CN107722194A - A kind of high diminishing poly-carboxylic-acid cement dispersant and preparation method thereof - Google Patents
A kind of high diminishing poly-carboxylic-acid cement dispersant and preparation method thereof Download PDFInfo
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- CN107722194A CN107722194A CN201710968236.8A CN201710968236A CN107722194A CN 107722194 A CN107722194 A CN 107722194A CN 201710968236 A CN201710968236 A CN 201710968236A CN 107722194 A CN107722194 A CN 107722194A
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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
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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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
Abstract
The invention discloses a kind of high diminishing poly-carboxylic-acid cement dispersant and preparation method thereof.Preparation method of the present invention comprises the following steps：Main chain is obtained by methacrylic acid polyethylene glycol ester monomer and the progress copolyreaction of unsaturated alcohol monomer first and carries hydroxyl, side chain is the comb polymer molecule polymer of polyethers；Then under the effect of semi-commercial (semiworks) production thiocarbamide, the hydroxyl in comb polymer molecule polymer is converted into sulfydryl, and main chain is made and carries sulfydryl, side chain is the comb shape Macromolecular chain transfer agent of polyethers；Radical polymerization is carried out finally by comb shape Macromolecular chain transfer agent regulation and control unsaturated acid monomer, finally gives the high diminishing poly-carboxylic-acid cement dispersant.Volume is low, water-reducing rate is high, slump retaining is good in concrete application for high diminishing poly-carboxylic-acid cement dispersant of the present invention, can greatly save concrete production cost；Production process green non-pollution, technique are simple, production stability is strong, beneficial to industrialized production.
Description
Technical field
The invention belongs to cement concrete additive technical field, and in particular to a kind of high diminishing poly-carboxylic-acid cement disperses
Agent and preparation method thereof.
Background technology
Poly-carboxylic-acid cement dispersant, because its volume is low, water-reducing rate is high, slump retaining is good, molecular structure adjustability is strong, green
The advantages that environmentally friendly, turn into the most important product in current concrete additive market.Japanese catalyst company carries out to poly- carboxylic earliest
The research of acid, its patent CN1148329, CN1821149, CN1303875 describe synthesis and the application technology of polycarboxylic acids in detail.
Since 21 century, the polycarboxylic acids research in China is also rapidly developed, and many has the polycarboxylic acids product quilt of excellent properties
Invent, such as patent CN103467671A reports the synthesis of big diminishing polycarboxylic acids, patent CN102977263A is reported
The long synthesis for protecting the polycarboxylic acids that collapses, patent CN104861127A report the synthesis of anti-chamotte mould polycarboxylic acids.
With the fast development of concrete technology, the pursuit of the polycarboxylic acids product more excellent to performance is endless
's.The most important demand of existing market is that the water reducing ability of polycarboxylate dispersant can or can not be substantially improvedAsked for this
Topic, it is also necessary to return on the most basic molecular structure of polycarboxylic acids to look for method, because in essence, the water reducing ability of polycarboxylic acids
Determined by its molecular structure.Polycarboxylic acids is a kind of comb polymer molecule, and its main chain is rich in hydroxy-acid group, and side chain is polyoxyethylene
Alkene ether, when it is added into cement slurry, electronegative main chain can with oriented attachment positively charged cement particle surface, lead to
Cross the electrostatic repulsion of main chain and the steric repulsion of aquation adsorption layer that polyether lateral chain is formed plays peptizaiton.Managed more than
From the point of view of, the water reducing ability of polycarboxylic acids can be improved from the adsorption capacity of main chain or the repulsive force of side chain is lifted.It is but actual
Research shows that side chain molecular weight increases to a certain extent, and its repulsive force would not increase and be lifted with molecular weight.Therefore, can only
The water reducing ability of polycarboxylic acids is improved from the adsorption capacity of lifting main chain.By increasing the carboxyl ratio in polycarboxylic acids main chain, show
The adsorption capacity of polycarboxylic acids can be so improved, so as to lift water reducing ability.But actual result is really not so, because synthesizing
When, with the rise of carboxylic acid monomer's dosage, its autohemagglutination greatly improves than regular meeting, so make on the contrary in polycarboxylic acids product it is effective into
Divide (atactic polymer of carboxylic acid monomer and polyether monomer copolymerization generation) to reduce, deteriorate water reducing ability.To solve this problem, specially
Sharp CN104387536B reports a kind of method that carboxyl ratio in polycarboxylic acids product is improved using beta-unsaturated esters monomer Hydrolyze method,
But this method equally exists the autohemagglutination problem of beta-unsaturated esters monomer and carboxyl ratio improves still insufficient problem.
