CN1847187A - Polycarboxylic acid cement dispersant and its prepn process - Google Patents
Polycarboxylic acid cement dispersant and its prepn process Download PDFInfo
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- CN1847187A CN1847187A CN 200510024894 CN200510024894A CN1847187A CN 1847187 A CN1847187 A CN 1847187A CN 200510024894 CN200510024894 CN 200510024894 CN 200510024894 A CN200510024894 A CN 200510024894A CN 1847187 A CN1847187 A CN 1847187A
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Abstract
The present invention discloses polycarboxylicacid cement dispersant and its preparation process. The cement dispersant is prepared with unsaturated polyoxyethylene ether monomer, unsaturated binary carboxylic acid monomer and other monomer capable of copolymerizing with the said monomers, and through copolymerization in redox system. The cement dispersant of the present invention has high water reducing rate, low slump loss and other advantages, and the preparation process has low power consumption, high efficiency, high repeatability and other advantages and is suitable for producing polycarboxylicacid cement dispersant.
Description
Technical field
The present invention relates to a kind of water reducer and prepare the method for this agent, specifically a kind of poly-carboxylic-acid cement dispersant and preparation method thereof.
Background technology
The development of cement dispersants (claiming water reducer again) has long history.Nineteen thirty-five U.S. E.W. Si Kelipuche at first is developed into the fluidizer that sulfonated lignin are main component, is widely used in C20～C40 concrete, is promoting concrete and is developing to medium tenacity; 1962, Japan successfully developed the naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent, and such water reducer has advantages such as production cost is lower, and water-reducing rate is effective, thereby is widely used in C30～C60 concrete, is promoting concrete and is developing 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 recent years, concrete admixture research develops to high-performance, pollution-free direction day by day with production in the world.Polycarboxylate water-reducer is because the water-reducing rate height, and function of slump protection is 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.
A kind of preparation method of allyl ester ether monomer and the method for preparing water reducer with this monomer are disclosed in patent CN1412175: 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 this multipolymer and alkyl polyalkylene glycol obtained 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.
A kind of method for preparing poly-carboxylic-acid cement dispersant is disclosed in patent CN1167739A, 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 polycarboxylate water-reducer 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 monomer, and with the polycarboxylate water-reducer slump of this prepared through the time lose excessive.
Announced a kind of method that carboxylic acid, hydroxyl, sulfonic group polyfunctional group prepare in oxidation-reduction system that contains in patent CN1288870A, its temperature of reaction is 70～110 ℃, and oxygenant is hydrogen peroxide or persulphate, and 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 raw material sources and be easy to get, production cost is low, the cement dispersants of the easy application performance effect excellence that is easy to industrialization, environmentally safe, the finished product of technology and preparation method thereof.
The object of the present invention is achieved like this:
A kind of poly-carboxylic-acid cement dispersant, be will be by weight 50～95% by the unsaturated polyalkylene oxide base ether monomer (a) of general formula (1) expression, by weight be 4～49% by the unsaturated dicarboxylic acid of general formula (2) expression and derivatives monomer (b) thereof but and be that other monomer (c) copolymerization under redox system of 1～45% copolymerization gets by weight, the total amount of (a) and (b), (c) is 100% by weight;
R
1O(R
2O)nR
3 (1)
R wherein
1Expression comprises the thiazolinyl of 2～4 carbon atoms, R
2O represents to have the oxyalkylene group of 2～4 carbon atoms or the mixture of a plurality of oxyalkylene groups, R
3Represent hydrogen or alkyl group, phenyl group or the alkyl phenyl group of 1～12 carbonatoms are arranged, n is the average addition mole number of oxyalkylene group, and it represents arbitrary number of 1～350; In multipolymer, monomer (a) can be that wherein a kind of independent use or two or more mixing are used;
R wherein
4Represent OM
2Perhaps O (R
5O)
mR
6, M wherein
1, M
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine separately, R
5O represents to have the oxyalkylene group of 2～4 carbon atoms or the mixture of a plurality of oxyalkylene groups, R
6Represent hydrogen or alkyl group, phenyl group or the alkyl phenyl group of 1～12 carbonatoms are arranged, m is the average addition mole number of oxyalkylene group, and it represents arbitrary number of 1～350 ,-COOM
1With-COR
4Can form an anhydride group between the carbon atom that group connects respectively replaces-COOM
1With-COR
4Group.In multipolymer, monomer (b) can be that wherein a kind of independent use or two or more mixing are used.
