The alcohol
Class organic solvent is made of one or more of methanol, ethyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, glycerine.
6. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：The increasing
Solvent is made of one or more of sodium tripolyphosphate, lauryl sodium sulfate, Stepanol MG.
7. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：The chain
Transfer agent by thioacetic acid, mercaptopropionic acid, mercaptoethanol, sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate,
One or more of sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonics, sodium hypophosphite form.
8. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：It is described to have
Machine peroxide initiator is organic peroxy class initiator of the 1h half life temperatures at 60-72 DEG C, specifically by peroxidating trimethylacetic acid uncle
One or more of butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate form.
9. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：In described
With agent by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanol amine, diethanol amine,
One or more of triethanolamine, triisopropanolamine form.
10. the preparation method of high-adaptability large arch dam polycarboxylic acid slump retaining agent according to claim 1, it is characterised in that：It is described
Solution A time for adding a is 2-3h；The curing time b is 4-6h.
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| CN110922546A (en) * | 2019-11-21 | 2020-03-27 | 湖北工业大学 | Phenyl hydroxyl compound ATRP method modified polycarboxylic acid slump retaining agent and preparation method thereof |
| CN110951008A (en) * | 2019-11-19 | 2020-04-03 | 湖北工业大学 | Solid sheet-shaped polycarboxylic slump retaining agent prepared by soap-free emulsion polymerization method and method |
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| CN105254822A (en) * | 2015-11-20 | 2016-01-20 | 科之杰新材料集团有限公司 | Preparation method of polycarboxylate superplasticizer |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150291716A1 (en) * | 2012-12-05 | 2015-10-15 | Sobute New Materials Co., Ltd. | Slump retaining polycarboxylic acid superplasticizer |
| CN105254822A (en) * | 2015-11-20 | 2016-01-20 | 科之杰新材料集团有限公司 | Preparation method of polycarboxylate superplasticizer |
| 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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| CN110951008A (en) * | 2019-11-19 | 2020-04-03 | 湖北工业大学 | Solid sheet-shaped polycarboxylic slump retaining agent prepared by soap-free emulsion polymerization method and method |
| CN110922546A (en) * | 2019-11-21 | 2020-03-27 | 湖北工业大学 | Phenyl hydroxyl compound ATRP method modified polycarboxylic acid slump retaining agent and preparation method thereof |
| CN110922546B (en) * | 2019-11-21 | 2022-07-05 | 湖北工业大学 | Phenyl hydroxyl compound ATRP method modified polycarboxylic acid slump retaining agent and preparation method thereof |
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