CN100546934C - Cement dispersants and preparation method thereof - Google Patents
Cement dispersants and preparation method thereof Download PDFInfo
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- CN100546934C CN100546934C CNB2007100465988A CN200710046598A CN100546934C CN 100546934 C CN100546934 C CN 100546934C CN B2007100465988 A CNB2007100465988 A CN B2007100465988A CN 200710046598 A CN200710046598 A CN 200710046598A CN 100546934 C CN100546934 C CN 100546934C
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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
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
Abstract
The invention provides a kind of cement dispersants and preparation method thereof, be polyoxyalkylenes monoether (methyl) acrylate, unsaturated monocarboxylic acid or derivatives thereof monomer and other monomeric multipolymers.This cement dispersants has absorption, bleed, dispersion, wetting, solubilising, increases multiple functions such as steady, can make concrete have low water-cement ratio, low viscosity, high workability, slow setting, guarantor characteristics such as collapse, thereby can improve concrete workability, help realizing on-the-spot preparation and remote the conveying, can be used for preparing high strength, the long concrete of operable time.This preparation method has that energy consumption is low, efficient is high, high repeatability and other advantages.
Description
Technical field
The present invention relates to relate to a kind of polyocarboxy acid type polymer water cement dispersant and preparation method thereof.
Background technology
The development of cement dispersants (claiming cement water reducing agent again) has long history.Nineteen thirty-five U.S. E.W. Si Kelipuche at first develops the fluidizer that sulfonated lignin are main component, is widely used in the C20-C40 concrete, has promoted concrete and has developed to medium tenacity; Japan successfully developed the naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent in 1962, and such water reducer has advantages such as production cost is lower, and water-reducing rate is effective, thereby is widely used in the C30-C60 concrete, has promoted concrete and has developed to high strength.But, use the concrete slump loss of this water reducer preparation fast, can't satisfy construction requirements such as pumping, can not be used to prepare high performance concrete.
Abroad since 20th century the mid-80 research and develop polymeric superplasticizer of new generation, as high-efficiency water-reducing agent of poly-carboxylic acid such as (methyl) acrylic acid series, maleic anhydride series, to formally suitability for industrialized production and the application of the mid-90 in 20th century.In this year, concrete admixture research develops to high-performance, pollution-free direction day by day with production in the world.Polycarboxylate water-reducer is because water-reducing rate height, function of slump protection are good, and later strength increases big, and suitable preparation is high-strength, super high strength concrete, high workability and self-compacting concrete, thereby is subjected to the extensive concern of domestic and international concrete works circle.
Patent CN1412175 discloses a kind of preparation method of allyl ester ether monomer and the method for preparing cement water reducing agent with this monomer: at first handle allyl alcohol polyether and its peroxide value is reached below the 5.0meq/kg with sorbing materials such as aluminum oxide, carry out esterification with the aliphatics monocarboxylic acid again and make allyl ester ether monomer.To make weight-average molecular weight under the initiator be 13500 multipolymer making of Diisopropyl azodicarboxylate under 80 ℃ with this refined allyl ester ether monomer and maleic anhydride again, again its multipolymer and alkyl polyalkylene glycol made a kind of cement dispersants 100 ℃ of following esterifications.The reaction times that this arts demand is very long is also expended a large amount of energy, makes that the cost of the finished product is very high.
Patent CN1167739A discloses a kind of method for preparing poly-carboxylic-acid cement dispersant, at first alkoxyl group multi alkylidene diol and (methyl) acrylate are carried out transesterification reaction under the effect of basic catalyst and prepare alkoxyl group multi alkylidene diol list (methyl) acrylate, mix with (methyl) vinylformic acid, copolymerization makes the polycarboxylate dispersant under the effect of ammonium persulphate again.But, a large amount of excessive (methyl) acrylate of needs when preparing this alkoxyl group multi alkylidene diol list (methyl) acrylate, and with the polycarboxylate water-reducer slump of this prepared through the time lose excessive.
Patent CN1288870A discloses a kind of method that carboxyl, hydroxyl, sulfonic group polyfunctional group prepare that contains in oxidation-reduction system, its temperature of reaction is at 70-110 ℃, oxygenant is hydrogen peroxide or persulphate, reductive agent is Hypophosporous Acid, 50 or its salt, but, it is insufficient adopting the water-reducing property of the water reducer of this method preparation, could obtain good dispersive ability under the higher solids volume.