Example as comonomer (c) has: thiazolinyl carboxylic acid, its salt or ester; (methyl) vinyl cyanide; Unsaturated sulfonic acid or its salt are as (first generation) allyl sulphonic acid or its salt, styrene sulfonic acid or its salt; Unsaturated amides is as (methyl) acrylamide; Vinyl ester is as vinyl-acetic ester, propionate; Vinyl aromatic compounds is as vinylbenzene, vinyl toluene etc.; In multipolymer, monomer (c) can be that wherein a kind of independent use or two or more mixing are used.
The method for preparing above-mentioned dispersion agent is: adopt redox system to make monomer component carry out polymerization in the aqueous solution as initiator down at 25～70 ℃ and make.
Oxygenant in the redox system is hydroperoxide, as hydrogen peroxide, tertbutyl peroxide etc.; Reductive agent in the redox system is the sub-compound of sulphur, closes sodium bisulfite, sodium hyposulfate etc. as sodium bisulfite, Sulfothiorine, formaldehyde.
When enforcement is of the present invention, the oxygenant consumption is 0.1%～20% of a total monomer weight, the reductive agent consumption is 0.05～10% of a total monomer weight, and the preferred oxidant consumption is 0.2%～10% of a total monomer weight, and the reductive agent consumption is 0.1～5% of a total monomer weight.
Implementing when of the present invention, monomer (a) adds when being preferably in the reaction beginning, and monomer (b) (c) can add when the reaction beginning, also can add after the reaction beginning in batches or continuously, perhaps these adding methods is combined and carries out.When enforcement was of the present invention, the temperature of polyreaction was 25～70 ℃, preferred 30～60 ℃.
Poly-carboxylic-acid cement dispersant of the present invention not only has high water-reducing rate, also has excellent slump hold facility.Preparation method of the present invention has advantages such as less energy-consumption, high-level efficiency, repetition stability be good, is suitable for producing polycarboxylate water-reducer.
Embodiment
Following examples will the present invention is further described, but the present invention is not produced any restriction.
Listed abbreviation below having used in an embodiment:
The oxirane additive product of AE-1:1 mole vinyl carbinol and 25 moles
The oxirane additive product of AE-2:1 mole vinyl carbinol and 50 moles
AE-3:1 mole vinyl carbinol earlier with 3 moles propylene oxide addition again with 35 moles oxirane additive product
The oxirane additive product of AE-4:1 mole methallyl alcohol and 35 moles
The oxirane additive product of AE-5:1 mole 4-hydroxyl butyl vinyl and 35 moles
Embodiment 1
The hydrogen peroxide that adds 120gAE-1,120g deionized water, 3.0g 27.5% in the four-hole boiling flask of the 500ml that disposes agitator, thermometer, Dropping feeder stirs and is warming up to 50 ℃.Drip simultaneously and mixed 14.7g maleic anhydride, 7.1g Rocryl 410, the monomer solution of 50.0g deionized water and the sodium formaldehyde sulphoxylate solution of 20g 10%, the dropping time was controlled at about 90 minutes, and temperature of reaction is controlled at 48～52 ℃.After dropwising, 48～52 ℃ down insulation made polyreaction complete in about 30 minutes, after insulation finishes, add among the 36g 30%NaOH and about PH to 6.5, obtain poly-carboxylic-acid cement dispersant PC-1 of the present invention.
Embodiment 2
The hydrogen peroxide that adds 120gAE-2,120g deionized water, 2.0g 27.5% in the four-hole boiling flask of the 500ml that disposes agitator, thermometer, Dropping feeder stirs and is warming up to 50 ℃.Drip simultaneously and mixed 9.8g maleic anhydride, the monomer solution of 50.0g deionized water and the sodium formaldehyde sulphoxylate aqueous solution of 4.4g methyl acrylate and 15g 10%, the dropping time was controlled at about 90 minutes, and temperature of reaction is controlled at 48～52 ℃.After dropwising, 48～52 ℃ down insulation made polyreaction complete in about 30 minutes, after insulation finishes, add among the 27.0g 30%NaOH and about PH to 6.5, obtain poly-carboxylic-acid cement dispersant PC-2 of the present invention.
