CN102181020B - Method for synthesizing polycarboxylic acid high-property water reducer by copolymerization of amidated active monomers - Google Patents
Method for synthesizing polycarboxylic acid high-property water reducer by copolymerization of amidated active monomers Download PDFInfo
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Abstract
The invention discloses a method for synthesizing polycarboxylic acid high-property water reducer by copolymerization of amidated active monomers, belonging to the field of water reducer. In the invention, the polycarboxylic acid high-property water reducer material is prepared by a method of first amidation and second copolymerization, namely, taking a (methyl) acrylic monomer and methoxyl polyoxyethylene ether with the other end containing amino as reactant, preparing a polymerizable monomer by amidation reaction under the action of catalyst, then copolymerizing the polymerizable monomer with the (methyl) acrylic monomer and a chain transfer monomer in water solution under the action of initiator, and then neutralizing with alkaline solution, thus preparing the polycarboxylic acid high-property water reducer. The method is low in cost, environment-friendly and free from pollution and achieves high polymerization degree and strong controllability; by copolymerization of amidated active monomer, an amide structure is introduced into the molecular structure of polycarboxylic acid water reducer, cement can obtain good flowing property, the flowing capacity maintaining capability of neat cement paste is improved obviously, excellent cement adaptivity is shown, and excellent flowing effect can be obtained under low doping quantity and low water-ash ratio.
Description
Technical field
The present invention relates to the technical field of a kind of cement concrete, specially refer to a kind of concrete preparation method who adopts the synthetic high performance water reducing agent of polyocarboxy acid of amidation reactive monomer copolyreaction with high performance water reducing agent of polyocarboxy acid.
Background technology
Dynamics along with continuous attention in various countries in recent years and increasing scientific and technical innovation; Economic strength of China and infrastructure construction are also in simultaneous growth; Variation with rapid changepl. never-ending changes and improvements is taking place in the domestic construction industry, has the buildings emerge in multitude of the high construction quality of excellent in strength, weather resistance, and the performance requriements of concrete high-performance water reducer is improved constantly; Demand also increasing year by year, presents the trend of sharp increase in recent years.
In the face of the expensive realistic problem of the external prices of raw and semifnished materials of high performance water reducing agent of polyocarboxy acid; Press for domestic raw material market and release mature and stable product innovation; And develop the high performance water reducing agent of polyocarboxy acid product that has independent intellectual property right that adapts to the domestic construction industry market, the high performance water reducing agent of polyocarboxy acid of realizing the starting material production domesticization is imported product outside the subrogate country partially or completely.
Patent CN101475664 (open day: on July 8th, 2009) reported a kind of preparation method who is used for the high performance water reducing agent of polyocarboxy acid of prefabricated components.This patent is that the two-stage process through first esterification post polymerization prepares a kind of polycarboxylate water-reducer; The first step is earlier methoxy polyoxyethylene ether and vinylformic acid down esterification to be taken place at 100-140 ℃, prepares the macromer methoxyl-polyethyleneglycol propenoate that has side chain; Second step was under action of evocating; The macromer methoxyl-polyethyleneglycol propenoate that the first step is made mixes the back and carries out Raolical polymerizable in heated in water solution to 70-85 ℃ with vinylformic acid, unsaturated sulfonic acid (salt), unsaturated amides etc.; Finally making vinylformic acid-methoxy poly (ethylene glycol) Yodo Sol GH 28, is a kind of with the polycarboxylate water-reducer material of high-polymerization degree methoxy poly (ethylene glycol) as graft side chain.The water reducer that makes has effectively shortened concrete time of coagulation under the situation that does not reduce concrete initial flow degree, improved concrete ultimate compression strength.But the needed esterification condition of this patent the first step is harsh relatively, is prone to produce side reaction, and reversibility is stronger, is unfavorable for meticulous control.
Patent CN101386488 (open day: on March 18th, 2009) reported a kind of preparation method of novel carboxylic acid modified melamine high-efficiency water-reducing agent.This patent is to be major ingredient with the trimeric cyanamide; Be aided with thionamic acid, sodium sulfite anhy 96, Whitfield's ointment, Hydrocerol A, phenol, the agent of self-control modification sulphonation, formaldehyde and liquid caustic soda; According to certain proportioning; Series of chemical such as process methylolation, sulfonation, polycondensation, stable rearrangement under 60-90 ℃, the concrete high efficiency water reducing agent material that makes.This water reducer has that water-reducing rate height, flexibility are good, the characteristics of good water-retaining property.Although the inventive method of this patent has also been introduced amino functionalization in reaction; Improved polarity of chain; But the water reducer of preparation belongs to trimeric cyanamide system, thus do not possess such as the guarantor collapse effective, mobile excellent, through the time have higher polycarboxylate high performance water-reducing agent inherent advantages such as water-reducing rate under loss little, the low-dosage.
