CN102010487B - Method for preparing polycarboxylate water reducing agent - Google Patents
Method for preparing polycarboxylate water reducing agent Download PDFInfo
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Abstract
The invention discloses a polycarboxylate water reducing agent for a gobi desert environment. The polycarboxylate water reducing agent is mainly prepared by the following steps of: synthesizing poly(ethylene glycol methyl ether) maleic anhydride active macromonomer (PAM) by performing esterification reaction on poly(ethylene glycol methyl ether) (MPEG) and maleic anhydride (MAH) which serve as main raw materials; preparing a terpolymer by copolymerization of the PAM, sodium methallyl sulfonate (MAS) and itaconic acid (ITA) which serve as raw materials by free radicals; and neutralizing the terpolymer with a base solution. The polycarboxylate water reducing agent has excellent performance, such as high water reducing ratio, little cement paste gradual loss, high cost performance and the like, so that the problem that monomer with large activity difference is difficult to control is solved, and the requirement of construction in the gobi desert environment can be met.
Description
Technical field
The present invention relates to the preparation field of concrete admixture, be specifically related to a kind of preparation method of polycarboxylate water-reducer.
Background technology
Polycarboxylic acids dehydragent is as third generation high efficiency water reducing agent, because of its water-reducing rate is high, slump-loss is little, the adaptation of cement well, high-performance such as environmental protection becomes the new direction of domestic and international concrete admixture area research.
Recently come, external its technical development of poly carboxylic acid series water reducer is rapider, the control comparative maturity of production technique.It is reported; Japan's polycarboxylic acid series product accounts for more than 70% of product sum; The research centre in North America and Europe also begins to the exploitation of this direction and shifts, and China is in the stage of research and development, its synthetic product over-all properties with also have sizable gap abroad.The performance of at present domestic polycarboxylate water-reducer also is present in the problem of cement adaptability, sharply accelerates sometimes like concrete slump-loss speed.Therefore be necessary polycarboxylate water-reducer is carried out molecular structure control, utilize the structure control performance, reach the purpose of optimizing performance.
In order to give high-strength, good weather resisteant of concrete and workability; Research and develop out have bigger diminishing, high function of slump protection, with the good high efficiency water reducing agent of cement adaptability; Thereby make concrete each item performance satisfy the requirement that Lanzhou-Xinjiang line Gobi desert environment is constructed, significant.
The polycarboxylate water-reducer of present domestic research is difficult to take into account the advantage of protect plasticity and high water reducing rate.In patent CN1948209B, disclose a kind of method that maleic anhydride prepares polycarboxylate water-reducer that is used for,, do not reached the effect of normal water reducer with other polymer of monomers though maleic anhydride is easy to alcohols generation esterification in this method; Disclose a kind of preparation method of poly carboxylic acid series concrete diminishing among the patent CN1636922, though acrylic acid cheap in the compound method, monomer whose self characteristics of molecular structure makes that the protect plasticity of product can not get improving all the time; Patent CN101434465A discloses the design of a kind of time of coagulation of controlled polycarboxylate water-reducer with synthetic; Design and the water reducer that synthesizes different time of coagulation according to the practical application needs; Reach the purpose of control water reducer slump hold facility, but synthetic water reducer water-reducing rate is lower.These water reducers only are suitable for the use under the general condition, for abominable natural condition, still can't satisfy the requirement of construction.
Summary of the invention
For overcome prior art deficiency; The invention discloses a kind of preparation method of polycarboxylate water-reducer; This method synthetic polycarboxylate water-reducer is started with from the angle of Molecular Selection, structure control; Comprehensively adjusted the protect plasticity and the water-reducing rate of water reducer, realized concrete be difficult to realize simultaneously high diminishing, high function of slump protection, with the good problem of cement adaptability, for Gobi desert environment Concrete Construction provides technical guarantee.
