CN102924669A - Preparation method of polycarboxylate superplasticizer - Google Patents
Preparation method of polycarboxylate superplasticizer Download PDFInfo
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- CN102924669A CN102924669A CN2011102287464A CN201110228746A CN102924669A CN 102924669 A CN102924669 A CN 102924669A CN 2011102287464 A CN2011102287464 A CN 2011102287464A CN 201110228746 A CN201110228746 A CN 201110228746A CN 102924669 A CN102924669 A CN 102924669A
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Abstract
The invention discloses a preparation method of a polycarboxylate superplasticizer, and belongs to the building material field. The method comprises the following steps: copolymerizing unsaturated polyoxyalkyl ether (A), unsaturated monocarboxylic acid and its derivative (B), unsaturated dicarboxylic acid and its derivative (C) and unsaturated sulfonate (D) in an aqueous solution under the initiation of an initiator at 60-90DEG C for 2.5-5h; maintaining the temperature for 1-3h; cooling to 40-45DEG C; and adding an aqueous sodium hydroxide solution having a concentration of 30% to adjust the pH value to 6.0-8.0 to prepare the polycarboxylate superplasticizer. The method has the characteristics of no use of nitrogen protection, no use of deionized water, one-step synthesis, solving of problems comprising fast concrete fluidity loss and large concrete slump loss, simplicity, less equipment investment, easily-controlled reaction condition, high water reducing rate, good cost performance, safety, and environmental protection.
Description
Technical field
The present invention relates to a kind of cement dispersants, relate in particular to a kind of polycarboxylic acid super-plasticizer and preparation method thereof.
Background technology
Now, oneself is widely used in the concrete technology field high-efficiency water-reducing agent of poly-carboxylic acid, and its distinguishing feature just is to improve the workability of concrete mix.Admixture a small amount of (cement quality 1%) high efficiency water reducing agent in concrete is on the one hand because its special flowability can prepare self-compacting concrete; On the other hand because its extremely low water-cement ratio can prepare high-performance even ultra-high performance concrete.High efficiency water reducing agent has been applied to high-speed railway at present as the additive of concrete mix, bridge spanning the sea, and skyscraper etc. need high-intensity concrete structure engineering.
This concept of high efficiency water reducing agent be in invention with naphthalenesulfonate formaldehyde condensation compound, melamine sulfonate and formaldehyde condenses puts forward first for the water reducer of representative, this is because their water-reducing property significantly is higher than ligno-sulfate based plasticizer.Naphthalene system, the research of the efficient water reducers such as sweet ammonia system starts from nineteen sixties, and the research of various countries has been gradually improved at present with using, and corresponding structure and property development change little; In the 1980s, Nippon Shokubai etc. has invented the high-efficiency water-reducing agent of poly-carboxylic acid that contains the PEO side chain, its dispersive ability is far above other water reducers such as naphthalene systems, because the water-reducing rate of high-efficiency water-reducing agent of poly-carboxylic acid is more much higher than naphthalene water reducer, and mobile retention is good, little loss of slump is particularly useful for making precast concrete.
The preparation method of high-efficiency water-reducing agent of poly-carboxylic acid can be divided into two classes substantially: a class is take maleic anhydride as the different polyoxyethylene groups of main chain grafting (EO) or polyoxypropylene base (PO) side chain; Another kind of is take methacrylic acid (vinylformic acid) as main chain grafting EO or the PO side chain.These macromonomers are introduced the carboxyl with negative charge at organic solvent system or water solution system, sulfonic group and water is had the polymer lateral chain of good affinity interaction, polymerization under the initiator initiation is through the final product that obtains desired properties of neutralization.