The content of the invention
The problem of further can not being lifted for current poly-carboxylic-acid cement dispersant water reducing ability to meet engine request, this
Invention provides a kind of high diminishing poly-carboxylic-acid cement dispersant and preparation method thereof, and the high diminishing poly-carboxylic-acid cement dispersant can
Water-reducing rate than existing polycarboxylic acids product improves more than 30%, and this method has that technique is simple, cost is low, pollution is small etc. is excellent
Point.
Many experiments show that the adsorption capacity of polycarboxylic acids molecule is an important factor for influenceing its water reducing ability.Based on this, this
A high proportion of carboxylic acid monomer is introduced polycarboxylic acids point by invention by the chain transfer of the high molecular polymer rich in mercapto groups
In son, avoid directly with the autohemagglutination problem of carboxylic acid monomer at high proportion and carboxylic acid monomer caused by polyether monomer copolymerization, final system
It is standby go out a kind of high diminishing poly-carboxylic-acid cement dispersant.
The invention provides a kind of high diminishing poly-carboxylic-acid cement dispersant, the high diminishing poly-carboxylic-acid cement dispersant has
General formula of molecular structure as follows；
Wherein, R1For-H or-CH3, R2For-CH2- or-CH2CH2-, R3For-H or-COOH, R4For-H ,-CH3Or-
CH2COOH, x, y, z, n represent the number of repeat unit of each repeat unit, x=5~40, y=2~20, z=20~40, n=22
~25.
The weight average molecular weight of high diminishing poly-carboxylic-acid cement dispersant of the present invention is 15000~50000, molecular weight mistake
It is big or too small, it can all deteriorate properties of product.
A kind of preparation method of high diminishing poly-carboxylic-acid cement dispersant of the present invention, including：
(1) copolyreaction is carried out by methacrylic acid polyethylene glycol ester monomer and unsaturated alcohol monomer first and obtains main chain
With hydroxyl, side chain is the comb polymer molecule polymer of polyethers；
(2) under then being acted on by semi-commercial (semiworks) production thiocarbamide, by the hydroxyl in comb polymer molecule polymer made from step (1)
Sulfydryl is converted into, main chain is made and carries sulfydryl, side chain is the comb shape Macromolecular chain transfer agent of polyethers；
(3) free radical is carried out finally by comb shape Macromolecular chain transfer agent regulation and control unsaturated acid monomer made from step (2)
Polymerization so that the polymer segment of unsaturated acid monomer polymerization generation is connected with the sulphur atom in sulfydryl, finally gives the height
Diminishing poly-carboxylic-acid cement dispersant.
The molecular structure of methacrylic acid polyethylene glycol ester monomer of the present invention meets formula (1)
In formula (1) n be repeat unit number of repeat unit, n=22~45；
The methacrylic acid polyethylene glycol ester monomer weight average molecular weight is 1000~2000, and molecular weight is too small or crosses mostly
Properties of product can be caused bad；
The unsaturated alcohol monomer is any one in allyl alcohol, methallyl alcohol, 3- methyl-3-butene-1-alcohols；
The unsaturated acid monomer is in acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride
At least one.
The detailed preparation method of high diminishing poly-carboxylic-acid cement dispersant of the present invention, specifically by following three step groups
Into：
(1) unsaturated alcohol monomer and water are made into the solution that mass concentration is 40%, are warming up to 60~80 DEG C, are then added dropwise
The mass concentration being made up of methacrylic acid polyethylene glycol ester monomer, initiator I, chain-transferring agent and water is 40% mixed solution,
Time for adding 2h, the comb polymer molecule polymer that main chain carries hydroxyl is produced after being then incubated 1h；
(2) keeping temperature is constant, and thiocarbamide and dense sulphur are added in the comb polymer molecule polymer solution prepared to step (1)
Acid, after stirring reaction 12h, the sodium hydroxide solution neutralization reaction liquid that mass concentration is 40% is added, main chain is produced and carries sulfydryl
Comb shape Macromolecular chain transfer agent；
(3) keeping temperature is constant, is added dropwise in the comb shape Macromolecular chain transfer agent solution then prepared to step (2) by insatiable hunger
The mixed solution that mass concentration with acid monomers, initiator II and water composition is 40%, time for adding 1h, is then incubated 1h, adds
The high diminishing poly-carboxylic-acid cement dispersant is produced after entering the sodium hydroxide solution neutralization reaction liquid that mass concentration is 40%；
The mol ratio of methacrylic acid polyethylene glycol ester monomer and unsaturated alcohol monomer described in step (1) for (2~
4):1, the chain-transferring agent dosage be methacrylic acid polyethylene glycol ester monomer and unsaturated alcohol monomer integral molar quantity 1%~
4%；
The respective mole dosage of thiocarbamide, the concentrated sulfuric acid and sodium hydroxide described in step (2) with insatiable hunger described in step (1)
Close that the mole dosage of alcohol monomer is identical, and dosage is very few and be unfavorable for hydroxyl and be converted into sulfydryl, dosage is too high to cause wastage of material and not
Properties of product can be lifted；
The mol ratio of unsaturated acid monomer dosage described in step (3) and unsaturated alcohol monomer dosage described in step (1)
For (20~40):1；
The dosage of initiator I be unsaturated alcohol monomer and methacrylic acid macrogol ester monomer gross mass 0.1%~
0.5%, the dosage of initiator II is the 0.1%~0.5% of unsaturated acid monomer quality.