For realizing that above-mentioned purpose the present invention adopts following technical scheme
1, a kind of preparation method of polycarboxylate water-reducer is characterized in that: may further comprise the steps:
(1) poly glycol monomethyl ether MPEG, maleic anhydride MAH, catalyzer toluenesulphonic acids PTSA are put in the reaction kettle; Stir; Normal pressure, temperature are under 90～110 ℃ of conditions esterification to take place, and obtain containing the mixture of poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM, take away moisture through rare gas element as the band aqua in the reaction process; Require esterification yield greatly to more than 90%; Wherein, poly glycol monomethyl ether: maleic anhydride: the mol ratio of toluenesulphonic acids is 1: (1～1.2): (0.01～0.02), and the reaction times is 6～8 hours;
(2) with the poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM, the methallylsulfonic acid sodium MAS that make in the step (1); Be added to the water successively and stir; Be mixed with the mix monomer aqueous solution of (40-60) %; Wherein, the mol ratio of poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM and methallylsulfonic acid sodium MAS is 1: (1～1.2);
(3) take by weighing methylene-succinic acid and be added to the water, stir, be mixed with the methylene-succinic acid monomer solution of (20-30) %;
(4) with H
2O
2Being added to the water with Vitamin C mixture stirs, and is mixed with (20-30) % redox initiator aqueous solution, wherein, and H
2O
2With ascorbic mol ratio be (1.5-2.5): 1;
(5) the methylene-succinic acid aqueous solution of the redox initiator aqueous solution of step (4) configuration and step (3) preparation is added drop-wise in the mix monomer aqueous solution that step (2) prepares through copolyreaction successively; Obtain the required terpolymer aqueous solution; Temperature of reaction is 30～50 ℃; Pressure is normal pressure, 3～4 hours reaction times;
Wherein, poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM: methallylsulfonic acid sodium MAS: the mol ratio of methylene-succinic acid ITA=1: (1-1.2): (1-1.5);
The add-on of redox initiator is the 0.8-1.2% of poly glycol monomethyl ether MPEG, maleic anhydride MAH, catalyzer toluenesulphonic acids PTSA gross weight;
(6) regulate pH=8～9 of the terpolymer aqueous solution with alkali, cooling obtains the poly carboxylic acid series water reducer finished product.
2, the preparation method of polycarboxylate water-reducer according to claim 1 is characterized in that:
Poly glycol monomethyl ether MPEG described in the step (1) is selected from one or more mixing among the different poly glycol monomethyl ether MPEG of four kinds of molecular weight of poly glycol monomethyl ether MPEG400, poly glycol monomethyl ether MPEG800, poly glycol monomethyl ether MPEG1200, poly glycol monomethyl ether MPEG2000; Described esterification temperature is 90 ℃; Reaction time of esterification is 8h; The mol ratio of MPEG: MAH: PTSA is 1: 1.2: 0.012;
The mix monomer concentration of aqueous solution of poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM described in the step (2) and methallylsulfonic acid sodium MAS is 50%;
Step selects for use methylene-succinic acid as polymerization single polymerization monomer in (3), and its concentration of aqueous solution is 20%;
Step is selected " H for use in (4)
2O
2-vitamins C " redox initiator, the concentration of its aqueous solution is 20%, H
2O
2With ascorbic mol ratio be 2: 1;
H
2O
2Account for 1% of poly glycol monomethyl ether MPEG, maleic anhydride MAH, catalyzer toluenesulphonic acids PTSA gross weight with the vitamins C add-on;
40 ℃ of the described polymeric reaction temperatures of step (5), polymerization time 3.5h;
The pH=8 of the described terpolymer aqueous solution of step (6).