Japan is research and the maximum country of application high-efficiency water-reducing agent of poly-carboxylic acid, and oneself has turned to high-efficiency water-reducing agent of poly-carboxylic acid basically from naphthalene system the research of high efficiency water reducing agent.Patent [JP 9012642] has reported that in solvent system the multipolymer to maleic anhydride and petroleum naphtha carries out modification and makes the high-performance high efficiency water reducing agent.The development of U.S.'s high efficiency water reducing agent is compared Japan a little later, and patent [US 5158996] has reported that also modification obtains well behaved high-efficiency water-reducing agent of poly-carboxylic acid to montmorillonite in solvent system.Current, the water reducer research centre content of various countries is gradually from the modification of sulfonic acid series high-efficiency water-reducing agent to the polycarboxylic acid series high efficiency water reducing agent transition.
With methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic, vinylformic acid, the monomer copolymerization of different oxyethylene group chain lengths have prepared polycarboxylic acid series high efficiency water reducing agent at Li Chongzhi of China Tsing-Hua University etc., and water-reducing rate reaches 25%.Wang Youkui etc. are take ammonium persulphate as initiator, and the synthetic high-efficiency water-reducing agent of poly-carboxylic acid of aqueous solution copolymerization that drips simultaneously mix monomer and chain-transfer agent can make almost free of losses in the slump 1h of fresh concrete.Ma Baoguo etc. with the large monomer of homemade maleic anhydride polyoxyethylene glycol and methacrylic acid copolymerization high-efficiency water-reducing agent of poly-carboxylic acid, its can make cement paste initial flow degree higher and through the time fluidity loss little.
At present, use maximum still naphthalene series high-efficiency water-reducing agents on China's engineering, the product application degree of other kind is relatively less.Because environmental protection, the needs of economy and engineering, concrete is towards high-performance, multifunction, International standardization future development, the in addition defective of naphthalene water reducer, not high such as flowability, degree of mobilization is fast through time loss, and slump-loss is large etc., research and development, promoting the use of the more excellent high-efficiency water-reducing agent of poly-carboxylic acid of performance becomes a kind of trend.
Summary of the invention
For above-mentioned situation, the object of the invention is to, providing a kind of has than high water reducing rate under low-dosage, novel high-efficiency water-reducing agent of poly-carboxylic acid and a kind of technique good to concrete raw material adaptability are simple, easy and simple to handle, more in applying environmental friendliness, the preparation method of this high efficiency water reducing agent that cost performance is high.
Fast for solving fluidity loss, the technical problem that slump-loss is large, the technical scheme of technical solution problem of the present invention is:
A kind of preparation method of polycarboxylic acid super-plasticizer, it is characterized in that, 1), each reaction raw materials of this superplasticizer by weight percentage: unsaturated polyester oxyalkyl ether (A) accounts for 45-95%, unsaturated monocarboxylic acid and derivative thereof (B) account for 0-20%, unsaturated dicarboxylic acid and derivative thereof (C) account for 0-30%, and unsaturated sulfonic acid and salt thereof (D) account for 0-10%;
2), the said components mixed raw material got mixed monomer solution after, add initiator, the add-on of initiator accounts for 0.5～10% of used monomer weight, by copolyreaction, makes polycarboxylic acid super-plasticizer;
3), the preparation of polycarboxylic acid super-plasticizer comprises the steps: certain water gaging is dropped in the reaction flask, be warmed up to 60-90 ℃, dropping contains unsaturated polyester oxyalkyl ether (A) and unsaturated monocarboxylic acid and derivative (B) thereof, unsaturated dicarboxylic acid and derivative thereof (C), the aqueous solution of unsaturated sulfonic acid and salt thereof (D) and metering initiator, time for adding is 2.5-5h, after dripping end, enter subsequently the insulation of 1-3h, insulating process is down to 40-45 ℃ to temperature after finishing, and adding concentration is 30% aqueous sodium hydroxide solution, adjust the pH value to 6.0-8.0, obtain the polycarboxylic acid super-plasticizer that disperses as cement.
This polycarboxylic acid super-plasticizer is that reaction raw materials copolymerization in the aqueous solution forms by following monomer under the effect of initiator.
Described unsaturated polyester oxyalkyl ether (A) is expressed by the following formula
In the formula, m represents arbitrary integer between 9-120, R=CH
3H
In multipolymer, monomer (A) is the mixture combination of the one or two or more in the compound that is represented by general formula.
