CN102731008A - Concrete polycarboxylate superplasticizer and preparation method thereof - Google Patents
Concrete polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN102731008A CN102731008A CN2012102024213A CN201210202421A CN102731008A CN 102731008 A CN102731008 A CN 102731008A CN 2012102024213 A CN2012102024213 A CN 2012102024213A CN 201210202421 A CN201210202421 A CN 201210202421A CN 102731008 A CN102731008 A CN 102731008A
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Abstract
The present invention discloses a concrete polycarboxylate superplasticizer and a preparation method thereof. In the prior, the existing polycarboxylate superplasticizers have poor slump keeping performances, compounding of retarding components in the superplasticizer is a commonly used method for controlling concrete slump loss, and sometimes the long setting time can not meet the engineering construction requirements. The preparation method for the superplasticizer in the present invention comprises: adopting methylbutenol polyoxyethylene ether, an unsaturated carboxylic acid, an unsaturated sulfonate and a maleate as polymerization monomers, dissolving in deionized water, adding an aqueous solution of an initiator in a dropwise manner for 1.0-4.0 hours at a temperature of 60-80 DEG C, carrying out thermal insulation aging, cooling to the temperature of 40-50 DEG C, and adopting an alkali solution to carry out neutralization until the pH value is 5-7 to obtain the concrete polycarboxylate superplasticizer. According to the present invention, the maleate is introduced into the main chain of the polycarboxylate superplasticizer molecule, such that the concrete fluidity is improved significantly after a certain time due to hydrolysis of the ester bond so as to provide an excellent slump keeping effect.
Description
Technical field
The present invention relates to concrete admixture, specifically a kind of concrete polycarboxylate water-reducer and preparation method thereof.
Background technology
The research of China's polycarboxylate high performance water-reducing agent starts from the middle and later periods nineties 20th century, and suitability for industrialized production and application start from the early 21st century, and it applies process at present just with the quite unexpected speed fast development of people.Polycarboxylate high performance water-reducing agent had obtained fast-developing and had successfully applied at concrete works construction fields such as high-speed railway, bridge, port and pier, water conservancy and hydropower, public works because of its over-all properties advantage that has and the environmental protection characteristics of himself in recent years; And in engineerings such as self-compacting concrete, clear-water concrete, high-strength concrete, high durability concrete, maritime concrete, concrete prefabricated element, also begin to be applied, present " four vertical four horizontal strokes " railway personal rapid transit passage and three intercity personal rapid transit system engineerings are almost all used poly carboxylic acid series water reducer completely more than 1.2 ten thousand kilometers.Divert water from the south to the north project, great oceanographic engineering; Priority projects such as waterway between mountains engineering, Beijing Capital International Airport, Chinese Central Television (CCTV) Xin Tai location, Shanghai World Financial Center all are successfully to use the case of poly carboxylic acid series water reducer, also have a large amount of engineerings from now on and will use polycarboxylate high performance water-reducing agent.
Along with the raising of China's rapid economy development and building level, require increasingly high to concrete quality.But because the minimizing of quality sand and stone resources and the complicacy of concrete composition; In ready mixed concrete industry; The slump-loss problem of fresh concrete is the difficult problem of puzzlement engineering construction always; Particularly transportation can cause concrete slump loss excessive for a long time, influences concrete workability.Add water reducer before water reducer consumption or the construction and reinvent concrete and can make concrete recover serviceability preferably through increasing; But the consumption that strengthens water reducer at the stirring initial stage can cause concrete segregation, bleeding; Destroyed concrete homogeneity; Make the intensity of concrete each several part there are differences, reduced concrete bending and compressive strength.Through composite slow setting component in water reducer the method for the control concrete slump loss used always, but the long requirement that can not satisfy engineering construction time of coagulation sometimes.The retemper concrete not only can improve concrete wc before the construction, also can increase concrete air content, reduces concrete impermeability.Concrete in a word slump-loss has caused bigger influence to concrete serviceability and endurance quality, improves the concrete slump and keeps performance to become the major issue that ready mixed concrete industry faces.
