CN100519464C - Method for preparing metal-free ion type polycarboxylic acid series high efficiency water reducing agent - Google Patents
Method for preparing metal-free ion type polycarboxylic acid series high efficiency water reducing agent Download PDFInfo
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- CN100519464C CN100519464C CNB2007100458630A CN200710045863A CN100519464C CN 100519464 C CN100519464 C CN 100519464C CN B2007100458630 A CNB2007100458630 A CN B2007100458630A CN 200710045863 A CN200710045863 A CN 200710045863A CN 100519464 C CN100519464 C CN 100519464C
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- reducing agent
- acid
- water reducing
- high efficiency
- efficiency water
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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
Abstract
The invention pertains to the preparation method field of polycarboxylic acid type high efficiency water reducing agent. The steps of the preparation method of non- metal ions polycarboxylic acid type high efficiency water reducing agent provided by the invention are that: a. liquid acidic catalyst and inhibitor are added in polyethylene glycol methyl ether, methacrylic acid or acrylic acid to do esterification and poly(ethyleneglycol monoethylether) methacrylate or acrylic acid polyethylene glycol monomethyl ether is obtained; b. the catalyst is removed by adding organic or inorganic weak base-olyte; c. under the effect of free radical initiator, compound obtained in step b is grafted and polymerized with other needed comonomer unsaturated acid or unsaturated esters to form binary copolymer and terpolymer; d. the pH value is adjusted to 7.5-8.5 by organic or inorganic weak base-olyte. The invention adopts the novel method, banishes a plurality of traditional additives to reduce the electric conductivity of the water reducing agent, thereby increasing the withstanding voltage of electric porcelain high insulation product to 80kv and the storage period of product to half year or two years after the product is added to concrete.
Description
Technical field
The present invention relates to a kind of concrete admixture, i.e. preparation method's technical field of polycarboxylic acid series high efficiency water reducing agent.
Background technology
Polycarboxylate high performance water-reducing agent because his superperformance, promptly be subjected to the extensive concern of building, water conservancy, bridge fine strain of millet, railway, civil engineering work industry after its comes out, and beginning is being applied in a lot of major projects.This has also further promoted domestic and international scientific research institution and manufacturing enterprise competitively Development and Production and application service, but remains in some problems with regard to the polycarboxylic acid series high efficiency water reducing agent of present production, has influenced the production and the application of polycarboxylic acid series high efficiency water reducing agent.
The common preparation technology of polycarboxylic acid series high efficiency water reducing agent is with polyethylene glycol monomethyl ether (MPEG) and methacrylic acid (MAA) or vinylformic acid (AA), at catalyzer, carry out esterification under the stopper existence condition, make Methylacrylic acid polyethylene glycol single armor ether ester (MAMPEG) or polyalkylene glycol acrylate monomethyl ether ester, and then with this type of carboxylate (MAMPEG) under action of free radical initiator, carry out graft copolymerization with other comonomer unsaturated acid and unsaturated acid ester, form binary, terpolymer, separate matter with the highly basic of metal ion again and carry out neutralizing treatment, adjusting PH is that meta-alkalescence makes polycarboxylic acid series high efficiency water reducing agent.This preparation technology has had a large amount of reports and has been the main synthesis and preparation process of the polycarboxylic acid series high efficiency water reducing agent of present domestic production.
But the processing method that this kind prepares still exists some problems.At first be after esterification finishes, the storage period of carboxylate Methylacrylic acid polyethylene glycol single armor ether ester (MAMPEG) is short, utilizes this carboxylate (MAMPEG) to transport to the scene, strange land and produces and be restricted.It two is, has a large amount of metal ions in the finished product polycarboxylic acid series high efficiency water reducing agent, as sodium ion or potassium ion etc., is unfavorable for that product the applying of High-Voltage Insulation electroceramics industry, influences the expansion of range of application.
Summary of the invention
Purpose of the present invention provides a kind of storage period long exactly for addressing the above problem, and can be applied to the preparation method of the polycarboxylic acid series high efficiency water reducing agent of High-Voltage Insulation electroceramics industry.
The present inventor finds through experimental study, existing high efficiency water reducing agent is shorter storage period, generally has only 3 months time, its major cause is to rock owing to reaching fierce transportation under the condition that exists at catalyzer, and carboxylate methyl-prop diluted acid poly glycol monomethyl ether ester (MAMPEG) can inferior polymeric phenomenons such as generation skinning, thickening and gelationization.Therefore seek a kind of new preparation technology, remaining catalyzer removal in the MAMPEG then can be addressed this problem.