Described unsaturated monocarboxylic acid and derivatives monomer thereof (B) are the mixture combinations of wherein one or two or more; Preferred vinylformic acid, methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamide, methacrylic acid, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, the mixture of one or more in the methyl acrylamide monomer.Described unsaturated dicarboxylic acid and derivatives monomer thereof (C) are the mixture combinations of wherein one or two or more; Preferred fumaric acid, methylene-succinic acid, toxilic acid, fumaric acid anhydride, one or more mixtures in the maleic anhydride monomer.
Described unsaturated sulfonic acid salt monomer (D) is the mixture combination of wherein one or two or more; Preferred allylsulfonate, methallyl sulfonate, 2-vinylformic acid amido-2-methyl propane sulfonic acid salt, the mixture of one or more in the p styrene sulfonic acid salt.
Described initiator is persulfuric acid salt initiator, comprising: Potassium Persulphate, ammonium persulphate, any one or two kinds of or multiple mixture in the Sodium Persulfate; The consumption of described persulphate accounts for the 0.5-10% of used total monomer weight, and persulphate is mixed with the aqueous solution that mass percent concentration is 1-20%.
In the preparation of this superplasticizer, the mixture aqueous solution of one or two or more monomer is disposable to feed intake, and all the other at least a monomers add continuously.
Beneficial effect of the present invention:
According to the high-efficiency water-reducing agent of poly-carboxylic acid of the inventive method preparation, cost is low, and water-reducing rate is high, slump-loss is low, workability is good, and is good with cement adaptability, adopts one-step synthesis, technical process is simple, need not lead to nitrogen, without deionized water, easy and simple to handle, product performance are constant, are easy to suitability for industrialized production.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1
Disposing agitator, thermometer, Dropping feeder, add 60g water in the vial of reflux exchanger, 117.6g maleic anhydride, dissolving, stirring is warming up to 85 ℃, with 300g allyl polyethenoxy ether (m=23), 7.9g sodium p styrene sulfonate and 21.3g acrylamide are dissolved in the 400g water and are mixed with mixed monomer solution, the 17.8g ammonium persulphate are dissolved in the initiator solution that is mixed with 8% concentration in the 200g tap water, drip monomer solution and initiator solution at 85 ℃ to above-mentioned vial internal control speed, 3h drips off, 85 ℃ of lower isothermal reactions 1.5 hours, reaction is cooled to 45 ℃ after finishing, and adding the 256g30% sodium hydroxide solution, to regulate pH be 7.0, obtain high-efficiency water-reducing agent of poly-carboxylic acid product P C-1, its solid content is 40%.
Embodiment 2
Disposing agitator, thermometer, Dropping feeder, add 120g water in the vial of reflux exchanger, 51.1g maleic anhydride, dissolving, stirring is warming up to 75 ℃, with 150g allyl polyethenoxy ether (m=23) and 180g allyl polyethenoxy ether (m=46), 7.94 ethyl propenoate and 15.97g acrylamide are dissolved in the 330g water and are mixed with mixed monomer solution, the 16.2g ammonium persulphate are dissolved in the initiator solution that is mixed with 9.4% concentration in the 157g tap water, drip monomer solution and initiator solution at 75 ℃ to above-mentioned vial internal control speed, 3h drips off, 75 ℃ of lower isothermal reactions 1.5 hours, reaction is cooled to 45 ℃ after finishing, and adding the 118.2g30% sodium hydroxide solution, to regulate pH be 7.0, obtain high-efficiency water-reducing agent of poly-carboxylic acid product P C-2, its solid content is 40%.