The preparation method of the poly carboxylic acid series water reducer of describing in most patents still be mostly through methoxy polyoxyethylene ether as raw material, polymerisate has long T 46155 base side chain, its strongly hydrophilic can obviously improve the dispersion effect to cement slurry.Yet, react higher with Soxylat A 25-7 compounds cost, kind is single, and the flowing property during sometimes at low-dosage or than low water-cement ratio but descends to some extent.Though the patent that has adopts non-polycarboxylic acid series raw material synthetic method to solve the problem of cost, the water reducer that makes still can't be realized the overall equilbrium of Cost And Performance.In addition, Soxylat A 25-7 prepares unsaturated big monomer, carrying out polymerization with double bond containing carboxylic acid again, to prepare water reducer be method nowadays relatively commonly used for passing through of reporting in the patent, yet; Big monomeric synthesizing is confined to the esterification mode more, and some building-up process is very complicated too, and is difficult to meticulous control; Production cycle is long; Part technology does not meet environmental requirement, is badly in need of the new synthesis mode that some can keep the product excellent properties, and relevant this respect work does not appear in the newspapers both at home and abroad.
Summary of the invention
The purpose of this invention is to provide a kind of preparation technology through the synthetic high performance water reducing agent of polyocarboxy acid of amidation reactive monomer copolyreaction; Prepare behind the polymerisable monomer again and the copolymerization of (methyl) Acrylic Acid Monomer through end being contained amino Soxylat A 25-7 and (methyl) Acrylic Acid Monomer elder generation amidation, obtain all graftomer of excellence of structure and performance.This method is also regulated ethylene oxide number of repeating units on distribution and the side chain of the carboxylic group on the main chain in building-up process; Effectively improve the ubiquitous dispersed not good problem that keeps of traditional polycarboxylate water-reducer, enriched the preparation method of synthetic high performance water reducing agent of polyocarboxy acid.Adopt that present method synthetic water reducer has that technological operation is simple and easy to control, the synthetic safety and environmental protection of preparation, energy-saving and cost-reducing, advantage such as the diminishing dispersion effect is obvious with low cost, when low-dosage or low water-cement ratio, cement not of the same race is had flexibility preferably.
The invention provides the synthetic high performance water reducing agent of polyocarboxy acid material of method that a kind of preparation method through the synthetic high performance water reducing agent of polyocarboxy acid of amidation reactive monomer copolyreaction adopts first amidation repolymerization, comprise following condition and step:
(1) amidate action: at first will hold amino Soxylat A 25-7 to join in the reactor drum; In reactor drum, add stopper, (methyl) vinylformic acid, catalyzer when being warmed up to 50-80 ℃ more successively; And each reinforced churning time at interval 10-20 minute; Add the band aqua when temperature is increased to 80-100 ℃, continue to be warming up to and carry out amidate action under 115-160 ℃, will react the gained water sepn in the time of reaction and go out; React and slough the band aqua through vacuumizing after 2-10 hour, obtain amidate action product (different) acryloyl Soxylat A 25-7 amine;
(2) polyreaction: product (different) the acryloyl Soxylat A 25-7 amine that above-mentioned amidate action is obtained joins in the reactor drum; Add entry again; Be warmed up to 50-65 ℃ and stir and to treat that it mixed in 15-30 minute, in reactor drum, add (methyl) vinylformic acid successively or its mixture, molecular weight regulator, massfraction with unsaturated carboxylic acid is the initiator persulfate solution of 1-30%, and each reinforced interval churning time 10-20 minute; Temperature rises to 70-90 ℃ and carries out polyreaction; Reaction 1.5-6 hour is used the basic soln of 10-50% to be neutralized to the pH value and is 6-8 when being cooled to 40-60 ℃, be cooled to 25-40 ℃; Obtain the polymeric bodies structure for gathering the product of (different) acryloyl Soxylat A 25-7 amine, add the polycarboxylate water-reducer that entry obtains desired concn at last.
