CN110436814A - A kind of concrete high-efficiency additive and preparation method thereof - Google Patents
A kind of concrete high-efficiency additive and preparation method thereof Download PDFInfo
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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
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3348—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing nitrogen in addition to sulfur
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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
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- 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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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/304—Air-entrainers
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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- 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
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/601—Agents for increasing frost resistance
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/65—Water proofers or repellants
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Abstract
The invention discloses a kind of preparation methods of concrete high-efficiency additive, include the following steps: the preparation of (one) chloro poly glycol monomethyl ether, (2) preparation of naphthalene sulfonic acids class compound is ionized, (3) preparation of condensation polymer, the preparation of (four) water-reducing agent product.The invention also discloses the concrete high-efficiency additives being prepared according to the preparation method of the concrete high-efficiency additive.Concrete high-efficiency additive water-reducing effect disclosed by the invention is significant, has high-thin arch dam, anti-bleeding, freezing tolerance are strong, it is good with the adaptability of cement, the dispersibility of cement can be effectively improved, the workability of concrete can be substantially improved, improves every mechanical property of concrete.
Description
Technical field
The present invention relates to concrete additive technical field more particularly to a kind of concrete high-efficiency additive and its preparation sides
Method.
Background technique
Concrete material is to use cement as gel rubber material, and sand, masonry are gathered materials, cooperated by a certain percentage with water, agitated
Gained.Since its compression strength is high, fire resistance is good, using flexible, easy for construction, abundant raw material, cheap, production technology is simple
The advantages that single, has become purposes most one of wide, the maximum construction material of dosage in the world today, and playing other materials can not
The effect and function of substitution.
Concrete in practical engineering applications, is commonly exposed to various more harsh environment, such as environment corrosivity
The intrusion of medium, the variation of ambient temperature and humidity, Frozen-thawed cycled destroy and part concrete works are worn often in heavy load
Deng these external conditions will seriously affect the service life of concrete.Therefore, it is necessary to add additive in concrete, mix
Solidifying soil additive is one of workability, intensity and the essential ingredient of durability for guaranteeing that concrete is excellent, can be effective
Ground improves and adjusts the performance of concrete.
Water-reducing agent is one kind more representative in concrete additive, is that concrete slump is being maintained to be basically unchanged
Under conditions of, it can be reduced the concrete admixture of mixing water amount.Currently used cement water reducing agent is polyether-type polycarboxylic acids
Class water-reducing agent, this kind of water-reducing agent dispersion slump retaining is good, at low cost but too fast due to adsorbing, to flyash, mountain flour, clay material
Expect that adaptability is very poor.That more or less there is volumes is big for other additives in the prior art, and water reducing ability is poor, and plasticization effect is poor,
Have a single function, it is perishable, mildew, rotten is easy in storage and transportational process, is then given out a foul smell, gently then reduced performance, it is heavy then
The shortcomings that completely losing effect is unable to satisfy the requirement in market.
Chinese patent CN102153711A reports a kind of by allyl sulphonic acid salt monomer, acrylic monomer, methyl
Polyalkylene glycol acrylate monomethyl ether ester polymeric monomer and maleic anhydride graft beta-cyclodextrin polymeric monomer are obtained by free radicals copolymerization reaction
To a kind of slow-setting polycarboxylic acid water reducing agent, make resulting polycarboxylate dehydragent that there is preferable retarding performance, micro- bleed performance
And better mobile performance, but the maleic anhydride graft beta-cyclodextrin polymeric monomer grafting rate of the invention is not high, and it is by temperature
Be affected, cannot fundamentally solve the problems, such as the concrete slump loss under different condition, be unfavorable for large-scale life
It produces and applies.
Therefore, it develops that a kind of water-reducing effect is more significant, volume is less, protects collapsing performance more preferably concrete high-efficiency additive
It accords with the demands of the market, there is extensive market value and application prospect, it is non-to promoting the development of concrete additive industry to have
Often important meaning.