The present invention compares with the prior art achievement, has following positive achievement:
(1) the present invention according to maleic anhydride can not homopolymerization characteristics; In the process of esterification synthetic macromolecule monomer PAM, need not add stopper, can not cause negative impact to radical polymerization; Greatly reduce the destructive rate of unsaturated double-bond; Reached the purpose of effectively utilizing polymerization single polymerization monomer, synthetic water reducer effective content increases, and concrete water-reducing rate and function of slump protection strengthen;
(2) in the esterification reaction process of the present invention, take away moisture as the band aqua, simplified the production technique of esterification, make the Product Green environmental protection that is synthesized and with low cost with rare gas element;
(3) be main raw material with the big monomer of esterification activity, methylene-succinic acid, methallylsulfonic acid sodium; Composition through the control multipolymer; Can make the slump retaining and the water-reducing rate of water reducer that a comprehensive adjustment is arranged to a certain extent, solve the big big problem of monomer synthetic control difficulty of activity difference;
(4) the present invention adopts methylene-succinic acid as one of copolymerization principal monomer; Because methylene-succinic acid is the bigger binary unsaturated acid of chemically reactive; The use of this diprotic acid has strengthened the ratio of carboxyl in the main chain, makes poly carboxylic acid gather stronger electric charge, and water-reducing rate and function of slump protection are further enhanced;
(5) adopt " H
2O
2-vitamins C " redox initiation system, both solve ester class water reducer and quoted the middle allochroic characteristics of illumination at the scene, reduced the activation energy of polyreaction again, shortened the time of polyreaction greatly.
(6) this water reducer is developed to great Northwest special geographical environment " Gobi desert environment "; Also be adapted to simultaneously other similar severe environment; Its preparation and invention have enlarged the Application Areas of polycarboxylate water-reducer; Enriched the kind of polycarboxylate water-reducer, for the construction of Gobi desert environment provides technical guarantee.
The method of practical implementation
Embodiment 1
Terpolymer polycarboxylate water-reducer PAM, MAS, the monomeric mol ratio of ITA are 1: (1-1.2): (1-1.5); Be that the implementing method of 1: 1: 1 synthetic polycarboxylate water-reducer is an example with PAM, MAS, ITA mol ratio below, the influence of the proportioning of polymerization single polymerization monomer to concrete performance is discussed;
(1) synthesizing of PAM: with 12000kg MPEG-1200), 1176kg MAH, 20.664kg catalyst P TSA drop into reaction kettle and stir; The mol ratio of control poly glycol monomethyl ether, maleic anhydride, toluenesulphonic acids is 1: 1.2: 0.012; In normal pressure, temperature is that esterification 8h takes place under 90 ℃ of conditions; Take away moisture through rare gas element as the band aqua, esterification yield is 90%, obtains 11682kg poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM; ,
(2), with step (1) 11682kg poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM and 1422kg methallylsulfonic acid sodium MAS, join successively in the 13102kg tap water evenly stir after, the mix monomer aqueous solution of preparation 50%; With 1171kg methylene-succinic acid ITA join the methylene-succinic acid monomer solution of back preparation 20% that stirs in the 4688kg tap water, simultaneously with H
2O
2The tap water of 44kg and vitamins C 99kg and 572kg stirs and prepares 20% " H
2O
2-vitamins C " the redox initiator aqueous solution;
(3) with 20% " H in the step (2)
2O
2-vitamins C " redox initiator aqueous solution 715kg and 20% methylene-succinic acid monomer solution 5859kg all be added drop-wise to the mix monomer aqueous solution 26206kg of preparation 50% in the step (2) successively; and the control temperature of reaction system is at 40 ℃; normal pressure is reaction 3.5h down, obtains the required terpolymer aqueous solution; Add the 20%NaOH aqueous solution, regulate the pH=8 of the terpolymer aqueous solution, cooling obtains the poly carboxylic acid series water reducer finished product.