Summary of the invention
The purpose of this invention is to provide a kind of cement dispersants and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
Cement dispersants of the present invention is polyoxyalkylenes monoether (methyl) acrylate of general formula (1) expression, unsaturated monocarboxylic acid and derivatives monomer and other monomeric multipolymers of general formula (2) expression;
Wherein: R in the formula
1Represent hydrogen atom or methyl, R
2O representative have the oxyalkylene group of 2-4 carbon atom or two or more oxyalkylene groups that contain 2-2 carbon atom mixture, R3 represents alkyl group, phenyl group or the alkyl phenyl group of hydrogen atom or 1～8 carbon atom, m is the average addition mole number of oxyalkylene group, the arbitrary number between m=1～35 integers;
In the formula: R
4Represent hydrogen atom or methyl, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amine.In multipolymer, the unsaturated monocarboxylic acid and the derivatives monomer thereof of general formula (2) expression can be wherein more than one;
Other monomers are selected from more than one in allyl sulphonic acid, methallylsulfonic acid, hydroxyalkyl acrylates, unsaturated amides, vinyl ester, propenyl ester or the vinyl aromatic compounds;
Polyoxyalkylenes monoether (methyl) acrylate of preferred general formula (1) expression is oxyethylene group monomethyl ether metacrylic acid ester, oxyethylene group monomethyl ether acrylate or oxypropylene group monomethyl ether metacrylic acid ester.
The unsaturated monocarboxylic acid and the derivative thereof of preferred general formula (2) expression are vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate.
Preferred other monomers are Propylene glycol monoacrylate, sodium allyl sulfonate or methallylsulfonic acid sodium.
Will be by weight, polyoxyalkylenes monoether (methyl) acrylate of general formula (1) expression is 40-90 part, and the unsaturated monocarboxylic acid and the derivatives monomer thereof of general formula (2) expression are 30-55 part, and other monomers are 5-30 part;
Prepare the method for cement dispersants of the present invention, comprise the steps:
(1) with polyoxyalkylenes monoether (methyl) acrylate of general formula (1) expression, unsaturated monocarboxylic acid and derivatives monomer and other monomer of general formula (2) expression, in nitrogen protection, 60-100 ℃, under the acting in conjunction of initiator and molecular weight regulator, carry out polymerization in the aqueous solution, polymerization time is 2-6 hour, adds alkaline matter then, the neutralization reaction system is 6-8 to pH, the acquisition product;
Said initiator is a kind of or its mixture in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, the hydrogen peroxide; Used molecular weight regulator is a kind of or its mixture in mercaptoethanol, 2 mercaptopropionic acid, 3-thiohydracrylic acid or the Thiovanic acid etc., and the consumption of initiator is the 0.1-5.0% of total monomer weight;
Said molecular weight regulator selected from mercapto ethanol, 2 mercaptopropionic acid or tri-thiol propionic acid, consumption is the 0.01-2.5% of total monomer weight;
The consumption of preferred initiator is 0.5-2.0%, and the consumption of molecular weight regulator is 0.1-1.0%;
Said alkaline matter is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide or triethylamine;
Cement dispersants of the present invention can be used for cement and disperse.
Cement dispersants of the present invention, when being used for the cement dispersion, have absorption, bleed, dispersion, wetting, solubilising, increase multiple functions such as steady, can make concrete have low water-cement ratio, low viscosity, high workability, slow setting, guarantor characteristics such as collapse, thereby can improve concrete workability, help realizing on-the-spot preparation and remote the conveying, can be used for preparing high strength, the long concrete of operable time.This preparation method has that energy consumption is low, efficient is high, high repeatability and other advantages.
Embodiment
Among the embodiment, if no special instructions, be weight part.
Embodiment 1
In the four-hole boiling flask that stirring, thermometer, breather and Dropping feeder are housed, add 140 parts of deionized waters and 30 parts of methallylsulfonic acid sodium, stirring, filling and be warming up to 60 ℃ under the nitrogen condition, drip simultaneously and mixed the mixed aqueous solution of being made up of 40 parts of polyoxyethylene thiazolinyl monomethyl ether metacrylic acid esters, 30 parts of vinylformic acid, 1 part of 3-thiohydracrylic acid and 10 and restrain 5% ammonium persulfate aqueous solution, the dropping time is controlled at 30min.After dropwising, making in 4 hours 60 ℃ of insulations to react completely, after reaction finishes, is about 30% sodium hydroxide solution neutralization solution pH value to 7.0 with 55 parts of weight concentrations, promptly gets cement dispersants sample 1.Test-results sees Table 1.