Summary of the invention
Present invention seek to address that the above problem, a kind of concrete high-efficiency additive and preparation method thereof, the concrete are provided
Efficient additive preparation cost is cheap, and raw material is easy to get, and simple process is easy to operate, is suitble to large-scale production, popularization with higher
Application value；The concrete high-efficiency additive water-reducing effect being prepared by this preparation method is significant, has high-thin arch dam, resists
Bleeding, freezing tolerance are strong, good with the adaptability of cement, can effectively improve the dispersibility of cement, can substantially improve the sum of concrete
Yi Xing improves every mechanical property of concrete.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of concrete high-efficiency additive, includes the following steps:
The preparation of I chloro poly glycol monomethyl ether: under nitrogen or inert gas atmosphere protection, successively into three-necked flask
Anhydrous pyridine, poly glycol monomethyl ether and dry toluene is added, is warming up in 35-45 DEG C of backward three-necked flask and dichloro is slowly added dropwise
Sulfoxide drips off in 2 hours, and isothermal reaction 3-5 hours；Stratification, by upper solution by filtering, revolving, mistake after cooling
Filter, obtains chloro poly glycol monomethyl ether after solvent is distilled off；
The preparation of II ionization naphthalene sulfonic acids class compound: by the chloro poly glycol monomethyl ether being prepared by step I,
7,7'- imido bis- (4- hydroxyl -2- naphthalene sulfonic acids) are added in acetone, are stirred to react at 40-60 DEG C 6-8 hours, back spin is evaporated off
Acetone is removed, with ether washed product 3-5 times, ether is evaporated off in back spin, obtains ionization naphthalene sulfonic acids class compound；
The preparation of III condensation polymer: ionization naphthalene sulfonic acids class compound, bis- (the 4- chlorine of 1,3- that will be prepared by step II
Phenyl) urea, basic catalyst be added in the there-necked flask for being connected to water segregator, then increase boiling point solvent and toluene, by reaction system
It is heated to 95-105 DEG C, stirred under nitrogen atmosphere reacts 3-5 hours, removes the Shui Hejia generated in reaction process by water segregator
Benzene eliminates water and reaction temperature is slowly increased to 135-145 DEG C later, continues return stirring reaction 12-15 hours, after reaction
Reaction system is cooled to room temperature, is precipitated in acetone, the polymer of precipitation is washed 3-5 times with ether, it is dry to be placed on vacuum
It dries at 60-80 DEG C of dry case to constant weight, obtains condensation polymer；
The preparation of IV water-reducing agent product: condensation polymer, polyacrylic acid, the attapulgite clay that will be prepared by step III
Powder, isopropyl alcohol and water are uniformly mixed, and are stirred to react 2-4 hours at 40-50 DEG C, are obtained concrete high-efficiency additive product.
Further, the mass ratio of anhydrous pyridine described in step I, poly glycol monomethyl ether, dry toluene, thionyl chloride
It is 2:4.24:(10-15): 1.
Further, the inert gas is selected from one of helium, neon, argon gas.
Further, chloro poly glycol monomethyl ether described in step II, 7,7'- imido bis- (4- hydroxyl -2- naphthalene sulfonic acids),
The mass ratio of acetone is 2.68:1:(12-16).
Further, ionization naphthalene sulfonic acids class compound described in step III, bis- (4- chlorphenyl) urea of 1,3-, alkalinity are urged
Agent, high boiling solvent, toluene mass ratio be 6:1:(0.8-1.2): (15-20): 8.
Preferably, the basic catalyst is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or several
Kind；The high boiling solvent is selected from dimethyl sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- crassitude
One or more of ketone.
Further, condensation polymer described in step IV, polyacrylic acid, attapulgite clay powder, isopropanol, water mass ratio be
1:0.5:0.1:(0.5-1):(3-5)。
Further, a kind of concrete high-efficiency additive is prepared using the preparation method of above-mentioned concrete high-efficiency additive
It forms.
The beneficial effects of adopting the technical scheme are that
(1) concrete high-efficiency additive provided by the invention, preparation cost is cheap, and raw material is easy to get, and simple process is easy to operate,
It is suitble to large-scale production, application value with higher.
