CN103059216B - A kind of dispersion agent, its preparation method and the application in anionic polyacrylamide water-dispersible emulsion polymerization thereof - Google Patents
A kind of dispersion agent, its preparation method and the application in anionic polyacrylamide water-dispersible emulsion polymerization thereof Download PDFInfo
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Abstract
The invention provides a kind of comb-grafted copolymer dispersion agent, the preparation method of described dispersion agent; And the application method of described dispersion agent in anionic polyacrylamide emulsion polymerization.Described comb-grafted copolymer is obtained by the copolyreaction of three kinds of monomer generation free radical additions.Dispersant molecule amount provided by the present invention is less, and negative charge density is low, and side chain space steric hindrance is strong; Viscosity is little, and dissolve fast, brine sensitivity is low, and rapidly, stabilization efficiency is high in diffusion absorption; Molecular structure is adjustable, can significantly reduce emulsion polymerization systems viscosity, improve product solid content and water-dispersion stability of emulsion.
Description
Technical field
The invention belongs to water-soluble polymer synthesis technical field, particularly relate to a kind of dispersion agent, its preparation method, and the polymerization process of anionic polyacrylamide water-dispersion emulsion.
Background technology
The constructional feature of polyacrylamide and complete kind make it to be widely applied in the every field of national economy, enjoy the title of " all trades auxiliary agent ".In China, the application of polyacrylamide in the large field of oil, water treatment and papermaking three is even more important.
The method of synthesis polyacrylamide comprises solution polymerization, inverse suspension polymerization and inverse emulsion polymerization.Solution polymerization later stage viscosity is very high, stir and dispel the heat very difficult, and need to use special equipment drying to make powder, complicated technical process often causes polyacrylamide chain that a series of side reactions such as crosslinked or degraded occur, when causing product to use dissolve difficulty, need for a long time with special dissolution equipment.Emulsion-type (water-in-oil) polyacrylamide has good solvability, but this kind of method needs to use a large amount of hydrocarbon organic solvents and tensio-active agent, easily causes secondary pollution to environment.
Because production efficiency is high, technique environmental protection, product dissolves aqueous dispersion polymerization (aqueous dispersion polymerization is also referred to as water-water polymerization or double-aqueous phase polymerization) and flocculating property excellence becomes various countries' research emphasis.At present, the synthesis of cationic polyacrylamide water-dispersion emulsion has obtained certain progress, European patent EP 0183466 and EP0657478, US Patent No. 4929655 and US5006590 all describe in the aqueous solution containing multivalent anions salt and polymer stabilizer, obtain water-in-water emulsion by acrylamide and acrylyl oxy-ethyl-trimethyl salmiac, the copolymerization of acryloxyethyldimethyl benzyl ammonium chloride.
Compared with cationic, the synthesis of anion-polyacrylamide in brine media, much more difficult owing to not easily choosing with the acrylamide derivative monomer copolymerization of hydrophobic grouping, correlative study is also more rare.CN101649024A promotes to separate out phase-splitting by adding esters of acrylic acid hydrophobic monomer, add simultaneously and there is surface-active function monomer, improve early stage stabilization efficiency, but the introducing of this type of hydrophobic monomer often reduces the molecular weight of product, solvability is deteriorated greatly simultaneously; CN1519259A is then by adopting the one package stabilizer of non-ionic type polymer and multicomponent alcoholics compound to improve stabilising effect, but multicomponent alcoholics compound exists chain transfer to radical polymerization, is unfavorable for the product obtaining high molecular.
As can be seen here, the selection of dispersion agent is to reaction important, current patent and document all adopt linear anionic polymer or non ionic polymer as dispersion agent, emulsion particle is stablized in the sterically hindered effect utilizing polymer adsorption to produce at particle surface, this just requires that dispersion agent has certain molecular weight (can up to 500,000 ~ 1,500,000), this brings series of problems: first, reaction is carried out in high salt medium, the too high dispersion agent of molecular weight is difficult to rapid solution, even if dissolve, its molecular conformation affects by salt concn and is in the state of rolling up, greatly reduce its adsorption rate and stabilization, secondly, the too high initial reaction stage system viscosity that causes of dispersant molecule amount is larger, add the mutual entanglement between macromolecular chain, and macromolecular chain is difficult to the feature of diffusion motion, initial reaction stage dispersant adsorption speed is very slow, and often because not stablize the emulsion particle of precipitation in time, the system viscosity of making explodes and causes being polymerized unsuccessfully.Again, the electric density of linear anionic polymer is higher, and itself and latex ion exist stronger electrical charge rejection effect, easily causes dispersant molecule in the desorption on latex particle surface, is unfavorable for the extended storage stability of water-dispersion emulsion.