Embodiment 2
In the four-hole boiling flask that stirring, thermometer, breather and Dropping feeder are housed, add 17 parts of deionized waters and 5 parts of methallylsulfonic acid sodium, stirring, filling and be warming up to 70 ℃ under the nitrogen condition, drip simultaneously and mixed the mixed aqueous solution of being made up of 90 parts of polyoxyethylene thiazolinyl monomethyl ether metacrylic acid esters, 30 parts of vinylformic acid, 0.625 part of 3-thiohydracrylic acid and 20 and restrain 5% ammonium persulfate aqueous solution, the dropping time is controlled at 40min.After dropwising, made in 3 hours 70 ℃ of insulations to react completely, reaction with about 55 part 30% potassium hydroxide solution neutralization solution pH value to 7.0, promptly gets cement dispersants sample 2 after finishing.Test-results sees Table 1.
Embodiment 3
In the four-hole boiling flask that stirring, thermometer, breather and Dropping feeder are housed, add 66 parts of deionized waters and 5 parts of methallylsulfonic acid sodium, stirring, filling and be warming up to 80 ℃ under the nitrogen condition, drip simultaneously and mixed the mixed aqueous solution be made up of 40 parts of polyoxyethylene thiazolinyl monomethyl ether metacrylic acid esters, 55 parts of vinylformic acid, 0.1 part of 3-thiohydracrylic acid and 40 part 5% ammonium persulfate aqueous solution, the dropping time is controlled at 50min.After dropwising, made in 2 hours 80 ℃ of insulations to react completely, reaction with about 101 part 30% solution of ammonium hydroxide neutralization solution pH value to 7.0, promptly gets cement dispersants sample 3 after finishing.Test-results sees Table 1.
Embodiment 4
In the four-hole boiling flask that stirring, thermometer, breather and Dropping feeder are housed, add 182 parts of deionized waters and 15 parts of methallylsulfonic acid sodium, stirring, filling and be warming up to 70 ℃ under the nitrogen condition, drip simultaneously and mixed the mixed aqueous solution be made up of 80 parts of polyoxytrimethylene base monomethyl ether metacrylic acid esters, 45 parts of vinylformic acid, 15 parts of Propylene glycol monoacrylates, 1 part of 2 mercaptopropionic acid and 37 part 5% ammonium persulfate aqueous solution, the dropping time is controlled at 1h.After dropwising, made in 3 hours 70 ℃ of insulations to react completely, reaction with about 83 part 30% sodium hydroxide solution neutralization solution pH value to 7.0, promptly gets cement dispersants sample 4 after finishing.Test-results sees Table 1.
Embodiment 5
In the four-hole boiling flask that stirring, thermometer, breather and Dropping feeder are housed, add 182 parts of deionized waters and 15 parts of methallylsulfonic acid sodium, stirring, filling and be warming up to 90 ℃ under the nitrogen condition, drip simultaneously and mixed the mixed aqueous solution be made up of 80 parts of polyoxytrimethylene base monomethyl ether metacrylic acid esters, 45 parts of vinylformic acid, 15 parts of Propylene glycol monoacrylates, 1 part of mercaptoethanol and 37 part 5% ammonium persulfate aqueous solution, the dropping time is controlled at 1h.After dropwising, made in 1.5 hours 90 ℃ of insulations to react completely, after reaction finishes, with in 83 parts of triethylamines with the pH value to 6.5 of system, promptly get cement dispersants sample 5.Test-results sees Table 1.
Clean slurry experiment:
Clean slurry degree of mobilization test (GB/T 8077-2000): adopt reference cement, according to the degree of mobilization of GB 8077-87 test cement paste.
Table one: the flowing degree of net paste of cement experiment of surveying different dispersion agents
Annotate: oily naphthalene series high-efficiency cement dispersants is the beta-oil sodium naphthalene sulfonate.
From table one as can be known, cement dispersants of the present invention is compared with the naphthalene series high-efficiency cement dispersants, and better dispersiveness and dispersion stabilization are arranged, and is fit to do cement dispersants.