Embodiment 3
Disposing agitator, thermometer, Dropping feeder, add 300g water in the vial of reflux exchanger, 300g allyl polyethenoxy ether (n=23), dissolving, stirring is warming up to 70 ℃, with 43.2g vinylformic acid, 4.74g sodium methallyl sulfonate and 21.3g acrylamide are dissolved in the 180g water and are mixed with mixed monomer solution, the 7.9g ammonium persulphate are dissolved in the initiator solution that is mixed with 9.8% concentration in the 73g tap water, drip monomer solution and initiator solution at 70 ℃ to above-mentioned vial internal control speed, 3h drips off, 70 ℃ of lower isothermal reactions 1.5 hours, reaction is cooled to 45 ℃ after finishing, and adding the 72g30% sodium hydroxide solution, to regulate pH be 7.0, obtain high-efficiency water-reducing agent of poly-carboxylic acid product P C-3, its solid content is 40%.
Contrast and experiment of the present invention is as follows:
Clean slurry test
Adopt reference cement, clean slurry degree of mobilization according to GB/T8077-2000 " Methods for testing uniformity of concrete admixture " test cement, water cement ratio is 0.29, and the volume of polycarboxylic acid super-plasticizer is 1%, and the flowing degree of net paste of cement comparative test result of doing according to top 3 embodiment sees Table:
Concrete test
Mix this polycarboxylate water-reducer PC that solid masses accounts for concrete gel material weight 0.4%, concrete water-reducing ratio can reach more than 35%.
Adopt cement: flyash: sand: stone=1: 0.1: 1.28: 2.48 concrete mix preparation C60 concrete, mix this polycarboxylic acid super-plasticizer PC-2 that solid masses accounts for concrete gel material weight 0.44%, can make the concrete slump of above-mentioned proportioning reach 220mm, the slump divergence reaches 600mm, the concrete slump and the rate of loss of slump divergence behind 2h are lower than 10%, concrete surface is without the bleeding line, workability is good, ultimate compression strength reached 81MPa in 28 days, and is strong to dissimilar cement adaptability.
The present invention is not limited to above-described embodiment, can select above-mentioned different proportioning or above-described embodiment different proportionings in addition according to the different occasions of using, but all not limit the scope of the invention in any form.
Claims (7)
1. the preparation method of a polycarboxylic acid super-plasticizer is characterized in that:
1), each reaction raw materials of this superplasticizer by weight percentage: unsaturated polyester oxyalkyl ether (A) accounts for 45-95%, unsaturated monocarboxylic acid and derivative thereof (B) account for 0-20%, unsaturated dicarboxylic acid and derivative thereof (C) account for 0-30%, and unsaturated sulfonic acid and salt thereof (D) account for 0-10%;
2), the said components mixed raw material got mixed monomer solution after, add initiator, the add-on of initiator accounts for 0.5～10% of used monomer weight, by copolyreaction, makes polycarboxylic acid super-plasticizer;
3), the preparation of polycarboxylic acid super-plasticizer comprises the steps: certain water gaging is dropped in the reaction flask, be warmed up to 60-90 ℃, dropping contains unsaturated polyester oxyalkyl ether (A) and unsaturated monocarboxylic acid and derivative (B) thereof, unsaturated dicarboxylic acid and derivative thereof (C), the aqueous solution of unsaturated sulfonic acid and salt thereof (D) and metering initiator, time for adding is 2.5-5h, after dripping end, enter subsequently the insulation of 1-3h, insulating process is down to 40-45 ℃ to temperature after finishing, and adding concentration is 30% aqueous sodium hydroxide solution, adjust the pH value to 6.0-8.0, obtain the polycarboxylic acid super-plasticizer that disperses as cement.
2. a kind of preparation method of polycarboxylic acid super-plasticizer as claimed in claim 1, it is characterized in that: described unsaturated polyester oxyalkyl ether (A) is by following general formula 1 expression
In the formula, m represents arbitrary integer between 9-120, R=CH
3H
In multipolymer, monomer (A) is the mixture combination by the one or two or more in the compound of general formula 1 expression.
3. the preparation method of polycarboxylic acid super-plasticizer as claimed in claim 1 is characterized in that: unsaturated monocarboxylic acid and derivative thereof (B) are the mixture combinations of wherein one or two or more; Preferred vinylformic acid, methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamide, methacrylic acid, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, the mixture of one or more in the methyl acrylamide monomer.