Summary of the invention
The invention provides a kind of dispersion agent, overcome above-mentioned shortcoming and defect; Present invention also offers the preparation method of described dispersion agent; And the application method of dispersion agent of the present invention in anionic polyacrylamide emulsion polymerization.
Dispersion agent of the present invention is comb-grafted copolymer, and its structure meets general formula (1),
R in general formula (1)
1, R
2, R
3represent H or CH independently of one another
3;
X represents O, CH
2o, CH
2cH
2o or COO;
Y represents H or CH
2cH
2n
+(CH
3)
3cl
-;
A: b: c=(2.5 ~ 7.5): (2.5 ~ 5): 1; N value is 5 ~ 25, and the molecular weight of described comb-grafted copolymer is 10000 ~ 100000.
Dispersion agent of the present invention, molecular weight, introduce sulfonic acid group or cation group in the structure, salt sensitivity is lower, and therefore can keep the chain conformation comparatively stretched in high salt, rate of diffusion and adsorption rate significantly improve; When being applied in emulsion polymerization, stabilization can be played rapidly to the emulsion particle that the polyreaction initial stage generates; Meanwhile, owing to having the graft side chain of larger steric hindrance, the relatively conventional linear polymeric of its stably dispersing effect is promoted further, is conducive to polymerization reaction late stage stable system, also improves emulsion extended storage stability simultaneously; Cation group in addition on dispersion agent chain link can strengthen the effect of dispersion agent and electronegative emulsion particle, reduces the desorption of stablizer, has obvious effect to raising reaction later transformation rate, product solid content and electric charge degree.
As improvement, the n value in general formula (1) is 10 ~ 20.
When n value is 5 ~ 10, the adsorption rate of dispersion agent is faster, is conducive to the fast and stable of the emulsion particle of early origin, makes early stage viscosity lower, but due to side chain shorter, the dispersion liquid viscosity finally obtained is slightly large; When n value is 20 ~ 25, dispersion agent side chain is longer, and early stage dispersion effect is slightly poor, and the latex particle size of formation is slightly large, and solvability has some to affect.
The preparation method of dispersion agent of the present invention: obtain described comb-grafted copolymer by the copolyreaction of three kinds of monomer generation free radical additions, described three kinds of monomers are: 2-acrylamide-2-methylpro panesulfonic acid (formula 2), with general formula 3, monomer shown in general formula 4;
The quality summation of comonomer accounts for 15 ~ 40% of the quality summation of the reactant of described free radical addition copolyreaction, general formula (2), with general formula (3), shown in general formula (4), the molar ratio of monomer is a: b: c, described a, b, c are a in general formula (1), b, c.
Described free radical addition copolyreaction initiator used be selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide any one.Initiator accounts for 0.5 ~ 5% of added monomer total mass.In described free radical addition copolyreaction, by adding the amount of initiator, regulate the molecular weight of described dispersion agent.
Monomer mixed solution and initiator solution are separately added dropwise in reaction vessel, and the time for adding of monomer mixed solution and initiator solution is 1.5 ~ 5.0 hours, and the solvent of described initiator solution is water, and initiator accounts for 0.5% ~ 5% of solution total mass.
The concentration requirement of initiator solution is little, as long as control to drip off within preset time: concentration height then drips slowly, hurry up, the too high amount of solution of concentration is less for the low dropping of concentration, and the more difficult control of rate of addition, therefore controls 0.5% ~ 5%.In principle particular requirement be there is no for mass concentration, as long as the time added can be controlled
Monomer mixture and initiator solution take the above-mentioned mode separately dripped, and control the homogeneity of the segment distribution of described dispersion agent and the stability of polyreaction.