(2) concrete high-efficiency additive provided by the invention, water-reducing effect is significant, has high-thin arch dam, anti-bleeding, freeze proof energy
Power is strong, good with the adaptability of cement, can effectively improve the dispersibility of cement, can substantially improve the workability of concrete, improve and
Improve every mechanical property of concrete.
(3) concrete high-efficiency additive provided by the invention, component is simple, each ingredient synergistic effect, vdiverse in function, effectively
The comprehensive performance for improving concrete not only acts as the effect for reducing agent, also has antifreeze, waterproof, bleed, slow setting, antirust etc.
Effect can dissolve alternation of wetting and drying, heat expansion and Frozen-thawed cycled to the damaging influence of concrete structure；And each ingredient be combined into it is whole
Body avoids influence of the loss of water-reducing agent to concrete performance stability.
(4) concrete high-efficiency additive provided by the invention introduces urea structures and naphthalene sulfonic acids structure, collaboration in strand
Effect can significantly improve the water-reducing rate of concrete material, and polyethylene glycol ether structure is introduced on its side chain, is adsorbed on concrete material
Expect surface, when cement granules close to when, adsorption layer starts to be overlapped, i.e., steric hindrance effect is generated between cement granules, overlapping gets over
More, steric hindrance repulsion is bigger, also bigger between the obstruction of cohesion cement granules, so that the slump of concrete keeps good
It is good；These structures are linked together in the form of chemical bond so that its stability is more preferable, can preferably be cooperateed with and be played a role；
This water-reducing agent is added in the form of condensation polymer, due to its molecular structure feature, can be significantly improved the compressive property of concrete, be prevented
Seep performance, toughness properties；The introducing of ionic group makes it be easier to adsorb, the polycarboxylic acids of condensation polymer and bear electricity with cation
Substance is keyed by ion, makes its storage and transportation stability more preferably, so that water-reducing agent steric effect is bigger, in cement water
In the high alkalinity environment of change, which can be ionized into ionic species, to release the polycarboxylic acid with peptizaiton and season
The dispersion effect of cement particle, antibiotic property, and control slump loss thus can be improved in ammonium salt；Attapulgite clay powder adds
Enter the adhesion strength that can enhance between concrete each component；It penetrates into concrete crack, so that concrete density is more preferable；It is excellent
Its different distinctive design feature, so that the concrete comprehensive performance of addition thereafter is more preferably.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Wherein, the raw material being related in embodiment is commercially available.
Embodiment 1
A kind of preparation method of concrete high-efficiency additive, includes the following steps:
The preparation of I chloro poly glycol monomethyl ether: under nitrogen atmosphere protection, anhydrous pyrrole is successively added into three-necked flask
Pyridine 20g, poly glycol monomethyl ether 42.4g and dry toluene 100g are warming up in 35 DEG C of backward three-necked flasks and dichloro are slowly added dropwise
Sulfoxide 10g, drips off in 2 hours, and isothermal reaction 3 hours；Stratification, by upper solution by filtering, revolving, mistake after cooling
Filter, obtains chloro poly glycol monomethyl ether after solvent is distilled off；
The preparation of II ionization naphthalene sulfonic acids class compound: the chloro poly glycol monomethyl ether that will be prepared by step I
Bis- (4- hydroxyl -2- naphthalene sulfonic acids) 10g of 26.8g, 7,7'- imido are added in acetone 120g, are stirred to react at 40 DEG C 6 hours,
Acetone is evaporated off in back spin, and with ether washed product 3 times, ether is evaporated off in back spin, obtains ionization naphthalene sulfonic acids class compound；
The preparation of III condensation polymer: ionization naphthalene sulfonic acids class compound 24g, 1,3- for being prepared by step II is bis-
(4- chlorphenyl) urea 4g, sodium hydroxide 3.2g are added in the there-necked flask for being connected to water segregator, then plus dimethyl sulfoxide 60g and toluene
Reaction system is heated to 95 DEG C by 32g, and stirred under nitrogen atmosphere reacts 3 hours, is removed in reaction process and is generated by water segregator
Water and toluene, eliminate and reaction temperature be slowly increased to 135 DEG C after water, continue return stirring and react 12 hours, reaction terminates
Reaction system is cooled to room temperature afterwards, is precipitated in acetone, the polymer of precipitation is washed 3 times with ether, it is dry to be placed on vacuum
It dries at 60 DEG C of dry case to constant weight, obtains condensation polymer；
The preparation of IV water-reducing agent product: condensation polymer 10g, the polyacrylic acid 5g, concave convex rod that will be prepared by step III
Clay powder 1g, isopropanol 5g and water 30g are uniformly mixed, and are stirred to react at 40 DEG C 2 hours, and the production of concrete high-efficiency additive is obtained
Product.