4. the preparation method of polycarboxylic acid super-plasticizer as claimed in claim 1 is characterized in that: unsaturated dicarboxylic acid and derivative thereof (C) are the mixture combinations of wherein one or two or more; Preferred fumaric acid, methylene-succinic acid, toxilic acid, fumaric acid anhydride, one or more mixtures in the maleic anhydride monomer.
5. the preparation method of polycarboxylic acid super-plasticizer as claimed in claim 1 is characterized in that: unsaturated sulfonic acid salt monomer (D) is the mixture combination of wherein one or two or more; Preferred allylsulfonate, methallyl sulfonate, 2-vinylformic acid amido-2-methyl propane sulfonic acid salt, the mixture of one or more in the p styrene sulfonic acid salt.
6. a kind of preparation method of polycarboxylic acid super-plasticizer as claimed in claim 1 is characterized in that, described initiator is persulfuric acid salt initiator, comprising: Potassium Persulphate, ammonium persulphate, any one or two kinds of or multiple mixture in the Sodium Persulfate; The consumption of described persulphate accounts for the 0.5-10% of used total monomer weight, and persulphate is mixed with the aqueous solution that mass percent concentration is 1-20%.
7. a kind of preparation method of polycarboxylic acid super-plasticizer as claimed in claim 1, it is characterized in that: the mixture aqueous solution of one or two or more monomer is disposable to feed intake, and all the other at least a monomers add continuously.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253886A (en) * | 2013-04-12 | 2013-08-21 | 奥克化学扬州有限公司 | Polycarboxylate superplasticizer synergist and preparation method thereof |
| CN103613307A (en) * | 2013-11-22 | 2014-03-05 | 武汉理工大学 | Slump type polycarboxylate superplasticizer and preparation method thereof |
| CN103613308A (en) * | 2013-11-22 | 2014-03-05 | 武汉理工大学 | Water-reducing polycarboxylic concrete slump retaining agent and preparation method thereof |
| CN108164173A (en) * | 2017-12-11 | 2018-06-15 | 湖北麦斯合普新材料股份有限公司 | A kind of concrete slump retaining agent and preparation method thereof |
| CN109336504A (en) * | 2018-10-30 | 2019-02-15 | 蚌埠市方阵商品混凝土有限公司 | A kind of high intensity anti-crack concrete |
| CN109422504A (en) * | 2017-08-31 | 2019-03-05 | 临安鼎昇建材有限公司 | A kind of quasi- self-compacting concrete of premixing and its production method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538134A (en) * | 2009-04-14 | 2009-09-23 | 大连市建筑科学研究设计院股份有限公司 | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538134A (en) * | 2009-04-14 | 2009-09-23 | 大连市建筑科学研究设计院股份有限公司 | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253886A (en) * | 2013-04-12 | 2013-08-21 | 奥克化学扬州有限公司 | Polycarboxylate superplasticizer synergist and preparation method thereof |
| CN103613307A (en) * | 2013-11-22 | 2014-03-05 | 武汉理工大学 | Slump type polycarboxylate superplasticizer and preparation method thereof |
| CN103613308A (en) * | 2013-11-22 | 2014-03-05 | 武汉理工大学 | Water-reducing polycarboxylic concrete slump retaining agent and preparation method thereof |
| CN103613308B (en) * | 2013-11-22 | 2015-04-08 | 武汉理工大学 | Water-reducing polycarboxylic concrete slump retaining agent and preparation method thereof |
| CN109422504A (en) * | 2017-08-31 | 2019-03-05 | 临安鼎昇建材有限公司 | A kind of quasi- self-compacting concrete of premixing and its production method |
| CN108164173A (en) * | 2017-12-11 | 2018-06-15 | 湖北麦斯合普新材料股份有限公司 | A kind of concrete slump retaining agent and preparation method thereof |
| CN109336504A (en) * | 2018-10-30 | 2019-02-15 | 蚌埠市方阵商品混凝土有限公司 | A kind of high intensity anti-crack concrete |
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Application publication date: 20130213 |