Summary of the invention
An object of the present invention is to solve the existing relatively poor defective of polycarboxylate water-reducer slump retaining, provide a kind of slump retaining excellent polycarboxylate water-reducer.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is: a kind of concrete polycarboxylate water-reducer is characterized in that it is formed by A, B, C, four kinds of monomer copolymerizations of D; Wherein, monomer A is a methyl alkene butanols Soxylat A 25-7; Monomers B is acrylic or methacrylic acid; Monomer C is a unsaturated sulfonic acid salt; Monomer D is a maleic acid ester; The mol ratio of monomer A, B, C, D is 1:1 ~ 3:0.1 ~ 1:1 ~ 5.Described monomer is the existing compound that routinizes, can be through commercial acquisition.
The number-average molecular weight of said monomer A is 2200 ~ 2500 (account for monomer total mass 54.8 ~ 91.5%).
Described monomer D is preferably dimethyl maleate, ethyl maleate or diisobutyl maleate.
Another purpose of the present invention provides the preparation method of the excellent concrete polycarboxylate water-reducer of a kind of said slump retaining, and its production technique is simple, pollution-free.
The preparation method of said concrete polycarboxylate water-reducer is characterized in that, with each monomer with described mol ratio under the condition that initiator exists, copolymerization in water solution system; Temperature of reaction is 60 ~ 80 ℃, and the reaction times is 1 ~ 4h, is cooled to 40～50 ℃ behind the preserving heat after reaction ends 2.5-3.5h; Regulate pH=5 ~ 7 with liquid caustic soda; Promptly obtain described concrete polycarboxylate water-reducer, described initiator is a persulphate, and its concrete steps are following:
1) in reactor drum, adds monomer A, B, C, D and water, be heated with stirring to design temperature; Wherein the mass ratio of monomer A and water is 0.1 ~ 1:1;
2) aqueous solution of dropping initiator in the reaction system that step 1) obtains, the dropping time is 1 ~ 4h;
3) insulation 2.5-3.5h was cooled to 40～50 ℃ after dropwise reaction finished, and regulated pH=5 ~ 7 with liquid caustic soda, promptly got described concrete polycarboxylate water-reducer.
The described liquid caustic soda of step 3) is preferably the NaOH aqueous solution of mass concentration 30%, and described initiator is preferably a kind of in ammonium persulphate, Sodium Persulfate or the Potassium Persulphate, the quality of its adding be monomer A add quality 1 ~ 10%.
Compare with existing polycarboxylate water-reducer, the present invention has following beneficial effect:
1. polycarboxylate water-reducer of the present invention is owing to be incorporated into unsaturated polyester on the polycarboxylate water-reducer molecular backbone, because the hydrolytic action of its ester bond obviously improves concrete flowability after for some time (about general 1h), has the excellent guarantor effect of collapsing.
2. the preparation method of polycarboxylate water-reducer of the present invention is simple, pollution-free, and monomer conversion is high.
Below in conjunction with embodiment the present invention is described further.
Embodiment
Embodiment 1
In reactor drum, add 250g water and 170g methyl alkene butanols Soxylat A 25-7 (molecular weight is 2200), 11.1g vinylformic acid; 12.2g methylpropene sodium sulfonate, the 27.8g dimethyl maleate is heated with stirring to 70 ℃; Drip the solution of 3.4g ammonium persulphate and 40g deionized water then, maintain the temperature at 70 ℃, the dropping time is 2h; Digestion time is 3h; Reaction is cooled to 40～50 ℃ after finishing, and regulates pH=5 ~ 7 values to neutral with the NaOH aqueous solution of mass concentration 30%, promptly gets polycarboxylate water-reducer of the present invention.
Embodiment 2
In reactor drum, add 148g water and 170g methyl alkene butanols Soxylat A 25-7 (molecular weight is 2400), 5.1g vinylformic acid; 5.6g methylpropene sodium sulfonate, the 25.5g dimethyl maleate is heated with stirring to 60 ℃; Drip the solution of 8.5g ammonium persulphate and 40g deionized water then, maintain the temperature at 60 ℃, the dropping time is 2h; Digestion time is 3h; Reaction is cooled to 40～50 ℃ after finishing, and regulates pH=5 ~ 7 values to neutral with the NaOH aqueous solution of mass concentration 30%, promptly gets polycarboxylate water-reducer of the present invention.