Described free radical addition copolyreaction is reacted 5 ~ 10 hours at 60 ~ 90 DEG C; Described temperature of reaction is decided by the decomposition temperature of foregoing initiators.
Apply dispersion agent of the present invention in the preparation method of anionic polyacrylamide water-dispersion emulsion, comprise the steps:
A) join in reactor by non-ionic monomer A, anionic monomer B, inorganic salt C, dispersion agent D in following ratio, be dissolved in water and obtain reaction solution, regulation system pH value is 6 ~ 7;
Monomer 15-30%,
Inorganic salt C 15-25%,
Dispersion agent 1-3%,
Water surplus;
Described monomer is made up of non-ionic monomer A and anionic monomer B, and described non-ionic monomer A is selected from acrylamide or Methacrylamide; Non-ionic monomer accounts for the 20-80% of whole monomer system total mass; Anionic monomer B is vinylformic acid, methacrylate, allyl sulphonic acid, 2-acrylamide-2-methylpro panesulfonic acid and sodium salt thereof one or several arbitrarily wherein;
Inorganic salt C is sodium, ammonium, lithium ion salt, is selected from one or more arbitrary combination in ammonium sulfate, sodium sulfate, Lithium Sulphate, sodium-chlor, ammonium chloride, Trisodium Citrate, sodium tartrate;
B) reaction solution through step (a) gained is warming up to 30-50 DEG C, logical nitrogen deoxygenation, add initiator I, the add-on of initiator accounts for the 0.01-0.1% of monomer mass;
C) through the reaction solution insulation reaction of step (b) after 5 ~ 10 hours, cool to room temperature, discharging, obtained anionic polyacrylamide water-dispersion product emulsion.
Described non-ionic monomer A is acrylamide.Adopt acrylamide, be more easy to get high molecular weight product, simultaneously better water-soluble.
Described anionic monomer B is acrylic acid and/or 2-acrylamide-2-methylpro panesulfonic acid.When adopting this two kinds of anionic monomers, the molecular weight of gained polyacrylamide is higher, better water-soluble.
Described inorganic salt C is selected from one or more arbitrary combination in ammonium sulfate, Lithium Sulphate, sodium-chlor.When adopting these several inorganic salt above-mentioned, the viscosity of gained anionic polyacrylamide water-dispersion emulsion is lower, dissolves rapider simultaneously.
Described initiator I is azo-initiator and/or redox initiator; When initiator employing azo-initiator and redox initiator, both amounts are not specially required, as long as total amount meets the demands.
Described azo-initiator is selected from azo diisobutyl amidine hydrochloride (V-50) or azo two isobutyl imidazoline hydrochloride (VA-044)
Described redox initiator is selected from the one in hydrogen peroxide/xitix, Potassium Persulphate/S-WAT, Potassium Persulphate/sodium bisulfite, ammonium persulphate/S-WAT, ammonium persulphate/sodium bisulfite, ammonium persulphate/trolamine, and in redox initiator, the mass ratio of oxygenant and reductive agent is 2: 1 ~ 1: 2.
Dispersant molecule amount provided by the present invention is less, and negative charge density is low, and another dispersion agent of the present invention is comb-grafted copolymer, and its side chain space steric hindrance is strong; Viscosity is little, and dissolve fast, brine sensitivity is low, and rapidly, stabilization efficiency is high in diffusion absorption; Make its molecular structure adjustable by regulating the molar ratio of a: b: c, when being applied in emulsion polymerization systems, can different structure be designed to different emulsion polymerization systems, with strong points, significantly reduce emulsion polymerization systems viscosity, improve product solid content and water-dispersion stability of emulsion.
By application of dispersant of the present invention in anionic polyacrylamide water-dispersible emulsion polymerization, can production dissolution rate fast, molecular weight is high, good fluidity and anionic polyacrylamide water-dispersion emulsion easy to use.