The chain-transferring agent is one kind in mercaptoethanol, TGA, mercaptopropionic acid；
The initiator I and initiator II are sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, azo diisobutyl amidine salt
Hydrochlorate (V-50), the isobutyl imidazoline hydrochloride (VA-044) of azo two, any one in azo dicyano valeric acid (V-501),
These initiators are dissolved in water.
After step (3) terminates, without purification, concentration, drying and other steps, can be directly used as cement dispersants makes reaction solution
With.Used after further being neutralized with the sodium hydrate aqueous solution that mass concentration is 40%, to strengthen the storage stability of product.
This is techniques known.The dosage of sodium hydroxide is advisable using the pH values for adjusting reaction product as 6~8.After neutralization, on
Carboxylate can be partly or entirely converted into by stating contained carboxyl in general structure (1).Due to neutralizing to the polycarboxylic acids nano-particle
Molecular weight effects very little, the present invention it is ignored.
The application process of high diminishing poly-carboxylic-acid cement dispersant of the present invention is identical with known cement dispersants, this
Art personnel generally know its application process.
High its volume of diminishing poly-carboxylic-acid cement dispersant of the present invention for total binder materials quality 0.05%~
0.3%, the volume is pure solid volume, and the percentage is mass percent.Volume is too low to deteriorate its performance, volume
The too high waste that can be caused economically and performance can not improve.
High diminishing poly-carboxylic-acid cement dispersant of the present invention can with commercially available other water reducers, such as lignosulfonic acid salt
Water reducer, naphthalene sulfonic salt water reducer, polycarboxylate water-reducer etc. are used in mixed way, and can also add air entraining agent, retarder, morning by force
Used after agent, swelling agent, tackifier, economization agent and defoamer.
The present invention has advantages below compared with prior art：
(1) volume is low, water-reducing rate is high, slump retaining in concrete application for high diminishing poly-carboxylic-acid cement dispersant of the invention
It is good, it can greatly save concrete production cost.
(2) high diminishing poly-carboxylic-acid cement dispersant production process green non-pollution of the invention, technique are simple, production is stable
Property is strong, beneficial to industrialized production.
Embodiment
The detailed preparation method of high diminishing poly-carboxylic-acid cement dispersant of the present invention given below, its object is to allow
One skilled in the art can understand present disclosure and implement according to this, but these embodiments are in no way intended to limit the present invention
Scope, any equivalent change or modification in accordance with the spirit of the invention, should all cover protection scope of the present invention it
It is interior.
In the embodiment of the present invention, polymer molecular weight is using 10 μm of (U.S. Agilent of outfit 3Mz-Gel SD plus
Company) gel permeation chromatograph (GPC, WATERS companies of the U.S.) of chromatographic column is measured, mobile phase：0.01M NaNO3's
The aqueous solution, flow velocity：1.0mL/min, sample mass percent concentration：0.50%.
Methacrylic acid polyethylene glycol ester monomer (double bond retention used in the embodiment of the present invention>98%) it is Nanjing Bo Te
New material Co., Ltd produces, and other raw materials are commercially available general analysis pure chemistry reagent.