Used stopper is Resorcinol, thiodiphenylamine, (sulfo-) pentanoic or MEHQ hydroquinone monomethyl ether in the amidate action described in the above-mentioned steps (1), and consumption is the 0.05-5% of (methyl) vinylformic acid quality; Catalyst system therefor is tosic acid, the vitriol oil, ETHYLE ACETATE, phosphoric acid or thionamic acid in the described amidate action, and consumption is the 1.5-10% of the amino Soxylat A 25-7 quality of end; Used band aqua is hexanaphthene, benzene or toluene in the described amidate action, and consumption is the 8-30% of reactant total mass, and the reactant of indication is (methyl) vinylformic acid and the amino Soxylat A 25-7 of end in the step (1); Described (methyl) vinylformic acid is 1.5-5 with the mol ratio of the amino Soxylat A 25-7 of end: 1.
The quality that adds entry described in the above-mentioned steps (2) be step (1) gained amidate action product and (methyl) vinylformic acid or itself and unsaturated carboxylic acid mixture quality and 80-120%; Described unsaturated carboxylic acid is one or more in methylene-succinic acid, toxilic acid (acid anhydride), the fumaric acid, and (methyl) the acrylic acid mol ratio that adds in consumption and the step (2) is 0.1-1: 1; Described molecular weight regulator is Thiovanic acid, thiohydracrylic acid or (methyl) sodium allyl sulfonate, and consumption is 0.1-0.8 with the mol ratio of the amino Soxylat A 25-7 of end: 1; Described initiator persulphate is ammonium persulphate, Potassium Persulphate or Sodium Persulfate, and consumption is the 1-15% of the mixture total mass of step (1) gained amidate action product and (methyl) vinylformic acid or itself and unsaturated carboxylic acid; The solute of described basic soln is sodium hydroxide, Pottasium Hydroxide, quadrol or trolamine, in consumption and the step (1) on reaction product (different) the acryloyl Soxylat A 25-7 amine in remaining carboxyl and the step (2) total mol ratio of the mixture of (methyl) vinylformic acid of adding or itself and unsaturated carboxylic acid be 0.7-1: 1; The mixture of described (methyl) vinylformic acid or itself and unsaturated carboxylic acid and the mol ratio of amidate action product (different) acryloyl Soxylat A 25-7 amine are 1.5-4: 1.
The number-average molecular weight of the amino Soxylat A 25-7 of the end in the inventive method is 500-3000.
The inventive method compared with prior art has following beneficial effect:
(1) the present invention relies on amidate action to prepare high performance water reducing agent of polyocarboxy acid fully; This amidation reactive monomer copolyreaction method adopts the mode of first amidation repolymerization; Be to be big monomer and unsaturated carboxylic acid polymerization in the aqueous solution with amidated products; The polymerisate that obtains can directly use, and is convenient and swift.Both reduced dependence, enriched the means of synthetic high performance water reducing agent of polyocarboxy acid, widened thinking and direction for the polycarboxylate water-reducer of follow-up study and developing new product variety again the esterification preparation method.
(2) adopt methoxy polyoxyethylene ether or allyl polyethenoxy ether to prepare high performance water reducing agent of polyocarboxy acid in the home market mostly as main raw material; And adopt the amino Soxylat A 25-7 of domestic end to replace methoxy polyoxyethylene ether as main raw material from production, greatly reduce production cost.Simultaneously, amino Soxylat A 25-7 of the end of use and the suitable molecular weight wide ranges of gathering (methyl) vinylformic acid raw material help the large-scale popularization and the application of diversified product, increase the market competitiveness of high performance water reducing agent of polyocarboxy acid.
(3) because the amino Soxylat A 25-7 of end itself is aqueous; Therefore the present invention has also save the step of the preceding heating and melting of traditional methoxy polyoxyethylene ether solid reaction; The entire operation step is simple and easy to control; The water reducer Product Status that obtains is stable, deposits non-crystallizablely under the low temperature, and performance is unaffected after the low-temperature storage.
(4) safe preparation process environmental protection, cleanliness without any pollution, reaction process need not nitrogen protection, and used band aqua also can be recycled after separatory separates, and has reduced wastage of material.The condensing reflux of band aqua can also keep system temperature steady, and can reduce the viscosity of HMW reaction system, makes to mix more fully, improves the uniformity coefficient and the speed of reaction of system.