Specific embodiment
Below in conjunction with embodiment, anionic polyacrylamide water-dispersion emulsion preparation process of the present invention is described in more detail, and these embodiments provide by way of illustration, its object is to person skilled in the art can be understood content of the present invention and implement according to this, but these embodiments never limit the scope of the invention.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
In synthesis example of the present invention, dispersant molecule amount uses aqueous gel permeation chromatography (GPC) to measure.Experiment condition is as follows:
Gel column: Shodex SB806+803 two root chromatogram column is connected
Eluant: 0.1M NaNO
3solution
Moving phase speed: 1.0ml/min
Injection: 20 μ l 0.5% aqueous solution
Detector: Shodex RI-71 type differential refraction detector
Standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
Raw material used in following synthesis example and embodiment and be called for short as shown in table 1, the anionic polyacrylamide water-dispersion emulsion of synthesis is referred to as APD.
Raw materials used in table 1 synthesis example and embodiment
Synthesis example is the synthetic method of dispersion agent D used in the present invention.
Synthesis example 1 (synthesis of dispersion agent D-1)
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 100 ml deionized water, stir while use nitrogen purging reaction vessel, and be warming up to 75 DEG C, then by 30 grams (B-4) and 7 grams (B-1) and 5 grams (F-1) and 80 milliliters, water, make the mix monomer aqueous solution, instilled reactor, time for adding is 2 hours, and drip 10% ammonium persulfate initiator solution 20 grams simultaneously, time for adding is 5 hours, dropwise rear insulation reaction and be cooled to room temperature in 5 hours, obtain dispersion agent D-1, its molecular weight is 15000.
Synthesis example 2-4 (synthesis of dispersion agent D-2-D-4)
Prepare D-2-D-4 of the present invention according to the step of synthesis example 1, feed intake according to the ratio described by table 2.
Ingredient proportion prepared by table 2 dispersion agent and molecular weight
Embodiment is the synthetic method of anionic polyacrylamide water-dispersion emulsion of the present invention.
Embodiment 1 (synthesis of APD-1)
In the glass reactor that thermometer, agitator, nitrogen ingress pipe and reflux exchanger are housed, add 59.84 grams (A-1), 15.16 grams (B-1), 100 grams (C-1) and 5 grams (C-4), 5 grams (D-1) and 315 grams of deionized waters, regulation system pH value is 6 ~ 7, stir while use nitrogen purging reaction vessel, and be warming up to 35 DEG C, then add 0.020 gram (I-1), insulation reaction was cooled to room temperature after 10 hours, obtained anionic polyacrylamide water-dispersion latex A PD-1.
Embodiment 2-12 (synthesis of APD-2-APD-12)
Prepare APD-2-APD-12 of the present invention according to the step of embodiment 1, feed intake according to the ratio described by table 3.
In the embodiment of the present invention, the molecular weight of all anionic polyacrylamide water-dispersion breasts adopts viscosity method to measure according to GB17514-2008.Must process sample before mensuration, to remove inorganic salt in sample and the complete monomer of unreacted.
Concrete treating processes is as follows: by soluble in water for anionic polyacrylamide water-dispersion breast, be made into the aqueous solution that mass concentration is 2%, then be poured in aqueous ethanolic solution (volume ratio of dehydrated alcohol and the aqueous solution is 3: 1) and be settled out polymkeric substance, then use washing with acetone.This process in triplicate, then by throw out vacuum-drying at 40 DEG C.
The viscosity measurement of anionic polyacrylamide water-dispersion emulsion adopts SNB AI intelligence Brookfield viscometer, and No. 27 rotors measure cloth network gram Field (Brookfield) viscosity under 10RPM.The viscosity of anionic polyacrylamide water-dispersion breast is lower, illustrates that its mobility is better
Each reactant ingredient proportion prepared by table 3 anionic polyacrylamide water-dispersion emulsion, the obtained viscosity of anionic polyacrylamide water-dispersion emulsion (being called for short dispersion liquid in table) and the molecular weight of polyacrylamide
Contrast synthesis example 1 (synthesis of common dispersants D-5)
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 250 ml deionized water, 45 grams of B-4 and 8.7 gram sodium hydroxide, stirring is after solid all dissolves, be warming up to 50 DEG C, purge nitrogen simultaneously, 0.01 gram of I-7 is added after half an hour, react and be warming up to 80 DEG C after 20 hours and react 6 hours again, obtain dispersion agent D-5 (the linear polymeric dispersion agent of 2-acrylamide-2-methylpro panesulfonic acid sodium homopolymer-routine) and measure limiting viscosity number according to GB 17514-2008, the MH Equation for Calculating molecular weight adopting document (Macromolecules 10 (1977) 949-954) is 750,000.