A kind of concrete high-efficiency additive is prepared using the preparation method of above-mentioned concrete high-efficiency additive.
Embodiment 2
A kind of preparation method of concrete high-efficiency additive, includes the following steps:
The preparation of I chloro poly glycol monomethyl ether: under helium atmosphere protection, anhydrous pyrrole is successively added into three-necked flask
Pyridine 20g, poly glycol monomethyl ether 42.4g and dry toluene 110g are warming up in 37 DEG C of backward three-necked flasks and dichloro are slowly added dropwise
Sulfoxide 10g, drips off in 2 hours, and isothermal reaction 3.5 hours；Stratification, by upper solution by filtering, revolving, after cooling
Filtering, obtains chloro poly glycol monomethyl ether after solvent is distilled off；
The preparation of II ionization naphthalene sulfonic acids class compound: the chloro poly glycol monomethyl ether that will be prepared by step I
Bis- (4- hydroxyl -2- naphthalene sulfonic acids) 10g of 26.8g, 7,7'- imido are added in acetone 130g, and it is small to be stirred to react 6.5 at 45 DEG C
When, acetone is evaporated off in back spin, and with ether washed product 4 times, ether is evaporated off in back spin, obtains ionization naphthalene sulfonic acids class compound；
The preparation of III condensation polymer: ionization naphthalene sulfonic acids class compound 24g, 1,3- for being prepared by step II is bis-
(4- chlorphenyl) urea 4g, potassium hydroxide 3.6g are added in the there-necked flask for being connected to water segregator, then plus n,N-Dimethylformamide 65g
With toluene 32g, reaction system is heated to 98 DEG C, stirred under nitrogen atmosphere reacts 3.5 hours, removes dereaction mistake by water segregator
The water and toluene generated in journey eliminates water and reaction temperature is slowly increased to 138 DEG C later, continues return stirring and reacts 13 hours,
Reaction system is cooled to room temperature after reaction, is precipitated in acetone, the polymer of precipitation is washed 4 times with ether, postposition
It dries at 65 DEG C of vacuum oven to constant weight, obtains condensation polymer；
The preparation of IV water-reducing agent product: condensation polymer 10g, the polyacrylic acid 5g, concave convex rod that will be prepared by step III
Clay powder 1g, isopropanol 7g and water 35g are uniformly mixed, and are stirred to react 2.5 hours at 43 DEG C, are obtained concrete high-efficiency additive
Product.
A kind of concrete high-efficiency additive is prepared using the preparation method of above-mentioned concrete high-efficiency additive.