Embodiment 1：
Add 11.6g allyl alcohols and 17.4g water in the reaction bulb equipped with agitator, it is well mixed and be warming up to 80 DEG C,
Then it is added dropwise by 400g methacrylic acid macrogol esters (Mw=1000), 1.44g potassium peroxydisulfates, 1.64g mercaptoethanols and
The mixed solution of 605g water composition, time for adding 2h, the comb-shaped copolymer that main chain carries hydroxyl is produced after being then incubated 1h；Connect down
To add 15.2g thiocarbamides and the 19.6g concentrated sulfuric acids into reaction solution, it is 80 DEG C to keep reaction temperature, after reacting 12h, adds 20g's
40% sodium hydroxide solution neutralization reaction liquid, produce the Macromolecular chain transfer agent that main chain carries sulfydryl；In most backward reaction solution
The mixed solution being made up of 288g acrylic acid, 0.288g potassium peroxydisulfates and 430g water is added dropwise, time for adding 1h, after being incubated 1h, adds
High diminishing poly-carboxylic-acid cement dispersant, solid content are produced after entering the sodium hydroxide solution neutralization reaction liquid of the 40% of 400 g
40.6%, molecular weight Mw=16200.
Embodiment 2：
Add 4.8g methallyl alcohols and 7.2g water in the reaction bulb equipped with agitator, it is well mixed and be warming up to 60
DEG C, then it is added dropwise by 400g methacrylic acid macrogol esters (Mw=2000), 0.81g VA-044,0.54g TGAs and
The mixed solution of 602g water composition, time for adding 2h, the comb-shaped copolymer that main chain carries hydroxyl is produced after being then incubated 1h；Connect down
To add 5.07g thiocarbamides and the 6.53g concentrated sulfuric acids into reaction solution, it is 60 DEG C to keep reaction temperature, after reacting 12h, adds 6.67g
40% sodium hydroxide solution neutralization reaction liquid, produce main chain carry sulfydryl Macromolecular chain transfer agent；Most backward reaction solution
It is middle that the mixed solution being made up of 200.6g methacrylic acids, 0.20g potassium peroxydisulfates and 302g water, time for adding 1h, insulation is added dropwise
After 1h, high diminishing poly-carboxylic-acid cement dispersant is produced after adding 233.3g 40% sodium hydroxide solution neutralization reaction liquid, Gu
Content 40.4%, molecular weight Mw=29400.
Embodiment 3：
5.73g 3- methyl-3-butene-1-alcohols and 8.6g water are added in the reaction bulb equipped with agitator, is well mixed simultaneously
60 DEG C are warming up to, is then added dropwise by 400g methacrylic acid macrogol esters (Mw=1500), 2.02gV-50,0.636g sulfydryl
The mixed solution of propionic acid and 604g water composition, time for adding 2h, comb shape copolymerization of the main chain with hydroxyl is produced after being then incubated 1h
Thing；Next 5.07g thiocarbamides and the 6.53g concentrated sulfuric acids are added into reaction solution, it is 60 DEG C to keep reaction temperature, after reacting 12h, is added
Enter the sodium hydroxide solution neutralization reaction liquid of the 40% of 6.67g, produce the Macromolecular chain transfer agent that main chain carries sulfydryl；It is most backward
The mixed solution being made up of 96g acrylic acid, 57.3g methacrylic acids, 0.16g V-50 and 230g water, drop are added dropwise in reaction solution
1h between added-time, after being incubated 1 h, high diminishing polycarboxylic acids water is produced after adding 200g 40% sodium hydroxide solution neutralization reaction liquid
Cement dispersant, solid content 40.2%, molecular weight Mw=26500.
Embodiment 4：
Add 5.52g allyl alcohols and 8.29g water in the reaction bulb equipped with agitator, it is well mixed and be warming up to 70 DEG C,
Then it is added dropwise by 400g methacrylic acid macrogol esters (Mw=1200), 1.62g potassium peroxydisulfates, 1.54g mercaptopropionic acids and
The mixed solution of 605g water composition, time for adding 2h, the comb-shaped copolymer that main chain carries hydroxyl is produced after being then incubated 1h；Connect down
Come into reaction solution plus 7.24g thiocarbamides and the 9.33g concentrated sulfuric acids, holding reaction temperature are 70 DEG C, after reacting 12h, add 9.52g's
40% sodium hydroxide solution neutralization reaction liquid, produce the Macromolecular chain transfer agent that main chain carries sulfydryl；In most backward reaction solution
The mixed solution being made up of 309.5g itaconic acids, 0.31g potassium peroxydisulfates and 465g water is added dropwise, time for adding 1h, after being incubated 1h, adds
High diminishing poly-carboxylic-acid cement dispersant, solid content are produced after entering the sodium hydroxide solution neutralization reaction liquid of the 40% of 238g
40.5%, molecular weight Mw=18700.