By of the requirement of Gobi desert environment to high performance concrete, preparation C50 grade concrete.Wherein cement is Tianshan Mountains low alkali cement PO.42.5; Flyash is II ash (fineness 8%, water demand ratio are 105%), and sand is that fineness modulus is 2.8 medium sands (silt contents 2.0%); Stone is 5～20mm continuous grading silt content (0.5%), and the water reducer volume is 1.0% of a gel material content.The proportioning of polymerization single polymerization monomer is to the influence such as the table 1 of concrete performance, and test result is following:
The proportioning of table 1 polymerization single polymerization monomer is to the influence of concrete performance
Can be known by table 1 test result: the mol ratio of PAM/MAS/ITA is 1: 1.2: 1 o'clock, and the concrete slump is minimum through time loss, and water-reducing rate is higher.
Embodiment 2
It is 1: 1.2: 1 that terpolymer polycarboxylate water-reducer PAM, MAS, the monomeric mol ratio of ITA are controlled to be, and the molecular weight that MPEG is discussed is to the influence of the concrete performance of mixing polycarboxylate water-reducer; Be the synthetic polycarboxylate water-reducers of 1200 examples with the MPEG molecule below, other data can be analogized:
(1) PAM's is synthetic: respectively 12000kg MPEG-1200,1176kg MAH, 20.664kg catalyst P TSA are dropped in the reaction kettle and stir; The mol ratio of control poly glycol monomethyl ether, maleic anhydride, toluenesulphonic acids is 1: 1.2: 0.012; In normal pressure, temperature is that esterification 8h takes place under 90 ℃ of conditions; Take away moisture through rare gas element as the band aqua, esterification yield is 90%, obtains 11682kg poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM; ,
(2) with step (1) 11682kg poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM and 1706kg methallylsulfonic acid sodium MAS, join successively in the 13388kg tap water evenly stir after, the mix monomer aqueous solution of preparation 50%; With 1171kg methylene-succinic acid ITA join the methylene-succinic acid monomer solution of back preparation 20% that stirs in the 4688kg tap water, simultaneously with H
2O
2The tap water of 44kg and vitamins C 101kg and 580kg stirs and prepares 20% " H
2O
2-vitamins C " the redox initiator aqueous solution;
(3) with 20% " H in the step (2)
2O
2-vitamins C " redox initiator aqueous solution 725kg and 20% methylene-succinic acid monomer solution 5859kg all be added drop-wise to the mix monomer aqueous solution 26776kg of preparation 50% in the step (2) successively; and the control temperature of reaction system is at 40 ℃; normal pressure is reaction 3.5h down, obtains the required terpolymer aqueous solution; Add the 20%NaOH aqueous solution, regulate the pH=8 of the terpolymer aqueous solution, cooling obtains the poly carboxylic acid series water reducer finished product.
By of the requirement of Gobi desert environment to high performance concrete, preparation C50 grade concrete.Wherein cement is Tianshan Mountains low alkali cement PO.42.5; Flyash is II ash (fineness 8%, water demand ratio are 105%), and sand is that fineness modulus is 2.8 medium sands (silt contents 2.0%); Stone is 5～20mm continuous grading silt content (0.5%), and the water reducer volume is 1.0% of a gel material content.The molecular weight size of poly glycol monomethyl ether is to the influence such as the table 2 of product performance, and test result is following:
Table 2 poly glycol monomethyl ether (MPEG) molecular weight is to the influence of concrete performance
Can find out increase from table 2 test result along with the MPEG molecular weight; Its water-reducing rate, the slump, divergence present elder generation and increase the trend that afterwards reduces; The slump and divergence are little through time loss; When the MPEG molecular weight was 1200, its concrete water-reducing rate was up to 38%, the slump through the time loss minimum.