Embodiment 3
In reactor drum, add 187g water and 170g methyl alkene butanols Soxylat A 25-7 (molecular weight is 2400), the 18.3g methylacrylic acid; 1.1g methylpropene sodium sulfonate, the 60.8g ethyl maleate is heated with stirring to 60 ℃; Drip the solution of 13.6g Sodium Persulfate and 40g deionized water then, maintain the temperature at 60 ℃, the dropping time is 3h; Digestion time is 3h; Reaction is cooled to 40～50 ℃ after finishing, and regulates pH=5 ~ 7 values to neutral with the NaOH aqueous solution of mass concentration 30%, promptly gets polycarboxylate water-reducer of the present invention.
Embodiment 4
In reactor drum, add 200g water and 170g methyl alkene butanols Soxylat A 25-7 (molecular weight is 2300), 16g vinylformic acid; The 7g methylpropene sodium sulfonate, the 12.7g ethyl maleate is heated with stirring to 80 ℃; Drip the solution of 10.2g Potassium Persulphate and 40g deionized water then, maintain the temperature at 80 ℃, the dropping time is 1h; Digestion time is 3h; Reaction is cooled to 40～50 ℃ after finishing, and regulates pH=5 ~ 7 values to neutral with the NaOH aqueous solution of mass concentration 30%, promptly gets a polycarboxylate water-reducer of the present invention.
Embodiment 5
In reactor drum, add 127g water and 170g methyl alkene butanols Soxylat A 25-7 (molecular weight is 2400), 11.7g vinylformic acid; 4.5g methylpropene sodium sulfonate, the 16.2g diisobutyl maleate is heated with stirring to 70 ℃; Drip the solution of 2.8g ammonium persulphate and 40g deionized water then, maintain the temperature at 60 ℃, the dropping time is 4h; Digestion time is 3h; Reaction is cooled to 40～50 ℃ after finishing, and regulates pH=5 ~ 7 values to neutral with the NaOH aqueous solution of mass concentration 30%, promptly gets a polycarboxylate water-reducer of the present invention.
Embodiment 6
In reactor drum, add 226g water and 170g methyl butene polyoxyethylenated alcohol (molecular weight is 2200), the 15.5g methylacrylic acid; 12.2g methylpropene sodium sulfonate, the 88.1g diisobutyl maleate is heated with stirring to 70 ℃; Drip the solution of 17g ammonium persulphate and 40g deionized water then, maintain the temperature at 60 ℃, the dropping time is 2h; Digestion time is 3h; Reaction is cooled to 40～50 ℃ after finishing, and regulates pH=5 ~ 7 values to neutral with the NaOH aqueous solution of mass concentration 30%, promptly gets a polycarboxylate water-reducer of the present invention.
Embodiment 7
In reactor drum, add 170g water and 170g methyl butene polyoxyethylenated alcohol (molecular weight is 2300), 10.6g vinylformic acid; 2.34g methylpropene sodium sulfonate, the 26.6g dimethyl maleate is heated with stirring to 70 ℃; Drip the solution of 3g ammonium persulphate and 40g deionized water then, maintain the temperature at 60 ℃, the dropping time is 2h; Digestion time is 3h; Reaction is cooled to 40～50 ℃ after finishing, and regulates pH=5 ~ 7 values to neutral with the NaOH aqueous solution of mass concentration 30%, promptly gets a polycarboxylate water-reducer of the present invention.
Product application is estimated
Measure the water reducer of (it is 10% that test specimens concentration is all diluted) embodiment of the invention 1-7 preparation under 1.8% volume and the clean slurry degree of mobilization of Comparative Examples; Experiment is operated according to GB/T8077-2000 " Methods for testing uniformity of concrete admixture "; Cement is used reference cement; Wc is 0.29, and measuring result is seen table 1:
Table 1
Annotate: Comparative Examples 1 is the coventional type polycarboxylate water-reducer 8101B that our company produces, and Comparative Examples 2 is external coventional type polycarboxylate water-reducers.