Embodiment 5：
Add 7.2g methallyl alcohols and 10.8g water in the reaction bulb equipped with agitator, it is well mixed and be warming up to 80
DEG C, then it is added dropwise by 400g methacrylic acid macrogol esters (Mw=1600), 1.02g ammonium persulfates, 0.594g mercaptopropionic acids
With the mixed solution of 604g water composition, time for adding 2h, the comb-shaped copolymer that main chain carries hydroxyl is produced after being then incubated 1h；Connect
Get off into reaction solution plus 7.6g thiocarbamides and the 9.8g concentrated sulfuric acids, holding reaction temperature are 80 DEG C, after reacting 12h, add 10g's
40% sodium hydroxide solution neutralization reaction liquid, produce the Macromolecular chain transfer agent that main chain carries sulfydryl；In most backward reaction solution
The mixed solution being made up of 352g acrylic acid, 0.352 g ammonium persulfates and 528g water is added dropwise, time for adding 1h, after being incubated 1h, adds
High diminishing poly-carboxylic-acid cement dispersant, solid content are produced after entering the sodium hydroxide solution neutralization reaction liquid of the 40% of 350g
40.8%, molecular weight Mw=40600.
Embodiment 6：
5.97g 3- methyl-3-butene-1-alcohols and 8.96g water are added in the reaction bulb equipped with agitator, is well mixed
And 80 DEG C are warming up to, then it is added dropwise by 400g methacrylic acid macrogol esters (Mw=1800), 0.81g ammonium persulfates,
The mixed solution of 0.728g mercaptoethanols and 603g water composition, time for adding 2h, then produce main chain after insulation 1h and carry hydroxyl
Comb-shaped copolymer；Next 5.28g thiocarbamides and the 6.81g concentrated sulfuric acids are added into reaction solution, it is 80 DEG C to keep reaction temperature, instead
After answering 12h, 6.94g 40% sodium hydroxide solution neutralization reaction liquid is added, macromolecular chain of the main chain with sulfydryl is produced and turns
Move agent；It is added dropwise in most backward reaction solution by 100 g acrylic acid, 59.7g methacrylic acids, 0.16g ammonium persulfates and 240g water groups
Into mixed solution, time for adding 1h, be incubated 1h after, produced after adding 208g 40% sodium hydroxide solution neutralization reaction liquid
High diminishing poly-carboxylic-acid cement dispersant, solid content 40.1%, molecular weight Mw=22700.
Embodiment 7：
Add 4.64g allyl alcohols and 8.96g water in the reaction bulb equipped with agitator, it is well mixed and be warming up to 80 DEG C,
Then it is added dropwise by 400g methacrylic acid macrogol esters (Mw=2000), 1.01g sodium peroxydisulfates, 0.218g mercaptoethanols and
The mixed solution of 603g water composition, time for adding 2h, the comb-shaped copolymer that main chain carries hydroxyl is produced after being then incubated 1h；Connect down
Come into reaction solution plus 6.08g thiocarbamides and the 7.84g concentrated sulfuric acids, holding reaction temperature are 80 DEG C, after reacting 12h, add 8g's
40% sodium hydroxide solution neutralization reaction liquid, produce the Macromolecular chain transfer agent that main chain carries sulfydryl；In most backward reaction solution
The mixed solution being made up of 115.2g acrylic acid, 185.6g fumaric acid, 0.3g sodium peroxydisulfates and 240g water, time for adding is added dropwise
1h, after being incubated 1 h, add after 320g 40% sodium hydroxide solution neutralization reaction liquid and produce high diminishing poly-carboxylic-acid cement and disperse
Agent, solid content 40.4%, molecular weight Mw=48900.
Embodiment 8：
4.8g methallyl alcohols and 7.2g water are added in the reaction bulb equipped with agitator, is well mixed and heats up 70 DEG C,
Then it is added dropwise by 400g methacrylic acid macrogol esters (Mw=2000), 0.41g V-501,0.288 g mercaptoethanols and
The mixed solution of 603g water composition, time for adding 2h, the comb-shaped copolymer that main chain carries hydroxyl is produced after being then incubated 1h；Connect down
Come into reaction solution plus 5.07g thiocarbamides and the 6.53g concentrated sulfuric acids, holding reaction temperature are 70 DEG C, after reacting 12h, add 6.67g's
40% sodium hydroxide solution neutralization reaction liquid, produce the Macromolecular chain transfer agent that main chain carries sulfydryl；In most backward reaction solution
The mixed solution being made up of 192g acrylic acid, 0.19 g V-501 and 288g water is added dropwise, time for adding 1h, after being incubated 1h, adds
High diminishing poly-carboxylic-acid cement dispersant, solid content are produced after the sodium hydroxide solution neutralization reaction liquid of the 40% of 266.7g
40.3%, molecular weight Mw=42500.