(5) through not comprising ester bond in the synthetic structure that obtains water reducer of amidate action method; Comprise carboxyl and amide structure etc. higher dispersion effect and the functional group that keeps effect can be provided; At low water-cement ratio with than all showing good mobility and hold facility under the low-dosage, and the cement of different varieties is shown very strong flexibility.This method synthetic product still has excellent each item performance index when reducing cost, help the enforcement of suitability for industrialized production, therefore has good economic benefits and social effect.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but enforcement of the present invention is not limited thereto.
Embodiment 1
Hold amino Soxylat A 25-7 (molecular weight is 2000) to join in the reactor drum 120g; In reactor drum, add 0.26g MEHQ hydroquinone monomethyl ether, 12.96g vinylformic acid, the 1.84g vitriol oil (concentration 98%) when being warmed up to 50 ℃ more successively; And each reinforced churning time at interval 10 minutes; Add the 26.59g hexanaphthene when temperature is increased to 80 ℃, continue to be warming up to and carry out amidate action under 145 ℃, will react the gained water sepn in the time of reaction and go out; React and slough hexanaphthene through vacuumizing after 6 hours, obtain amidate action product acryloyl Soxylat A 25-7 amine; The product acryloyl Soxylat A 25-7 amine that above-mentioned amidate action is obtained joins in the reactor drum; Add 100.69g water again; Be warmed up to 60 ℃ and stir and to treat that it mixed in 20 minutes, in reactor drum, add 6.48g vinylformic acid, 2.76g Thiovanic acid, 92.24g massfraction successively and be 15% potassium persulfate solution, and each reinforced churning time at interval 10 minutes; Temperature rises to 70 ℃ and carries out polyreaction; Reacted 6 hours, use when being cooled to 40 ℃ 35.28g concentration be 30% potassium hydroxide solution to be neutralized to the pH value be 7, be cooled to 30 ℃; Obtain the product that the polymeric bodies structure is a polyacrylamide Soxylat A 25-7 amine, adding 2.38g water dilution at last, to obtain concentration be 45% polycarboxylate water-reducer.
Embodiment 2
The concentration that embodiment 1 is obtained be 45% polycarboxylate water-reducer after depositing 40 days under 6 ℃, measure its implementation result.
Embodiment 3
Hold amino Soxylat A 25-7 (molecular weight is 3000) to join in the reactor drum 180g; In reactor drum, add 0.39g Resorcinol, 7.74g methylacrylic acid, 9g phosphoric acid when being warmed up to 80 ℃ more successively; And each reinforced churning time at interval 20 minutes; Add 15.02g toluene when temperature is increased to 100 ℃, continue to be warming up to and carry out amidate action under 160 ℃, will react the gained water sepn in the time of reaction and go out; React and slough toluene through vacuumizing after 2 hours, obtain the different acryloyl Soxylat A 25-7 of amidate action product amine; The different acryloyl Soxylat A 25-7 of the product amine that above-mentioned amidate action is obtained joins in the reactor drum; Add 201.51g water again; Be warmed up to 50 ℃ and stir and to treat that it mixed in 30 minutes, the mixture, 0.64g thiohydracrylic acid, the 6.72g massfraction that in reactor drum, add 12.9g methylacrylic acid and 1.95g methylene-succinic acid successively are 30% ammonium persulfate solution, and each reinforced interval churning time 20 minutes; Temperature rises to 90 ℃ and carries out polyreaction; Reacted 1.5 hours, use when being cooled to 60 ℃ 54.6g concentration be 10% sodium hydroxide solution to be neutralized to the pH value be 6, be cooled to 25 ℃; Obtaining the polymeric bodies structure is the product of polyisobutylene acyl Soxylat A 25-7 amine, and adding 73.18g water dilution at last, to obtain concentration be 40% polycarboxylate water-reducer.
Embodiment 4
The concentration that embodiment 3 is obtained be 40% polycarboxylate water-reducer after depositing 30 days under 5 ℃, measure its implementation result.