Embodiment 3
The hydrogen peroxide that adds 120gAE-3,120g deionized water, 3.0g 27.5% in the four-hole boiling flask of the 500ml that disposes agitator, thermometer, Dropping feeder stirs and is warming up to 50 ℃.Drip simultaneously and mixed 14.7g maleic anhydride, 7.1g acrylamide, the monomer solution of 50.0g deionized water and the sodium formaldehyde sulphoxylate solution of 4.4g methyl acrylate and 20g 10%, the dropping time was controlled at about 90 minutes, and temperature of reaction is controlled at 48～52 ℃.After dropwising, 48～52 ℃ down insulation made polyreaction complete in about 30 minutes, after insulation finishes, add among the 36g 30%NaOH and about PH to 6.5, obtain poly-carboxylic-acid cement dispersant PC-3 of the present invention.
Embodiment 4
The hydrogen peroxide that adds 120gAE-4,120g deionized water 2.5g 27.5% in the four-hole boiling flask of the 500ml that disposes agitator, thermometer, Dropping feeder stirs and is warming up to 50 ℃.Drip simultaneously and mixed 14.7g maleic anhydride, 7.1g acrylamide, the monomer solution of 50.0g deionized water and the sodium formaldehyde sulphoxylate solution of 15g 10%, the dropping time was controlled at about 90 minutes, and temperature of reaction is controlled at 48～52 ℃.After dropwising, 48～52 ℃ down insulation made polyreaction complete in about 30 minutes, after insulation finishes, add among the 36g 30%NaOH and about PH to 6.5, obtain poly-carboxylic-acid cement dispersant PC-4 of the present invention.
Embodiment 5
The hydrogen peroxide that adds 120gAE-5,120g deionized water 2.5g 27.5% in the four-hole boiling flask of the 500ml that disposes agitator, thermometer, Dropping feeder stirs and is warming up to 50 ℃.Drip simultaneously and mixed 14.7g maleic anhydride, the monomer solution of 50.0g deionized water and the sodium formaldehyde sulphoxylate solution of 2.5g vinylbenzene and 15g 10%, the dropping time was controlled at about 90 minutes, and temperature of reaction is controlled at 48～52 ℃.After dropwising, 48～52 ℃ down insulation made polyreaction complete in about 30 minutes, after insulation finishes, add among the 36g 30%NaOH and about PH to 6.5, obtain poly-carboxylic-acid cement dispersant PC-5 of the present invention.
Embodiment 6
The hydrogen peroxide that adds 60gAE-2,60gAE-4,120g deionized water 2.5g 27.5% in the four-hole boiling flask of the 500ml that disposes agitator, thermometer, Dropping feeder stirs and is warming up to 50 ℃.Drip simultaneously and mixed 14.7g maleic anhydride, 10.3 gram Sodium styrene sulfonate, the monomer solution of 50.0g deionized water and the sodium formaldehyde sulphoxylate solution of 15g 10%, the dropping time was controlled at about 90 minutes, and temperature of reaction is controlled at 48～52 ℃.After dropwising, 48～52 ℃ down insulation made polyreaction complete in about 30 minutes, after insulation finishes, add among the 36g 30%NaOH and about PH to 6.5, obtain poly-carboxylic-acid cement dispersant PC-6 of the present invention.
Clean slurry test
Clean slurry degree of mobilization test (GB/T 8077-2000): adopt reference cement, according to the clean slurry degree of mobilization of GB8077-87 test to cement.
Test result sees Table 1.