Embodiment 9：
4.3g 3- methyl-3-butene-1-alcohols and 6.5g water are added in the reaction bulb equipped with agitator, is well mixed simultaneously
80 DEG C of heating, is then added dropwise by 400g methacrylic acid macrogol esters (Mw=2000), 0.81g ammonium persulfates, 1.06g sulfydryls
The mixed solution of propionic acid and 603g water composition, time for adding 2h, comb shape copolymerization of the main chain with hydroxyl is produced after being then incubated 1h
Thing；Next 3.8g thiocarbamides and the 4.9g concentrated sulfuric acids are added into reaction solution, it is 80 DEG C to keep reaction temperature, after reacting 12h, adds 5g's
40% sodium hydroxide solution neutralization reaction liquid, produce the Macromolecular chain transfer agent that main chain carries sulfydryl；In most backward reaction solution
The mixed solution being made up of 108g acrylic acid, 0.19g ammonium persulfates and 162g water is added dropwise, time for adding 1h, after being incubated 1h, adds
Produce high diminishing poly-carboxylic-acid cement dispersant after the sodium hydroxide solution neutralization reaction liquid of the 40% of 150g, solid content 40.2%,
Molecular weight Mw=20500.
Comparative example 1：
Method synthesis with reference to shown in the B embodiments 2 of patent CN 104387536, the product are to utilize beta-unsaturated esters monomer
The poly-carboxylic-acid cement dispersant of high-carboxyl-content prepared by Hydrolyze method.
Comparative example 2：
Methyl allyl polyoxyethylene ether (M is added into the flask equipped with agitatorw=2400) 240g, hydrogen peroxide
0.34g and water 240g are sufficiently mixed, and are warming up to 45 DEG C, are added dropwise by acrylic acid 28.8g, mercaptopropionic acid 1.32g and L-AA
The mixed solution of 0.44g and water 148g compositions, 3h are added dropwise, are then incubated 1h, are eventually adding 40% NaOH solution 40g
Neutralization reaction liquid, product solid content 40.2%, molecular weight Mw=30400, the product is to utilize the commercially available general of common process preparation
Logical poly-carboxylic-acid cement dispersant.
Comparative example 3：
Methyl allyl polyoxyethylene ether (M is added into the flask equipped with agitatorw=2400) 240g, hydrogen peroxide
0.884g and water 240g are sufficiently mixed, and are warming up to 45 DEG C, are added dropwise by acrylic acid 86.4g, mercaptopropionic acid 3.45g and L- Vitamin C
The mixed solution of sour 1.14g and water 218g compositions, 3h are added dropwise, are then incubated 1h, are eventually adding 40% NaOH solution
120g neutralization reaction liquid, product solid content 40.1%, molecular weight Mw=33100, the product is the height prepared using common process
The poly-carboxylic-acid cement dispersant of carboxyl-content.
Application Example
In Application Example, used cement is small wild field P II 52.5, and miberal powder is the production of south of the River grinding Co., Ltd
S95 type miberal powders, flyash are the I level flyash of Jiangsu Huaneng Group Utilities Electric Co. production, and sand is modulus of fineness M=2.6 middle sand,
Stone is the basalt of particle diameter 5~20mm continuous gradings.
Application Example 1：
The high diminishing poly-carboxylic-acid cement dispersant of the present invention is according to GB/T8077-2000《Concrete admixture homogenieity is tried
Proved recipe method》Paste flowing degree is measured, the fixed ratio of mud is 0.27, adjusts polycarboxylic acids volume, initial flow degree is existed
Between 200-250mm, as a result such as table 1.
The flowing degree of net paste of cement test result of table 1
As can be seen from Table 1, the carboxyl-content in embodiment is conventional products comparative example 2 generally in more than 3mmol/g
More than twice of (1.49mmol/g).And from the point of view of the result of product paste flowing degree, embodiment 1-9, volume be 0.10~
In the case of 0.12%, initial flow degree is up to 250mm, and comparative example is in the case of addition ratio embodiment high more than 40%,
The fluidity similar with embodiment is can be only achieved, this proves that the poly-carboxylic-acid cement dispersant of the present invention has low-dosage, high diminishing
Excellent properties.It is important to note that comparative example 3 and embodiment have similar carboxyl-content, but water-reducing property is very
Difference, the polycarboxylic acids of this high-carboxyl-content for showing to be synthesized with common process can't bring the lifting of properties of product, it is necessary to use
Method of the present invention, it can just synthesize the product of high-carboxyl-content and high diminishing.