Comparative example 1:
Use common dispersants D-5 to synthesize the anionic polyacrylamide water-dispersion latex A PD-13 of composition similar to Example 1, survey its viscosity and molecular weight by the detection method of embodiment to gained anionic polyacrylamide water-dispersion emulsion, the data obtained sees the following form:
Table 4 embodiment 1 and comparative example 1 each reactant ingredient proportion, the obtained viscosity of anionic polyacrylamide water-dispersion emulsion (being called for short dispersion liquid in table) and the molecular weight of polyacrylamide
Known by viscosity data listed by table 4: the viscosity of the anionic polyacrylamide water-dispersion emulsion using common dispersants to obtain is comparatively large, and namely its mobility is bad.
Comparative example 2 (using common dispersants D-5 to synthesize the anionic polyacrylamide water-dispersion emulsion of composition similar to Example 4)
Synthetic method and proportioning, according to APD-4, just change dispersion agent D-2 into D-5, find adding initiator for reaction after 10 hours in experiment, system viscosity increases suddenly, form a large amount of oyster white block, polymerization system loses macroscopic stability, cannot obtain stable water-dispersion emulsion.Use common dispersants cannot obtain stable water-dispersion emulsion when anion degree is higher.
Comparative example 3 (using common dispersants D-5 to synthesize the anionic polyacrylamide water-dispersion emulsion of composition similar to Example 9)
Synthetic method and proportioning, according to APD-9, just change dispersion agent D-2 into D-5, and find in experiment adding initiator after two hours, system viscosity increases suddenly, form transparence gel, occur serious rod climbing phenomenon simultaneously, cannot obtain stable water-dispersion emulsion.Use common dispersants cannot obtain stable water-dispersion emulsion when monomeric charge is higher and salt concn is higher.
Claims (10)
1. apply the method that comb-shaped graft copolymer dispersion agent prepares anionic polyacrylamide water-dispersion emulsion, it is characterized in that comprising the steps:
A) join in reactor by non-ionic monomer A, anionic monomer B, inorganic salt C, dispersion agent D by following mass ratio, be dissolved in water and obtain reaction solution, regulation system pH value is 6 ~ 7;
Described monomer is made up of non-ionic monomer A and anionic monomer B, and described non-ionic monomer A is selected from acrylamide or Methacrylamide; Non-ionic monomer accounts for the 20-80% of whole monomer system quality; Anionic monomer B is vinylformic acid, methacrylic acid, allyl sulphonic acid, 2-acrylamide-2-methylpro panesulfonic acid and sodium salt thereof one or several arbitrarily wherein;
Inorganic salt C is sodium, ammonium, lithium ion salt, is selected from one or more arbitrary combination in ammonium sulfate, sodium sulfate, Lithium Sulphate, sodium-chlor, ammonium chloride, Trisodium Citrate, sodium tartrate;
B) reaction solution through step a) gained is warming up to 30-50 DEG C, logical nitrogen deoxygenation, add initiator I, the add-on of initiator accounts for the 0.01-0.1% of monomer total mass;
C) through step b) reaction solution insulation reaction after 5 ~ 10 hours, cool to room temperature, discharging, obtained anionic polyacrylamide water-dispersion product emulsion;
Described dispersion agent is comb-grafted copolymer, and its structure meets general formula (1),
R in general formula (1)
1, R
2, R
3represent H or CH independently of one another
3;
X represents O, CH
2o, CH
2cH
2o or COO;
Y represents H or CH
2cH
2n
+(CH
3)
3cl
-;
A:b:c=(2.5 ~ 7.5): (2.5 ~ 5): 1; N value is 5 ~ 25, and the molecular weight of described comb-grafted copolymer is 10000 ~ 100000.
2. method according to claim 1, is characterized in that: the n value in described general formula (1) is 10 ~ 20.