Embodiment 3
A kind of preparation method of concrete high-efficiency additive, includes the following steps:
The preparation of I chloro poly glycol monomethyl ether: under neon atmosphere protection, anhydrous pyrrole is successively added into three-necked flask
Pyridine 20g, poly glycol monomethyl ether 42.4g and dry toluene 135g are warming up in 40 DEG C of backward three-necked flasks and dichloro are slowly added dropwise
Sulfoxide 10g, drips off in 2 hours, and isothermal reaction 4 hours；Stratification, by upper solution by filtering, revolving, mistake after cooling
Filter, obtains chloro poly glycol monomethyl ether after solvent is distilled off；
The preparation of II ionization naphthalene sulfonic acids class compound: the chloro poly glycol monomethyl ether that will be prepared by step I
Bis- (4- hydroxyl -2- naphthalene sulfonic acids) 10g of 26.8g, 7,7'- imido are added in acetone 145g, are stirred to react at 50 DEG C 7 hours,
Acetone is evaporated off in back spin, and with ether washed product 4 times, ether is evaporated off in back spin, obtains ionization naphthalene sulfonic acids class compound；
The preparation of III condensation polymer: ionization naphthalene sulfonic acids class compound 24g, 1,3- for being prepared by step II is bis-
(4- chlorphenyl) urea 4g, sodium carbonate 3.9g are added in the there-necked flask for being connected to water segregator, then plus n,N-dimethylacetamide 70g and
Reaction system is heated to 99 DEG C by toluene 32g, and stirred under nitrogen atmosphere reacts 4 hours, is removed in reaction process by water segregator
The water and toluene of generation eliminate water and reaction temperature are slowly increased to 140 DEG C later, continue return stirring and react 14 hours, reaction
After reaction system is cooled to room temperature, be precipitated in acetone, the polymer of precipitation washed 4 times with ether, be placed on true
It dries at 70 DEG C of empty drying box to constant weight, obtains condensation polymer；
The preparation of IV water-reducing agent product: condensation polymer 10g, the polyacrylic acid 5g, concave convex rod that will be prepared by step III
Clay powder 1g, isopropanol 8g and water 40g are uniformly mixed, and are stirred to react at 45 DEG C 3 hours, and the production of concrete high-efficiency additive is obtained
Product.
A kind of concrete high-efficiency additive is prepared using the preparation method of above-mentioned concrete high-efficiency additive.
Embodiment 4
A kind of preparation method of concrete high-efficiency additive, includes the following steps:
The preparation of I chloro poly glycol monomethyl ether: under argon atmosphere protection, anhydrous pyrrole is successively added into three-necked flask
Pyridine 20g, poly glycol monomethyl ether 42.4g and dry toluene 145g are warming up in 43 DEG C of backward three-necked flasks and dichloro are slowly added dropwise
Sulfoxide 10g, drips off in 2 hours, and isothermal reaction 4.5 hours；Stratification, by upper solution by filtering, revolving, after cooling
Filtering, obtains chloro poly glycol monomethyl ether after solvent is distilled off；
The preparation of II ionization naphthalene sulfonic acids class compound: the chloro poly glycol monomethyl ether that will be prepared by step I
Bis- (4- hydroxyl -2- naphthalene sulfonic acids) 10g of 26.8g, 7,7'- imido are added in acetone 155g, and it is small to be stirred to react 7.8 at 55 DEG C
When, acetone is evaporated off in back spin, and with ether washed product 5 times, ether is evaporated off in back spin, obtains ionization naphthalene sulfonic acids class compound；
The preparation of III condensation polymer: ionization naphthalene sulfonic acids class compound 24g, 1,3- for being prepared by step II is bis-
(4- chlorphenyl) urea 4g, basic catalyst 4.5g are added in the there-necked flask for being connected to water segregator, then increase boiling point solvent 75g and first
Reaction system is heated to 103 DEG C by benzene 32g, and stirred under nitrogen atmosphere reacts 4.5 hours, removes reaction process by water segregator
The water and toluene of middle generation eliminate water and reaction temperature are slowly increased to 143 DEG C later, continue return stirring and react 14.5 hours,
Reaction system is cooled to room temperature after reaction, is precipitated in acetone, the polymer of precipitation is washed 5 times with ether, postposition
It dries at 75 DEG C of vacuum oven to constant weight, obtains condensation polymer；The basic catalyst is sodium hydroxide, potassium hydroxide, carbon
The mixture that sour sodium, potassium carbonate 2:1:3:2 in mass ratio are mixed；The high boiling solvent is dimethyl sulfoxide, N, N- diformazan
The mixture that base formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone 1:3:2:1 in mass ratio are mixed；
The preparation of IV water-reducing agent product: condensation polymer 10g, the polyacrylic acid 5g, concave convex rod that will be prepared by step III
Clay powder 1g, isopropanol 9.5g and water 48g are uniformly mixed, and are stirred to react at 48 DEG C 3.5 hours, and concrete high-efficiency addition is obtained
Agent product.