Claims (7)
1. a concrete polycarboxylate water-reducer is characterized in that, it is formed by A, B, C, four kinds of monomer copolymerizations of D; Wherein, monomer A is a methyl alkene butanols Soxylat A 25-7; Monomers B is acrylic or methacrylic acid; Monomer C is a unsaturated sulfonic acid salt; Monomer D is a maleic acid ester; The mol ratio of monomer A, B, C, D is 1:1 ~ 3:0.1 ~ 1:1 ~ 5.
2. concrete polycarboxylate water-reducer according to claim 1 is characterized in that, the number-average molecular weight of said monomer A is 2200 ~ 2500.
3. concrete polycarboxylate water-reducer according to claim 1 is characterized in that, described monomer D is dimethyl maleate, ethyl maleate or diisobutyl maleate.
4. the preparation method of each said concrete polycarboxylate water-reducer of claim 1-3 is characterized in that, with each monomer with described mol ratio under the condition that initiator exists, copolymerization in water solution system; Temperature of reaction is 60 ~ 80 ℃, and the reaction times is 1 ~ 4h, is cooled to 40～50 ℃ behind the preserving heat after reaction ends 2.5-3.5h, regulates pH=5 ~ 7 with liquid caustic soda, promptly obtains described concrete polycarboxylate water-reducer, and described initiator is a persulphate.
5. the preparation method of concrete polycarboxylate water-reducer according to claim 4, its concrete steps are following:
1) in reactor drum, adds monomer A, B, C, D and water, be heated with stirring to design temperature; Wherein the mass ratio of monomer A and water is 0.1 ~ 1:1;
2) aqueous solution of dropping initiator in the reaction system that step 1) obtains, the dropping time is 1 ~ 4h;
3) insulation 2.5-3.5h was cooled to 40～50 ℃ after dropwise reaction finished, and regulated pH=5 ~ 7 with liquid caustic soda, promptly got described concrete polycarboxylate water-reducer.
6. the preparation method of concrete polycarboxylate water-reducer according to claim 5, it is characterized in that: the described liquid caustic soda of step 3) is the NaOH aqueous solution of mass concentration 30%.
7. the preparation method of concrete polycarboxylate water-reducer according to claim 5 is characterized in that, described initiator is a kind of in ammonium persulphate, Sodium Persulfate or the Potassium Persulphate, the quality of its adding be monomer A add quality 1 ~ 10%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787608A (en) * | 2012-10-30 | 2014-05-14 | 辽宁奥克化学股份有限公司 | Polycarboxylic acid water reducer used for high mud concrete and synthetic method |
| CN106400780A (en) * | 2016-08-31 | 2017-02-15 | 华北水利水电大学 | Pressure-reduction and shock-resistant sheet-pile wall structure |
| CN109535343A (en) * | 2018-11-27 | 2019-03-29 | 四川奥克石达化学股份有限公司 | A kind of diester-type polycarboxylate water-reducer and preparation method thereof |
Citations (1)
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| CN101205127A (en) * | 2007-11-21 | 2008-06-25 | 厦门市建筑科学研究院集团股份有限公司 | Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101205127A (en) * | 2007-11-21 | 2008-06-25 | 厦门市建筑科学研究院集团股份有限公司 | Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same |
Non-Patent Citations (1)
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| 邱杰: "聚羧酸高效减水剂的合成及性能研究", 《福建建筑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787608A (en) * | 2012-10-30 | 2014-05-14 | 辽宁奥克化学股份有限公司 | Polycarboxylic acid water reducer used for high mud concrete and synthetic method |
| CN103787608B (en) * | 2012-10-30 | 2016-01-20 | 辽宁奥克化学股份有限公司 | A kind of high containing cement concrete polycarboxylate water-reducer and synthetic method thereof |
| CN106400780A (en) * | 2016-08-31 | 2017-02-15 | 华北水利水电大学 | Pressure-reduction and shock-resistant sheet-pile wall structure |
| CN109535343A (en) * | 2018-11-27 | 2019-03-29 | 四川奥克石达化学股份有限公司 | A kind of diester-type polycarboxylate water-reducer and preparation method thereof |
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Application publication date: 20121017 |