Embodiment 5
Hold amino Soxylat A 25-7 (molecular weight is 500) to join in the reactor drum 50g; In reactor drum, add 0.02g thiodiphenylamine, 36g vinylformic acid, 5g tosic acid when being warmed up to 65 ℃ more successively; And each reinforced churning time at interval 15 minutes; Add 25.8g benzene when temperature is increased to 80 ℃, continue to be warming up to and carry out amidate action under 115 ℃, will react the gained water sepn in the time of reaction and go out; React and slough benzene through vacuumizing after 10 hours, obtain amidate action product acryloyl Soxylat A 25-7 amine; The product acryloyl Soxylat A 25-7 amine that above-mentioned amidate action is obtained joins in the reactor drum; Add 146.16g water again; Be warmed up to 65 ℃ and stir and to treat that it mixed in 15 minutes, the mixture, 12.64g methallylsulfonic acid sodium, the 121.8g massfraction that in reactor drum, add 14.4g vinylformic acid and 23.2g toxilic acid successively are 1% Sodium Persulfate solution, and each reinforced interval churning time 15 minutes; Temperature rises to 80 ℃ and carries out polyreaction; Reacted 3.5 hours, use when being cooled to 50 ℃ 79.47g concentration be 50% triethanolamine solution to be neutralized to the pH value be 8, be cooled to 40 ℃; Obtain the polymeric bodies structure for gathering the product of (different) acryloyl Soxylat A 25-7 amine, adding the dilution of 118.69g water at last, to obtain concentration be 30% polycarboxylate water-reducer.
Embodiment 6
The concentration that embodiment 5 is obtained be 30% polycarboxylate water-reducer after depositing 45 days under 7 ℃, measure its implementation result.
Implementation result:
1. flowing degree of net paste of cement
Be relatively water reducer to the plastification effect of different cement, test determination under identical volume each embodiment to the clean slurry degree of mobilization of different cement types.Test is undertaken by GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", W/C=0.29, and volume is the solid volume of folding.Select existing commercially available poly carboxylic acid series water reducer (comparative example) sample as a comparison for use.Test-results is seen table 1.
The different cement paste flowing property of table 1 result
From table, can find out that under identical volume, several kinds of polycarboxylate water-reducers of the inventive method synthetic all have better cement adaptability than comparison sample.
2. low water-cement ratio paste degree of mobilization
The maximum characteristics of this product are that under utmost point low water-cement ratio W/C=0.20-0.22 situation during with the identical volume of other polycarboxylic acids dehydragent, clean slurry still can keep higher dispersing property.Test is undertaken by GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", and cement is selected reference cement for use, and volume is the solid volume of folding.Select existing commercially available poly carboxylic acid series water reducer (comparative example) sample as a comparison for use.Test-results is seen table 2.
Cement paste flowing property result under table 2 low water-cement ratio
Can find out that from table under low water-cement ratio, several kinds of polycarboxylate water-reducers of the inventive method synthetic all have the mobile result of better clean slurry than comparison sample.
3. low-dosage is starched degree of mobilization only
The maximum characteristics of this product are that under low-dosage (0.10-0.16) situation during with the identical wc of other polycarboxylic acids dehydragent, clean slurry still can keep higher dispersing property.Test is undertaken by GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", and cement is selected reference cement for use, W/C=0.29.Select existing commercially available poly carboxylic acid series water reducer (comparative example) sample as a comparison for use.Test-results is seen table 3.
Cement paste flowing property result under table 3 low-dosage
Can find out that from table under low-dosage, several kinds of polycarboxylate water-reducers of the inventive method synthetic all have the mobile result of better clean slurry than comparison sample.