Claims (8)
1. a cement dispersants is characterized in that, is polyoxyalkylenes monoether (methyl) acrylate of general formula (1) expression, unsaturated monocarboxylic acid or derivatives thereof monomer and other monomeric multipolymers of general formula (2) expression;
Wherein: R in the formula
1Represent hydrogen atom or methyl, R
2The O representative has the oxyalkylene group of 2-4 carbon atom, and R3 represents alkyl group, phenyl group or the alkyl phenyl group of hydrogen atom or 1～8 carbon atom, and m is the average addition mole number of oxyalkylene group, the arbitrary number between m=1～35 integers;
In the formula: R
4Represent hydrogen atom or methyl, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amine, and in multipolymer, the unsaturated monocarboxylic acid and the derivatives monomer thereof of general formula (2) expression can be wherein more than one:
Other monomers are selected from more than one in allyl sulphonic acid, methallylsulfonic acid, hydroxyalkyl acrylates, unsaturated amides, vinyl ester, propenyl ester or the vinyl aromatic compounds.
2. cement dispersants according to claim 1, it is characterized in that polyoxyalkylenes monoether (methyl) acrylate of general formula (1) expression is oxyethylene group monomethyl ether metacrylic acid ester, oxyethylene group monomethyl ether acrylate or oxypropylene group monomethyl ether metacrylic acid ester.
3. cement dispersants according to claim 1 is characterized in that, said other monomers are Propylene glycol monoacrylate, sodium allyl sulfonate or methallylsulfonic acid sodium.
4. according to each described cement dispersants of claim 1～3, it is characterized in that, by weight, polyoxyalkylenes monoether (methyl) acrylate of general formula (1) expression is 40-90 part, the unsaturated monocarboxylic acid and the derivatives monomer thereof of general formula (2) expression are 30-55 part, and other monomers are 5-30 part.
5. the method for preparing each described cement dispersants of claim 1～4; it is characterized in that; comprise the steps: polyoxyalkylenes monoether (methyl) acrylate of general formula (1) expression, unsaturated monocarboxylic acid and derivatives monomer and other monomers of general formula (2) expression; in nitrogen protection; 60-100 ℃; under the acting in conjunction of initiator and molecular weight regulator; in the aqueous solution, carry out polymerization; polymerization time is 2-6 hour; add alkaline matter then; the neutralization reaction system is 6-8 to pH, the acquisition product.
6. method according to claim 5 is characterized in that, said initiator is a kind of or its mixture in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, the hydrogen peroxide; Used molecular weight regulator is a kind of or its mixture in mercaptoethanol, 2 mercaptopropionic acid, 3-thiohydracrylic acid or the Thiovanic acid.
7. method according to claim 5 is characterized in that, the consumption of initiator is the 0.1-5.0% of total monomer weight, and the molecular weight regulator consumption is the 0.01-2.5% of total monomer weight.
8. the application of each described cement dispersants of claim 1～4 is characterized in that, is used for cement and disperses.
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| CN101386489B (en) * | 2008-09-12 | 2011-09-28 | 苏州弗克新型建材有限公司 | Polycarboxylate dehydragent and preparation method thereof |
| CN101514090B (en) * | 2008-12-30 | 2012-07-18 | 上海东升新材料有限公司 | Ornamental model external thermal insulation rendering mortar composition |
| CN102120803B (en) * | 2010-11-19 | 2012-11-07 | 苏州博纳化学科技有限公司 | Method for preparing hydrophobic macromonomer carboxylic acid dispersing agent |
| JP2012207068A (en) * | 2011-03-29 | 2012-10-25 | Nippon Shokubai Co Ltd | Novel polymer and method of manufacturing the same |
| CN102276181A (en) * | 2011-05-18 | 2011-12-14 | 江苏名和集团有限公司 | Mud blocking agent for concrete and preparation method thereof |
| CN109537358B (en) * | 2018-11-07 | 2022-07-26 | 上海东升新材料有限公司 | Polymerization dispersant and environment-friendly surface sizing agent prepared by adopting same |
| CN113860789B (en) * | 2021-09-28 | 2023-01-03 | 江苏海能电力设计咨询有限责任公司 | Concrete admixture with water reducing and corrosion preventing functions and preparation method thereof |
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Effective date of registration: 20171102 Address after: Xinglongzhuang Town Industrial Park, Jining District of Yanzhou City, Shandong province 272100 Patentee after: Jining Ming Sheng new material Co., Ltd. Address before: 200235, room 2, building 100, 1107 Qinzhou Road, Shanghai, Xuhui District Patentee before: Shanghai Dongsheng new material Co., Ltd. |
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