Table 1 is mixed the clean slurry slump test of different cement dispersants
| Solid volume % | Clean slurry degree of mobilization | |||
| 5min | 30min | 60min | ||
| PC-1 | 0.24 | 250 | 245 | 240 |
| PC-2 | 0.22 | 240 | 245 | 240 |
| PC-3 | 0.22 | 245 | 245 | 230 |
| PC-4 | 0.24 | 250 | 255 | 255 |
| PC-5 | 0.22 | 230 | 235 | 240 |
| PC-6 | 0.20 | 235 | 245 | 245 |
| Certain naphthalene system | 0.80 | 225 | 190 | 165 |
As known from Table 1, poly-carboxylic-acid cement dispersant of the present invention is compared with naphthalene series high-efficiency water-reducing agent, has better dispersiveness and dispersion stabilization, is suitable as cement dispersants.
Concrete test
Gelatinous material adopts ordinary Portland cement, and fine aggregate adopts medium sand (fineness modulus 2.9, silt content 0.2%), and coarse aggregate uses rubble (particle diameter 5-25mm, continuous grade, voidage 43%).Concrete mix sees Table 2.
Table 2 concrete mix
| Water cement ratio | Sand coarse aggregate ratio | (the kg/m of unit 3) | |||
| Water | Cement | Sand | Stone | ||
| 0.42 | 0.43 | 165 | 390 | 733 | 967 |
Mix concrete under above-mentioned condition, and measure the concrete slump, air content, slump retention value, it the results are shown in Table 3.
Table 3 is mixed the concrete test of different poly-carboxylic-acid cement dispersants
| The multipolymer kind | Solid volume % | Initially | Behind the 60min | Slump retention value | ||
| The slump (cm) | Air content (%) | The slump (cm) | Air content (%) | |||
| PC-1 | 0.25 | 21.0 | 3.0 | 19.5 | 2.8 | 92.9％ |
| PC-2 | 0.24 | 21.5 | 3.2 | 20.0 | 3.0 | 93.0％ |
| PC-3 | 0.24 | 20.5 | 2.8 | 19.0 | 2.7 | 92.7％ |
| PC-4 | 0.26 | 21.0 | 3.6 | 19.0 | 3.4 | 90.5％ |
| PC-5 | 0.25 | 22.0 | 2.8 | 19.5 | 2.6 | 88.6％ |
| PC-6 | 0.23 | 21.0 | 2.9 | 18.0 | 2.8 | 85.7％ |
| Certain naphthalene system | 0.90 | 21.0 | 2.5 | 12.0 | 2.2 | 57.1％ |
Annotate: slump retention value: leave standstill the slump/initial slump * 100% behind the 60min
Above-mentioned test shows, adopts the poly-carboxylic-acid cement dispersant of the present invention's preparation just can obtain the high slump under lower volume, and has good slump hold facility.
Claims (5)
1, a kind of poly-carboxylic-acid cement dispersant, it is characterized in that be be by weight 50～95% by the unsaturated polyalkylene oxide base ether monomer (a) of general formula (1) expression, by weight be 4～49% by the unsaturated dicarboxylic acid and the derivatives monomer (b) thereof of general formula (2) expression and be that other comonomer (c) copolymerization of 1～45% gets by weight, the total amount of (a) and (b), (c) is 100% by weight;
R
1O(R
2O)nR
3 (1)
R wherein
1Expression comprises the thiazolinyl of 2～4 carbon atoms, R
2O represents to have the oxyalkylene group of 2～4 carbon atoms or the mixture of a plurality of oxyalkylene groups, R
3Represent hydrogen or alkyl group, phenyl group or the alkyl phenyl group of 1～12 carbonatoms are arranged, n is the average addition mole number of oxyalkylene group, it represents arbitrary number of 1～350, in multipolymer, monomer (a) can be that wherein a kind of independent use or two or more mixing are used;
R wherein
4Represent OM
2Perhaps O (R
5O)
mR
6, M wherein
1, M
2Represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine separately, R
5O represents to have the oxyalkylene group of 2～4 carbon atoms or the mixture of a plurality of oxyalkylene groups, R
6Represent hydrogen or alkyl group, phenyl group or the alkyl phenyl group of 1～12 carbonatoms are arranged, m is the average addition mole number of oxyalkylene group, and it represents arbitrary number of 1～350 ,-COOM
1With-COR
4Can form an anhydride group between the carbon atom that group connects respectively replaces-COOM
1With-COR
4Group.In multipolymer, monomer (b) can be that wherein a kind of independent use or two or more mixing are used.