The comparative example 3
Adopt the synthetic polycarboxylate water-reducer of AA comonomer substitute I TA (methylene-succinic acid), its comonomer PAM, MAS, the monomeric mol ratio of AA are controlled to be 1: 1.2: 1, and the Comparative Examples implementation step is following:
(1) PAM's is synthetic: respectively 1200kg MPEG-1200,117.6kg MAH, 2.0664kg catalyst P TSA are dropped among reaction kettle I, II, III, the IV and stir; The mol ratio of control poly glycol monomethyl ether, maleic anhydride, toluenesulphonic acids is 1: 1.2: 0.012; In normal pressure, temperature is that esterification 8h takes place under 90 ℃ of conditions; Take away moisture through rare gas element as the band aqua, esterification yield is 90%, obtains 1168.2kg poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM; ,
(2) with step (1) 1168.2kg poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM and 170.6kg methallylsulfonic acid sodium MAS, join successively in the 1338.8kg tap water evenly stir after, the mix monomer aqueous solution of preparation 50%; With 64.8kg vinylformic acid AA join the methylene-succinic acid monomer solution of back preparation 20% that stirs in the 259.2kg tap water, simultaneously with H
2O
2Prepare 20% " H 4.3kg stir with the tap water of vitamins C 9.7kg and 56kg
2O
2-vitamins C " the redox initiator aqueous solution;
(3) with 20% " H in the step (2)
2O
2-vitamins C " redox initiator aqueous solution 70kg and 20% Acrylic Acid Monomer aqueous solution 324kg all be added drop-wise to the mix monomer aqueous solution 2677.6kg of preparation 50% in the step (2) successively; and the control temperature of reaction system is at 40 ℃; normal pressure is reaction 3.5h down, obtains the required terpolymer aqueous solution; Add the 20%NaOH aqueous solution, regulate the pH=8 of the terpolymer aqueous solution, cooling obtains the poly carboxylic acid series water reducer finished product.
By of the requirement of Gobi desert environment to high performance concrete, preparation C50 grade concrete.Wherein cement is Tianshan Mountains low alkali cement PO.42.5; Flyash is II ash (fineness 8%; Water demand ratio is 105%), sand is that fineness modulus is 2.8 medium sands (silt contents 2.0%), stone is 5～20mm continuous grading silt content (0.5%); The water reducer volume is 1.0% of a gel material content, and mixing respectively with AA, ITA is that the testing concrete performance result of the synthetic polycarboxylate water-reducer of comonomer is following:
It is the testing concrete performance result of the synthetic polycarboxylate water-reducer of comonomer that table 3 is mixed respectively with AA, ITA
Can be known by table 1 test result: being at 1: 1.2: 1 o'clock in the comonomer mol ratio, is that the concrete water-reducing rate of comonomer synthetic polycarboxylate water-reducer is high with ITA, the slump through the time loss low little, air content is low; And mix with AA is that the concrete water-reducing rate of comonomer synthetic polycarboxylate water-reducer is lower, the slump through the time loss higher, air content is high.
Claims (2)
1. the preparation method of a polycarboxylate water-reducer is characterized in that: may further comprise the steps:
(1) poly glycol monomethyl ether MPEG, maleic anhydride MAH, catalyzer toluenesulphonic acids PTSA are put in the reaction kettle; Stir; Normal pressure, temperature are under 90～110 ℃ of conditions esterification to take place, and obtain containing the mixture of poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM, take away moisture through rare gas element as the band aqua in the reaction process; Require esterification yield greatly to more than 90%; Wherein, poly glycol monomethyl ether: maleic anhydride: the mol ratio of toluenesulphonic acids is 1: (1～1.2): (0.01～0.02), and the reaction times is 6～8 hours;
(2) with the poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM, the methallylsulfonic acid sodium MAS that make in the step (1); Be added to the water successively and stir; Be mixed with the mix monomer aqueous solution of (40-60) %; Wherein, the mol ratio of poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM and methallylsulfonic acid sodium MAS is 1: (1～1.2);
(3) take by weighing methylene-succinic acid and be added to the water, stir, be mixed with the methylene-succinic acid monomer solution of (20-30) %;
(4) with H
2O
2Being added to the water with Vitamin C mixture stirs, and is mixed with (20-30) % redox initiator aqueous solution, wherein, and H
2O
2With ascorbic mol ratio be (1.5-2.5): 1;
(5) the methylene-succinic acid aqueous solution of the redox initiator aqueous solution of step (4) configuration and step (3) preparation is added drop-wise in the mix monomer aqueous solution that step (2) prepares through copolyreaction successively; Obtain the required terpolymer aqueous solution; Temperature of reaction is 30～50 ℃; Pressure is normal pressure, 3～4 hours reaction times;
Wherein, poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM: methallylsulfonic acid sodium MAS: the mol ratio of methylene-succinic acid ITA=1: (1-1.2): (1-1.5);
The add-on of redox initiator is the 0.8-1.2% of poly glycol monomethyl ether MPEG, maleic anhydride MAH, catalyzer toluenesulphonic acids PTSA gross weight;
(6) regulate pH=8～9 of the terpolymer aqueous solution with alkali, cooling obtains the poly carboxylic acid series water reducer finished product.