Claims (1)
1. the method for the synthetic high performance water reducing agent of polyocarboxy acid of amidation reactive monomer copolyreaction is characterized in that, through the synthetic high performance water reducing agent of polyocarboxy acid material of the method for first amidation repolymerization, concrete steps are following:
(1) amidate action: at first will hold amino Soxylat A 25-7 to join in the reactor drum; In reactor drum, add stopper, (methyl) vinylformic acid, catalyzer when being warmed up to 50-80 ℃ more successively; And each reinforced churning time at interval 10-20 minute; Add the band aqua when temperature is increased to 80-100 ℃, continue to be warming up to and carry out amidate action under 115-160 ℃, will react the gained water sepn in the time of reaction and go out; React and slough the band aqua through vacuumizing after 2-10 hour, obtain amidate action product (methyl) acryloyl Soxylat A 25-7 amine;
(2) polyreaction: product (methyl) the acryloyl Soxylat A 25-7 amine that above-mentioned amidate action is obtained joins in the reactor drum; Add entry again; Be warmed up to 50-65 ℃ and stir and to treat that it mixed in 15-30 minute, in reactor drum, add (methyl) vinylformic acid successively or its mixture, molecular weight regulator, massfraction with unsaturated carboxylic acid is the initiator persulfate solution of 1-30%, and each reinforced interval churning time 10-20 minute; Temperature rises to 70-90 ℃ and carries out polyreaction; Reaction 1.5-6 hour is used the basic soln of 10-50% to be neutralized to the pH value and is 6-8 when being cooled to 40-60 ℃, be cooled to 25-40 ℃; Obtain the polymeric bodies structure for gathering the product of (methyl) acryloyl Soxylat A 25-7 amine, add the polycarboxylate water-reducer that entry obtains desired concn at last;
Wherein, used stopper is Resorcinol, thiodiphenylamine, (sulfo-) pentanoic or MEHQ hydroquinone monomethyl ether in the amidate action described in the step (1), and consumption is the 0.05-5% of (methyl) vinylformic acid quality; Catalyst system therefor is tosic acid, the vitriol oil, phosphoric acid or thionamic acid in the amidate action described in the step (1), and consumption is the 1.5-10% of the amino Soxylat A 25-7 quality of end; Used band aqua is hexanaphthene, benzene or toluene in the amidate action described in the step (1), and consumption is the 8-30% of reactant total mass, and the reactant of indication is (methyl) vinylformic acid and the amino Soxylat A 25-7 of end in the step (1); The quality that adds entry described in the step (2) be step (1) gained amidate action product and (methyl) vinylformic acid or itself and unsaturated carboxylic acid mixture quality and 80-120%; Unsaturated carboxylic acid described in the step (2) is one or more in methylene-succinic acid, toxilic acid (acid anhydride), the fumaric acid, and (methyl) the acrylic acid mol ratio that adds in consumption and the step (2) is 0.1-1:1; Molecular weight regulator described in the step (2) is Thiovanic acid, thiohydracrylic acid or (methyl) sodium allyl sulfonate, and consumption is 0.1-0.8:1 with the mol ratio of the amino Soxylat A 25-7 of end; Initiator persulphate described in the step (2) is ammonium persulphate, Potassium Persulphate or Sodium Persulfate, and consumption is the 1-15% of the mixture total mass of step (1) gained amidate action product and (methyl) vinylformic acid or itself and unsaturated carboxylic acid; The solute of the basic soln described in the step (2) is sodium hydroxide, Pottasium Hydroxide, quadrol or trolamine, in consumption and the step (1) on reaction product (methyl) the acryloyl Soxylat A 25-7 amine in remaining carboxyl and the step (2) total mol ratio of the mixture of (methyl) vinylformic acid of adding or itself and unsaturated carboxylic acid be 0.7-1:1;
Wherein, (methyl) vinylformic acid described in the step (1) is 1.5-5:1 with the mol ratio of the amino Soxylat A 25-7 of end;
The mixture of (methyl) vinylformic acid described in the step (2) or itself and unsaturated carboxylic acid and the mol ratio of amidate action product (methyl) acryloyl Soxylat A 25-7 amine are 1.5-4:1.
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| KR20080065815A (en) * | 2007-01-10 | 2008-07-15 | 주식회사 엘지화학 | Cement admixture, preparation method thereof, and cement composition containing the same |
| CN101293757A (en) * | 2008-06-17 | 2008-10-29 | 武汉理工大学 | Polyether modification type sulfamate water reducing agent and preparation method |
| CN101786824A (en) * | 2010-02-26 | 2010-07-28 | 北京新中岩建材科技有限公司 | Plastic retaining type polyether assemblage carboxylic acid high-performance water reducing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20080065815A (en) * | 2007-01-10 | 2008-07-15 | 주식회사 엘지화학 | Cement admixture, preparation method thereof, and cement composition containing the same |
| CN101293757A (en) * | 2008-06-17 | 2008-10-29 | 武汉理工大学 | Polyether modification type sulfamate water reducing agent and preparation method |
| CN101786824A (en) * | 2010-02-26 | 2010-07-28 | 北京新中岩建材科技有限公司 | Plastic retaining type polyether assemblage carboxylic acid high-performance water reducing agent and preparation method thereof |
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