2, cement dispersants according to claim 1 is characterized in that described other comonomer (c) comprising: thiazolinyl carboxylic acid or its salt; (methyl) acrylate; (methyl) vinyl cyanide; Unsaturated sulfonic acid or its salt; Unsaturated amides; Vinyl ester; The propenyl ester; Vinyl aromatic compounds.In multipolymer, comonomer (c) can be that wherein a kind of independent use or two or more mixing are used.
3, a kind of method for preparing the described poly-carboxylic-acid cement dispersant of claim 1 is characterized in that this method is to adopt redox system to make monomer component carry out polymerization in the aqueous solution as initiator under 25～70 ℃ of temperature.
4, according to the method described in the claim 3, it is characterized in that oxygenant in the redox system is a kind of or its mixture in the hydroperoxide, reductive agent is a kind of or its mixture in the sub-compound of sulphur.
5, method according to claim 4 is characterized in that described oxygenant consumption is 0.1%～20% of a total monomer weight, and the reductive agent consumption is 0.05～10% of a total monomer weight.
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| CN101906193A (en) * | 2010-08-06 | 2010-12-08 | 天津市飞龙砼外加剂有限公司 | Method for synthesizing polycarboxylic acid water reducing agent |
| CN101974135A (en) * | 2010-10-15 | 2011-02-16 | 北京工业大学 | Normal-temperature synthesis method for polycarboxylic acid water-reducing agent |
| CN102030496A (en) * | 2010-11-24 | 2011-04-27 | 上海三瑞高分子材料有限公司 | Polycarboxylic-acid copolymer dispersant and preparation method thereof |
| CN102146159A (en) * | 2010-11-24 | 2011-08-10 | 辽宁奥克化学股份有限公司 | Vinyl polyether and preparation method and application thereof |
| CN101570411B (en) * | 2009-05-31 | 2012-01-25 | 上海三瑞化学有限公司 | Polycarboxylic acid water reducing agent for gypsum and preparation method thereof |
| CN102477160A (en) * | 2010-11-23 | 2012-05-30 | 浙江老虎山建材有限公司 | Method for preparing dry high-performance water reducer powder of polycarboxylic acid |
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| CN101717220B (en) * | 2009-11-05 | 2012-10-03 | 上虞吉龙化学建材有限公司 | Polycarboxylic acid water-reducing agent and preparation method thereof |
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| CN101717220B (en) * | 2009-11-05 | 2012-10-03 | 上虞吉龙化学建材有限公司 | Polycarboxylic acid water-reducing agent and preparation method thereof |
| CN101906193A (en) * | 2010-08-06 | 2010-12-08 | 天津市飞龙砼外加剂有限公司 | Method for synthesizing polycarboxylic acid water reducing agent |
| CN101974135A (en) * | 2010-10-15 | 2011-02-16 | 北京工业大学 | Normal-temperature synthesis method for polycarboxylic acid water-reducing agent |
| CN102477160A (en) * | 2010-11-23 | 2012-05-30 | 浙江老虎山建材有限公司 | Method for preparing dry high-performance water reducer powder of polycarboxylic acid |
| CN102030496B (en) * | 2010-11-24 | 2013-01-09 | 上海三瑞高分子材料有限公司 | Polycarboxylic-acid copolymer dispersant and preparation method thereof |
| CN102030496A (en) * | 2010-11-24 | 2011-04-27 | 上海三瑞高分子材料有限公司 | Polycarboxylic-acid copolymer dispersant and preparation method thereof |
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| CN102504132A (en) * | 2011-09-30 | 2012-06-20 | 田国平 | Preparation method of polycarboxylate water reducing agent |
| CN103183791A (en) * | 2011-12-28 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Ternary random copolymer, its preparation method and application |
| CN103183791B (en) * | 2011-12-28 | 2015-11-25 | 辽宁奥克化学股份有限公司 | A kind of ternary atactic copolymer and its preparation method and application |
| CN103183818A (en) * | 2011-12-31 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Polyether and preparation method thereof |
| CN103183818B (en) * | 2011-12-31 | 2016-04-27 | 辽宁奥克化学股份有限公司 | A kind of polyethers and preparation method thereof |
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