Application Example 2：
Next the high diminishing poly-carboxylic-acid cement dispersant pair of the present invention is detected according to method as defined in GB8076-2008
The influence of fresh concrete.Fixed water-cement ratio 0.40, adjust polycarboxylic acids volume, make concrete initial slump 21 ± 1cm it
Between, 25 DEG C of test temperature, humidity 80%, concrete quality match ratio：Cement 267, miberal powder 53, flyash 60, sand 767, great Shi
800, gravelstone 260, concrete experiments the results are shown in Table 2.
The testing concrete performance result of table 2
From the concrete test result of table 2, embodiment 1-9 has in the case where volume is relatively low with comparative example 1-3
It is suitable initial and through when fluidity, this is consistent with net slurry result, show the present invention poly-carboxylic-acid cement dispersant have it is higher
Water-reducing property.In addition, from the point of view of the test result of air content and compression strength, embodiment and comparative example data all compare phase
Closely, without significant difference, this show the high diminishing poly-carboxylic-acid cement dispersant of the present invention do not interfere with concrete air content and
Mechanical strength.
Application Example 3：
Next adsorbance of the high diminishing poly-carboxylic-acid cement dispersant of the present invention in cement is tested.Method of testing：
The aqueous solution that 300g cement and 81g contain 0.45g polycarboxylate water-reducers is mixed, sampled after stirring special time, rapid dilution
10 times, (10000r/min) centrifuges 2min at a high speed at once, takes supernatant liquor 2g, is acidified with 1g HCl (1mol/L) solution, then adds
Sample is made after entering the dilution of 17g deionized waters, sample is measured with the total organic carbon analyzers of Multi N/C 3100 of Jena companies
Organic carbon content, draws adsorption rate of the cement granules to polycarboxylic acids molecule, and experimental result is shown in Table 3.
Adsorption rate test of the polycarboxylic acids of table 3 in cement
From the adsorption rate test result of table 3, embodiment 1-9 is in the case of volume identical, 30min saturation absorption
Rate is up to 60% or so, and comparative example at most can only achieve 45%.This show the present invention poly-carboxylic-acid cement dispersant have compared with
High carboxyl-content, so as to improve the adsorption efficiency of product.
Claims (7)
1. a kind of high diminishing poly-carboxylic-acid cement dispersant, it is characterised in that there is general formula of molecular structure as follows：
Wherein, R1For-H or-CH3, R2For-CH2- or-CH2CH2-, R3For-H or-COOH, R4For-H ,-CH3Or-CH2COOH, x,
Y, z, n represent the number of repeat unit of each repeat unit, x=5 ~ 40, y=2 ~ 20, z=20 ~ 40, n=22 ~ 25.
A kind of 2. high diminishing poly-carboxylic-acid cement dispersant according to claim 1, it is characterised in that the high poly- carboxylic of diminishing
The weight average molecular weight of sour water cement dispersant is 15000 ~ 50000.
A kind of 3. preparation method of high diminishing poly-carboxylic-acid cement dispersant described in claim 1 or 2, it is characterised in that including
Following steps：
（1）Main chain is obtained with the progress copolyreaction of unsaturated alcohol monomer by methacrylic acid polyethylene glycol ester monomer first to carry
Hydroxyl, side chain are the comb polymer molecule polymer of polyethers；
（2）Under then being acted on by semi-commercial (semiworks) production thiocarbamide, by step（1）Hydroxyl conversion in obtained comb polymer molecule polymer
For sulfydryl, main chain is made and carries sulfydryl, side chain is the comb shape Macromolecular chain transfer agent of polyethers；
（3）Finally by step（2）Obtained comb shape Macromolecular chain transfer agent regulation and control unsaturated acid monomer carries out radical polymerization,
So that the polymer segment of unsaturated acid monomer polymerization generation is connected with the sulphur atom in sulfydryl, finally gives the high diminishing and gather
Carboxylic acid cement dispersants；
Step（1）Described in the molecular structure of methacrylic acid polyethylene glycol ester monomer meet formula（1）
Formula（1）Middle n be repeat unit number of repeat unit, n=22 ~ 45；
Step（1）Described in unsaturated alcohol monomer be allyl alcohol, it is methallyl alcohol, any one in 3- methyl-3-butene-1-alcohols
Kind；
Step（3）Described in unsaturated acid monomer be acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic acid
At least one of acid anhydride.