The technical scheme that the present invention takes is as follows:
A kind of preparation method of metal-free ion type polycarboxylic acid series high efficiency water reducing agent the steps include:
A, in polyethylene glycol monomethyl ether (MPEG), methacrylic acid (MAA) or vinylformic acid (AA), add liquid an acidic catalyst and stopper carries out esterification, make Methylacrylic acid polyethylene glycol single armor ether ester (MAMPEG) or polyalkylene glycol acrylate monomethyl ether ester;
B, in Methylacrylic acid polyethylene glycol single armor ether ester that step a makes or polyalkylene glycol acrylate monomethyl ether ester, add organic or inorganic weak base and separate matter, remove catalyzer;
C, under action of free radical initiator, carry out graft copolymerization with removing the Methylacrylic acid polyethylene glycol single armor ether ester of catalyzer or polyalkylene glycol acrylate monomethyl ether ester and required other comonomer unsaturated acid or unsaturated acid ester, form binary, terpolymer;
D, use organic or inorganic weak base are separated matter and are adjusted pH to 7.5～8.5.
Among the above-mentioned step a, said liquid an acidic catalyst can be the vitriol oil (refer to concentration be 98% or above sulfuric acid), oleum, tosic acid, benzene sulfonyl chloride, Witco 1298 Soft Acid etc.
Among the above-mentioned step b, it can be NH that said organic or inorganic weak base is separated matter
3, NH
4(OH), NH
4HCO
3, (NH
4)
2SO
3H
2O, MEA (thanomin), C
4H
11NO
2(diethanolamine) etc.Adopt the reinforced down mode of liquid during processing, prevent that intense reaction from dashing material, the usage quantity that organic or inorganic weak base is separated matter is 1～1.5 times of catalyzer molar weight.
In the above-mentioned steps d, it can be NH that said organic or inorganic weak base is separated matter
3, NH
4(OH), NH
4HCO
3, (NH
4)
2SO
3H
2O, MEA (thanomin), C
4H
11NO
2(diethanolamine) etc.
Beneficial effect of the present invention:
The present invention is in reaction process, and some auxiliary agents of abandoning tradition adopt the different methods step, have solved two deficiencies of prior art:
A, reduced the content of metal ion in the water reducer, the electric conductivity of water reducer itself is descended.After product is adding concrete, can also make the proof voltage of the high insulating products of electroceramics be increased to 80,000 volts by 30,000 volts.
B, removed unnecessary catalyzer, make product keep stable, and performance has not descended.Extended to 9 month even one year by 3 months the storage period of the carboxylate that makes (MAMPEG).The finished product were increased to 2 years storage period.
Embodiment
One, the preparation of carboxylate
Example 1
Have in the glass reactor of agitator, thermometer, dropping funnel, reflux condensation mode apparatus at 250cc, add poly glycol monomethyl ether (MPEG) 75g, methacrylic acid (MAA) 25g, vitriol oil 0.75g, composite polymerization inhibitor TY (Shanghai Gujia Chemical Technology Co., Ltd.) 0.06g, heat temperature raising, make the reaction mass dissolving, start stirring heating and be warming up to 110～140 ℃, adopt direct melting esterification process rare gas element, get rid of the water that reaction generates, insulation reaction 5 hours.After 70 ℃ of reaction mass coolings, slowly add 35% ammonia soln, add-on is sulfuric acid: ammoniacal liquor=1:1～1.3 (mol ratios), is cooled to room temperature then, gets carboxylate Methylacrylic acid polyethylene glycol single armor ether ester (MAMPEG).
Example 2
Have in the glass reactor of agitator, thermometer, dropping funnel, reflux condensation mode apparatus at 250cc, add poly glycol monomethyl ether (MPEG) 75g, methacrylic acid (MAA) 25g, vitriol oil 0.75g, composite polymerization inhibitor TY (Shanghai Gujia Chemical Technology Co., Ltd.) 0.06g, heat temperature raising, make the reaction mass dissolving, start stirring heating and be warming up to 110～140 ℃, adopt direct melting esterification process, get rid of the water that reaction generates with rare gas element, insulation reaction 5 hours, after reaction mass is cooled to 70 ℃, slowly add 40%, NH
4HCO
4Solution, add-on are sulfuric acid: bicarbonate of ammonia=1:1～1.5, are cooled to room temperature then, get carboxylate Methylacrylic acid polyethylene glycol single armor ether ester (MAMPEG).
Two, the polymerization of polycarboxylic acid series high efficiency water reducing agent GJ-D80
Example 3
Have agitator at 500cc, thermometer, dropping funnel, in the glass reactor of reflux exchanger, add the 200cc deionized water, start stirring, temperature is risen to 75～85 ℃, drip Methylacrylic acid polyethylene glycol single armor ether ester (MAMPEG) 200g simultaneously through diluting, ammonium persulfate solution 80g, (3.7% concentration) initiator, control 3～3.5 hours respectively, continued insulation reaction 1～1.5 hour, be cooled to 50 ℃ then, the ammonia soln of slow Dropwise 35 %, to the PH to 7.5 that makes reaction mass～8.5, be cooled to room temperature, get the polycarboxylic acid series high efficiency water reducing agent GJ-D80 of metal-free ion type.