A kind of concrete high-efficiency additive is prepared using the preparation method of above-mentioned concrete high-efficiency additive.
Embodiment 5
A kind of preparation method of concrete high-efficiency additive, includes the following steps:
The preparation of I chloro poly glycol monomethyl ether: under nitrogen atmosphere protection, anhydrous pyrrole is successively added into three-necked flask
Pyridine 20g, poly glycol monomethyl ether 42.4g and dry toluene 150g are warming up in 45 DEG C of backward three-necked flasks and dichloro are slowly added dropwise
Sulfoxide 10g, drips off in 2 hours, and isothermal reaction 5 hours；Stratification, by upper solution by filtering, revolving, mistake after cooling
Filter, obtains chloro poly glycol monomethyl ether after solvent is distilled off；
The preparation of II ionization naphthalene sulfonic acids class compound: the chloro poly glycol monomethyl ether that will be prepared by step I
Bis- (4- hydroxyl -2- naphthalene sulfonic acids) 10g of 26.8g, 7,7'- imido are added in acetone 160g, are stirred to react at 60 DEG C 8 hours,
Acetone is evaporated off in back spin, and with ether washed product 5 times, ether is evaporated off in back spin, obtains ionization naphthalene sulfonic acids class compound；
The preparation of III condensation polymer: ionization naphthalene sulfonic acids class compound 24g, 1,3- for being prepared by step II is bis-
(4- chlorphenyl) urea 4g, potassium carbonate 4.8g are added in the there-necked flask for being connected to water segregator, then plus N-Methyl pyrrolidone 80g and first
Reaction system is heated to 105 DEG C by benzene 32g, and stirred under nitrogen atmosphere reacts 5 hours, is removed in reaction process by water segregator
The water and toluene of generation eliminate water and reaction temperature are slowly increased to 145 DEG C later, continue return stirring and react 15 hours, reaction
After reaction system is cooled to room temperature, be precipitated in acetone, the polymer of precipitation washed 5 times with ether, be placed on true
It dries at 80 DEG C of empty drying box to constant weight, obtains condensation polymer；
The preparation of IV water-reducing agent product: condensation polymer 10g, the polyacrylic acid 5g, concave convex rod that will be prepared by step III
Clay powder 1g, isopropanol 10g and water 50g are uniformly mixed, and are stirred to react 4 hours at 50 DEG C, are obtained concrete high-efficiency additive
Product.
A kind of concrete high-efficiency additive is prepared using the preparation method of above-mentioned concrete high-efficiency additive.
Comparative example 1
This example provides a kind of concrete additive, according to matching for 106396464 B embodiment 1 of Chinese invention patent CN
Side is prepared.
Comparative example 2
A kind of concrete additive, formula and preparation method are substantially the same manner as Example 1, the difference is that not having in formula
There is addition condensation polymer.
Comparative example 3
A kind of concrete additive, formula and preparation method are substantially the same manner as Example 1, the difference is that not having in formula
There is addition polyacrylic acid.
Comparative example 4
A kind of concrete additive, formula and preparation method are substantially the same manner as Example 1, the difference is that not having in formula
There is addition attapulgite clay powder.
Water-reducing agent described in embodiment 1-5 and comparative example 1-4 is tested for the property, test result is shown in Tables 1 and 2.Performance
Test method is carried out with reference to JG/T223-2007, and water-reducing agent volume is 1.5%.
Table 1
As seen from Table 1, concrete high-efficiency additive disclosed by the embodiments of the present invention is added with concrete in the prior art
Agent is compared, and water-reducing effect is more significant, can significantly increase the slump of concrete, to concrete body performance without negative effect.