4. the preparation method of a kind of high diminishing poly-carboxylic-acid cement dispersant according to claim 3, it is characterised in that described
The weight average molecular weight of methacrylic acid polyethylene glycol ester monomer is 1000 ~ 2000.
A kind of 5. preparation method of high diminishing poly-carboxylic-acid cement dispersant according to claim 3 or 4, it is characterised in that
Specifically it is made up of following three steps：
（1）Unsaturated alcohol monomer and water are made into the solution that mass concentration is 40%, 60 ~ 80 DEG C is warming up to, is then added dropwise by methyl
Polyalkylene glycol acrylate ester monomer, initiator I, the mass concentration of chain-transferring agent and water composition are 40% mixed solution, time for adding
2 h, the comb polymer molecule polymer that main chain carries hydroxyl is produced after being then incubated 1 h；
（2）Keeping temperature is constant, to step（1）Thiocarbamide and the concentrated sulfuric acid are added in the comb polymer molecule polymer solution of preparation, is stirred
After mixing 12 h of reaction, the sodium hydroxide solution neutralization reaction liquid that mass concentration is 40 % is added, produces the comb that main chain carries sulfydryl
Shape Macromolecular chain transfer agent；
（3）Keeping temperature is constant, then to step（2）It is added dropwise in the comb shape Macromolecular chain transfer agent solution of preparation by unsaturated acids
The mixed solution that the mass concentration of monomer, initiator II and water composition is 40%, the h of time for adding 1, is then incubated 1 h, adds matter
The high diminishing poly-carboxylic-acid cement dispersant is produced after measuring the sodium hydroxide solution neutralization reaction liquid that concentration is 40 %；
Step（1）Described in methacrylic acid polyethylene glycol ester monomer and the mol ratio of unsaturated alcohol monomer be（2~4）:1, institute
State 1% ~ 4% that chain-transferring agent dosage is methacrylic acid polyethylene glycol ester monomer and unsaturated alcohol monomer integral molar quantity；
Step（2）Described in thiocarbamide, the concentrated sulfuric acid and sodium hydroxide respective mole dosage and step（1）Described in unsaturated alcohol
The mole dosage of monomer is identical；
Step（3）Described in unsaturated acid monomer dosage and step（1）Described in the mol ratio of unsaturated alcohol monomer dosage be（20
~40）:1；
The dosage of initiator I is the 0.1% ~ 0.5% of unsaturated alcohol monomer and methacrylic acid macrogol ester monomer gross mass,
The dosage of initiator II is the 0.1% ~ 0.5% of unsaturated acid monomer quality.
6. the preparation method of a kind of high diminishing poly-carboxylic-acid cement dispersant according to claim 6, it is characterised in that described
Chain-transferring agent is one kind in mercaptoethanol, TGA, mercaptopropionic acid；
The initiator I and initiator II are sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, azo diisobutyl amidine hydrochloride
（V-50）, the isobutyl imidazoline hydrochloride (VA-044) of azo two, azo dicyano valeric acid（V-501）In any one.
A kind of 7. application process of high diminishing poly-carboxylic-acid cement dispersant of claim 1 or 2, it is characterised in that：The height
The volume of diminishing poly-carboxylic-acid cement dispersant is the 0.05% ~ 0.3% of total binder materials quality.
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|---|---|---|---|---|
| CN101492518A (en) * | 2009-02-27 | 2009-07-29 | 上海市建筑科学研究院(集团)有限公司 | Ethers polycarboxylic acid water reducing agent and preparation |
| JP2015129071A (en) * | 2014-01-08 | 2015-07-16 | 株式会社日本触媒 | Multi-branched polyalkylene glycol-based block copolymer |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492518A (en) * | 2009-02-27 | 2009-07-29 | 上海市建筑科学研究院(集团)有限公司 | Ethers polycarboxylic acid water reducing agent and preparation |
| JP2015129071A (en) * | 2014-01-08 | 2015-07-16 | 株式会社日本触媒 | Multi-branched polyalkylene glycol-based block copolymer |
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| CN113072666A (en) * | 2020-01-06 | 2021-07-06 | 江苏苏博特新材料股份有限公司 | Preparation method and application of high-water-reduction type polycarboxylic acid superplasticizer |
| CN113072666B (en) * | 2020-01-06 | 2022-05-31 | 江苏苏博特新材料股份有限公司 | Preparation method and application of high-water-reduction type polycarboxylic acid superplasticizer |
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