2. the preparation method of polycarboxylate water-reducer according to claim 1 is characterized in that:
Poly glycol monomethyl ether MPEG described in the step (1) is selected from one or more mixing among the different poly glycol monomethyl ether MPEG of four kinds of molecular weight of poly glycol monomethyl ether MPEG400, poly glycol monomethyl ether MPEG800, poly glycol monomethyl ether MPEG1200, poly glycol monomethyl ether MPEG2000; Described esterification temperature is 90 ℃; Reaction time of esterification is 8h; The mol ratio of MPEG: MAH: PTSA is 1: 1.2: 0.012;
The mix monomer concentration of aqueous solution of poly glycol monomethyl ether toxilic acid surface-active macromonomer PAM described in the step (2) and methallylsulfonic acid sodium MAS is 50%;
Step selects for use methylene-succinic acid as polymerization single polymerization monomer in (3), and its concentration of aqueous solution is 20%;
Step is selected " H for use in (4)
2O
2-vitamins C " redox initiator, the concentration of its aqueous solution is 20%, H
2O
2With ascorbic mol ratio be 2: 1;
H
2O
2Account for 1% of poly glycol monomethyl ether MPEG, maleic anhydride MAH, catalyzer toluenesulphonic acids PTSA gross weight with the vitamins C add-on;
40 ℃ of the described polymeric reaction temperatures of step (5), polymerization time 3.5h;
The pH=8 of the described terpolymer aqueous solution of step (6).
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| CN102585207A (en) * | 2011-09-14 | 2012-07-18 | 长沙加美乐素化工有限公司 | Preparation method of midbody of polycarboxylic acid water reducer |
| CN102807653B (en) * | 2012-08-21 | 2014-09-17 | 南京瑞迪高新技术有限公司 | Co-polycarboxylic acid high efficiency water reducer capable of compounding with naphthalene formaldehyde water reducer and method for preparing same |
| CN104193215B (en) * | 2014-09-02 | 2017-01-11 | 武汉理工大学 | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof |
| CN104829159B (en) * | 2015-03-24 | 2017-12-05 | 中铁四局集团有限公司 | A kind of template self-compacting concrete special slow release controllable type polycarboxylate water-reducers of CRTS III |
| CN105254819A (en) * | 2015-10-15 | 2016-01-20 | 中铁四局集团有限公司 | Room-temperature preparation method of early strength type polycarboxylate superplasticizer |
| CN106883403A (en) * | 2017-04-10 | 2017-06-23 | 甘肃九桓新材料有限公司白银分公司 | The preparation method of maleic acid mono alkyl ester polyether |
| CN116082624A (en) * | 2018-05-21 | 2023-05-09 | 上海联陆实业股份有限公司 | Preparation method for synthesizing water-soluble vitamin E polyethylene glycol succinate without solvent |
| CN113683736A (en) * | 2021-08-10 | 2021-11-23 | 安徽海螺新材料科技有限公司 | Viscosity reduction type polycarboxylate superplasticizer for high-strength concrete and preparation method thereof |
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| EP1200368A1 (en) * | 1999-06-15 | 2002-05-02 | W.R. Grace & Co.-Conn. | High early strength cement and additives and methods for making the same |
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