As seen from Table 1, concrete high-efficiency additive disclosed by the embodiments of the present invention, excellent physical property are each component associations
The result of same-action.
Table 2
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (8)
1. a kind of preparation method of concrete high-efficiency additive, which comprises the steps of:
The preparation of I chloro poly glycol monomethyl ether: it under nitrogen or inert gas atmosphere protection, is successively added into three-necked flask
Anhydrous pyridine, poly glycol monomethyl ether and dry toluene are warming up in 35-45 DEG C of backward three-necked flask and dichloro Asia are slowly added dropwise
Sulfone drips off in 2 hours, and isothermal reaction 3-5 hours；Stratification, by upper solution by filtering, revolving, cooled and filtered,
Chloro poly glycol monomethyl ether is obtained after solvent is distilled off；
The preparation of II ionization naphthalene sulfonic acids class compound: by the chloro poly glycol monomethyl ether being prepared by step I, 7,
7'- imido bis- (4- hydroxyl -2- naphthalene sulfonic acids) is added in acetone, is stirred to react at 40-60 DEG C 6-8 hours, back spin is evaporated off
Acetone, with ether washed product 3-5 times, ether is evaporated off in back spin, obtains ionization naphthalene sulfonic acids class compound；
The preparation of III condensation polymer: ionization naphthalene sulfonic acids class compound, bis- (the 4- chlorobenzenes of 1,3- that will be prepared by step II
Base) urea, basic catalyst be added in the there-necked flask for being connected to water segregator, then increase boiling point solvent and toluene, by reaction system plus
Heat arrives 95-105 DEG C, and stirred under nitrogen atmosphere reacts 3-5 hours, removes the Shui Hejia generated in reaction process by water segregator
Benzene eliminates water and reaction temperature is slowly increased to 135-145 DEG C later, continues return stirring reaction 12-15 hours, after reaction
Reaction system is cooled to room temperature, is precipitated in acetone, the polymer of precipitation is washed 3-5 times with ether, it is dry to be placed on vacuum
It dries at 60-80 DEG C of dry case to constant weight, obtains condensation polymer；
The preparation of IV water-reducing agent product: by the condensation polymer being prepared by step III, polyacrylic acid, attapulgite clay powder, different
Third alcohol and water is uniformly mixed, and is stirred to react 2-4 hours at 40-50 DEG C, is obtained concrete high efficiency water reducing agent product.
2. a kind of preparation method of concrete high-efficiency additive according to claim 1, which is characterized in that institute in step I
State anhydrous pyridine, poly glycol monomethyl ether, dry toluene, thionyl chloride mass ratio be 2:4.24:(10-15): 1；It is described lazy
Property gas be selected from one of helium, neon, argon gas.
3. a kind of preparation method of concrete high-efficiency additive according to claim 1, which is characterized in that institute in step II
State chloro poly glycol monomethyl ether, 7,7'- imido bis- (4- hydroxyl -2- naphthalene sulfonic acids), the mass ratio of acetone is 2.68:1:(12-
16)。
4. a kind of preparation method of concrete high-efficiency additive according to claim 1, which is characterized in that institute in step III
State the quality of ionization naphthalene sulfonic acids class compound, bis- (4- chlorphenyl) urea of 1,3-, basic catalyst, high boiling solvent, toluene
Than for 6:1:(0.8-1.2): (15-20): 8.
5. a kind of preparation method of concrete high-efficiency additive according to claim 1, which is characterized in that the alkalinity is urged
Agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
6. a kind of preparation method of concrete high-efficiency additive according to claim 1, which is characterized in that the higher boiling
Solvent is selected from one of dimethyl sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone or several
Kind.
7. a kind of preparation method of concrete high-efficiency additive according to claim 1, which is characterized in that institute in step IV
State condensation polymer, polyacrylic acid, attapulgite clay powder, isopropanol, water mass ratio be 1:0.5:0.1:(0.5-1): (3-5).
8. a kind of coagulation that the preparation method using the described in any item concrete high-efficiency additives of claim 1-7 is prepared
Native efficient additive.
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