3. method according to claim 1, it is characterized in that: obtain described comb-grafted copolymer by the copolyreaction of three kinds of monomer generation free radical additions, described three kinds of monomers are: 2-acrylamide-2-methylpro panesulfonic acid (formula 2), with general formula (3), monomer shown in general formula (4);
The quality summation of comonomer accounts for 15 ~ 40% of the quality summation of the reactant of described free radical addition copolyreaction, general formula (2), with general formula (3), shown in general formula (4), the molar ratio of monomer is a:b:c, described a, b, c are a in general formula (1), b, c.
4. method according to claim 3, it is characterized in that free radical addition copolymerization initiator used is selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide any one; Initiator accounts for 0.5 ~ 5% of added monomer total mass.
5. method according to claim 3, is characterized in that: monomer mixed solution and initiator solution are separately added dropwise in reaction vessel, and the time for adding of monomer mixed solution and initiator solution is 1.5 ~ 5.0 hours; The solvent of described initiator solution is water, and initiator accounts for 0.5% ~ 5% of solution total mass.
6. method according to claim 3, is characterized in that: free radical addition copolyreaction is reacted 5 ~ 10 hours at 60 ~ 90 DEG C.
7. method according to claim 1, is characterized in that: described non-ionic monomer A is acrylamide.
8. method according to claim 1, is characterized in that: described anionic monomer B is vinylformic acid and/or 2-acrylamide-2-methylpro panesulfonic acid.
9. method according to claim 1, is characterized in that: described inorganic salt C is selected from one or more arbitrary combination in ammonium sulfate, Lithium Sulphate, sodium-chlor.
10. method according to claim 1, is characterized in that: described initiator I is azo-initiator and/or redox initiator;
Described azo-initiator is selected from azo diisobutyl amidine hydrochloride or azo two isobutyl imidazoline hydrochloride; Described redox initiator be selected from hydrogen peroxide/xitix, Potassium Persulphate/S-WAT, Potassium Persulphate/sodium bisulfite, ammonium persulphate/S-WAT, ammonium persulphate/sodium bisulfite, ammonium persulphate/trolamine any one, in redox initiator, the mass ratio of oxygenant and reductive agent is 2:1 ~ 1:2.
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| CN103435749B (en) * | 2013-08-28 | 2015-09-09 | 江苏苏博特新材料股份有限公司 | Seed swelling legal system is for less salt low-viscosity polyacrylamide water-water dispersion liquid |
| CN103545470B (en) * | 2013-09-23 | 2015-10-14 | 超威电源有限公司 | A kind of colloidal lead-acid storage battery dividing plate and preparation method thereof |
| CN108083614B (en) * | 2018-02-05 | 2020-12-08 | 中国科学院长春应用化学研究所 | Water-dispersible diatomite composite flocculation dehydrating agent and application thereof |
| CN108690165B (en) * | 2018-06-08 | 2019-11-26 | 山东金元化工股份有限公司 | A kind of preparation method and applications of paper grade (stock) emulsion-type cationic dry strength agent |
| EP3789359A1 (en) * | 2019-09-03 | 2021-03-10 | Sika Technology AG | Use of comb polymers as inerting agents for non-swelling layer-silicates |
| CN113150207A (en) * | 2021-03-11 | 2021-07-23 | 西安长庆化工集团有限公司 | Water-in-water polymer dispersion and preparation method thereof |
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| CN102225988A (en) * | 2011-03-24 | 2011-10-26 | 中国海洋石油总公司 | Dispersant used in polymer cement mortar for oil field cementing, and preparation method thereof |
| CN102358768A (en) * | 2011-07-22 | 2012-02-22 | 广州市建筑科学研究院有限公司 | Modified ether polycarboxylic acid water reducing agent and preparation method thereof |
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| CN102225988A (en) * | 2011-03-24 | 2011-10-26 | 中国海洋石油总公司 | Dispersant used in polymer cement mortar for oil field cementing, and preparation method thereof |
| CN102358768A (en) * | 2011-07-22 | 2012-02-22 | 广州市建筑科学研究院有限公司 | Modified ether polycarboxylic acid water reducing agent and preparation method thereof |
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