Example 4
Have stirring at 500cc, thermometer, dropping funnel, in the glass reactor of reflux exchanger, add the 200cc deionized water, start stirring, temperature is risen to 75～85 ℃, drip Methylacrylic acid polyethylene glycol single armor ether ester (MAMPEG) 200g simultaneously through diluting, ammonium persulfate solution 80g, (3.7% concentration) initiator, control 3～3.5 hours respectively, continue insulation reaction 1～1.5 hour, and be cooled to 50 ℃ then, slowly drip PH to 7.5～8.5 that ethanolamine solutions makes reaction mass, be cooled to room temperature, get the polycarboxylic acid series high efficiency water reducing agent GJ-D80 of metal-free ion type.
Three, test data
1, starch degree of mobilization and only, see the following form 1 through time loss:
Table 1
Sample 1 closes the high efficiency water reducing agent ATR-2 that first chemical industry equipment Manufacturing Co., Ltd produces for Shanghai, sample 2 is the high efficiency water reducing agent KS-JS that Sichuan Ke Shuai admixture company limited produces, sample 3 is the high efficiency water reducing agent GJ-D80 (the little batch sample that produce in June, 2005 does not have inferior polymeric phenomenons such as skinning, thickening to testDate) of the inventive method preparation.Test cement p42.5R (fresh 7 days), testDate is in August, 2007.
2, the concrete crushing strength test data sees Table 2:
Table 2
Test is cement mill, Wujiang, a Zhejiang p42.5 cement with cement, sample 1 closes the high efficiency water reducing agent ATR-2 that first chemical industry equipment Manufacturing Co., Ltd produces (the product G J-80 that promptly solid good chemical company produces with traditional method, the predecessor who consolidates good chemical science and technology company because of Shanghai closes first chemical industry equipment Manufacturing Co., Ltd for Shanghai) for Shanghai.TestDate is in August, 2007.
3, certain high tension insulator insulated column Manufacturing Co., Ltd tries out the high efficiency water reducing agent GJ-D80 of method of the present invention preparation at the fixing immovable bed of high tension insulator insulated column and overcoat, and proof voltage is tested by general 30,000 volts and brought up to 80,000 volts.
Claims (2)
1, a kind of preparation method of metal-free ion type polycarboxylic acid series high efficiency water reducing agent the steps include:
A, in polyethylene glycol monomethyl ether, methacrylic acid or vinylformic acid, add liquid an acidic catalyst and stopper carries out esterification, make Methylacrylic acid polyethylene glycol single armor ether ester or polyalkylene glycol acrylate monomethyl ether ester, said liquid an acidic catalyst is meant the vitriol oil, oleum, tosic acid, benzene sulfonyl chloride or Witco 1298 Soft Acid;
B, add organic or inorganic weak base separate matter in Methylacrylic acid polyethylene glycol single armor ether ester that step a makes or polyalkylene glycol acrylate monomethyl ether ester, remove catalyzer, said organic or inorganic weak base is separated matter and is meant NH
3, NH
4(OH), NH
4HCO
3, (NH
4)
2SO
3H
2O, thanomin or diethanolamine;
C, under action of free radical initiator, carry out graft copolymerization with removing the Methylacrylic acid polyethylene glycol single armor ether ester of catalyzer or polyalkylene glycol acrylate monomethyl ether ester and required other comonomer unsaturated acid or unsaturated acid ester, form binary, terpolymer;
D, use organic or inorganic weak base are separated matter and are adjusted pH to 7.5～8.5.
2, the preparation method of metal-free ion type polycarboxylic acid series high efficiency water reducing agent as claimed in claim 1 is characterized in that: step b is adding organic or inorganic weak bases adopts mode reinforced under the liquid when separating matter, and usage quantity is 1～1.5 times of catalyzer molar weight.
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| CN100519464C true CN100519464C (en) | 2009-07-29 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293946B (en) * | 2008-06-20 | 2010-06-02 | 武汉理工大学 | Method for preparing bleed air controllable polycarboxylic acids water reducing agents |
| CN102093553B (en) * | 2010-12-02 | 2012-08-29 | 中国海洋石油总公司 | Method for synthesizing polycarboxylate series water-reducing agent macromonomer |
| CN105348508B (en) * | 2015-10-14 | 2017-10-31 | 广东红墙新材料股份有限公司 | A kind of surface-active macromonomer, its preparation method and application |
| CN106893048B (en) * | 2017-04-10 | 2019-04-02 | 上海台界化工有限公司 | A kind of preparation method of polycarboxylic acids dehydragent |
| CN107474196B (en) * | 2017-09-16 | 2020-02-21 | 四川砼道科技有限公司 | Polycarboxylate superplasticizer for low-slump concrete and preparation method thereof |
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