CN103992442A - Preparation method and application for amphoteric polycarboxylate water reducer containing anions and cations - Google Patents
Preparation method and application for amphoteric polycarboxylate water reducer containing anions and cations Download PDFInfo
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- CN103992442A CN103992442A CN201410179752.9A CN201410179752A CN103992442A CN 103992442 A CN103992442 A CN 103992442A CN 201410179752 A CN201410179752 A CN 201410179752A CN 103992442 A CN103992442 A CN 103992442A
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- polyethenoxy ether
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- allyl polyethenoxy
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Abstract
The invention discloses a preparation method and application for an amphoteric polycarboxylate water reducer containing anions and cations. The method is designed through a high-molecular structure, and the quaternary-ammonium-salt type carboxylate water reducer terminated with a cation is synthesized by performing modification on allyl polyethenoxy ether. According to the synthesized water reducer, anionic charges and cationic charges are both introduced into the molecular structure of the water reducer, when the water reducer is added into cement slurry, anionic charges at the main chain are adsorbed on the surface of cement particles with positive charges, and the anionic charges at the terminals of side chains are adsorbed on the surface of cement particles with negative charges, so that cement particles are dispersed. Cations are capable of inhibiting expansion of soil, so that adsorption of soil to additives is reduced. Because of the unique amphoteric structure of the water reducer, the water reducer possesses unique dispersing capability, high water reducing rate, good slump maintenance property and excellent performances. Also, the invention provides the amphoteric polycarboxylate water reducer prepared by employing the method, and application of the water reducer to concrete.
Description
Technical field
The present invention relates to a kind of preparation method of the reinforcement of concrete additive, especially a kind of preparation method of the reinforcement of concrete polycarboxylate water-reducer.
Background technology
Poly carboxylic acid series water reducer, as the new high performance water-reducing agent of releasing after naphthalene system, fatty family and amidosulfonic acid salt based water reducer, there is the outstanding advantages such as water-reducing rate is high, cement granules good dispersity, volume is low, concrete contraction percentage is low, molecular structure adjustability strong, high performance potentiality are large, be successfully applied in a series of Important Project such as high-speed railway, bridge, tunnel, dam at present.Yet high-efficiency water-reducing agent of poly-carboxylic acid has also run into a lot of technical barriers in actual applications, as to the adaptability of cement/adulterant, susceptibility to water reducer consumption and water consumption, and the impact equity of the aspect such as the silt content of gathering materials, temperature.
High performance water reducing agent of polyocarboxy acid is the multipolymer of a class ionic comb-type structure, different from the bridge joint mode between side chain according to main chain in comb-type structure, polycarboxylate water-reducer can be divided into lipid (side chain is connected with main chain with ester bond-COO-) and ethers (side chain is connected with main chain with ehter bond-O-), in poly carboxylic acid molecular structure, the grafting mode of master chain has very large impact to the performance of polycarboxylic acid graft copolymer.Ester class polycarboxylate water-reducer mostly is (methyl) vinylformic acid and methoxy poly (ethylene glycol) (methyl) acrylate macromonomer copolymerization and the macromolecular compound that obtains; Ethers polycarboxylic acid water reducing agent is mainly that allyl polyglycol and other monomer polymerization form high polymer.
Research report about polycarboxylate water-reducer is a lot, as side chain lengths, and electric density, the main chain polymerization degree, and functional group composition etc., but nearly all comb type polycarboxylate water-reducer all belongs to anionic polymer, other type, as both sexes or cationic admixture rarely have report.The preparation research of new type amphoteric polycarboxylate water-reducer becomes the study hotspot in concrete admixture field gradually.
About the study on the synthesis of both sexes polycarboxylate water-reducer, there are some reports.But be mainly synthesizing aminated or amides poly carboxylic acid both sexes water reducer, this class water reducer and cement, the dispersiveness of adulterant, adaptability are better, and slump retentivity is better, and shortcoming is that amides is unstable under highly basic condition, easily decomposes.
The water-reducing property of polycarboxylate water-reducer depends primarily on sterically hindered effect.
Common polycarboxylate water-reducer is the comb-shaped polymer that a kind of main chain being polymerized by electronegative methacrylic acid and peg molecule side chain form.In cement slurry, add polycarboxylate water-reducer, can be adsorbed on the surface of hydrated cementitious particle with the main chain of negative charge, side chain is stretched in cement slurry solution.The molecular side chain of polyoxyethylene glycol is longer, is more conducive to the dispersion of cement particle, and reason is that the steric exclusion power between the cement particle of absorption water reducer strengthens.The sterically hindered effect of side chain provides the dispersion force between cement granules.
In cement granules, comprise multiple grog phase, some cement granules are because C
2s and C
3siO in S
-group and on surface with negative charge.Other cement granules is because aluminium phase (C
3a) and iron phase (C
4aF) existence and on surface with positive charge.These different electric charges cause the reunion that cement granules is strong because there is a natural attraction between the sexes, cause concrete flowability to decline.
Common polycarboxylate water-reducer is responsive to earth.While running into earth, the negatively charged ion main chain of polycarboxylate water-reducer molecule is adsorbed on the cement particle surface with positive charge, and PEO side chain is inserted in the laminate structure of earth of expansion, and chain intercalation occurs.
The anionic polymer main chain of poly carboxylic acid is adsorbed on the cationic surface of cement granules, and the positively charged region of cement granules is neutralized by poly carboxylic acid.Subsequently, due to the sterically hindered and hydrophilic effects of side-chain of polyelycol, the dispersion of cement granules aggravation.
Research shows, the adsorptive capacity of polycarboxylate water-reducer is electrically charged relevant with cement minerals surface institute.Mineral C
3a and C
4aF surface, generally with positive charge, is conducive to its absorption to polycarboxylate water-reducer molecule, and mineral C
2s and C
3s surface, generally with negative charge, is often suppressed the absorption of polycarboxylate water-reducer molecule.
Compare with traditional water reducer, the advantage of polycarboxylate water-reducer maximum is that in its molecular structure, distinctive long side chain makes it have sterically hindered effect, thereby can be under relatively low volume, practical requirement.The superiority of polycarboxylate water-reducer is many-sided.Yet user finds in application process, the existence meeting of clay class has a negative impact to the effectiveness of polycarboxylate water-reducer, and then affects concrete performance.Clay has the characteristic of water-swelling, while containing clay in cement slurry, for reaching identical serviceability, need to increase unit consumption of water.Clay surface is with negative charge.Clay is approximately 100 times of cement to the adsorptive capacity of polycarboxylate water-reducer.The existence of polynite class objectionable impurities, the serious dispersing property that reduces conventional Polycarboxylic Superplasticizer.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art part and provide a kind of and introduce negatively charged ion and cationic charge simultaneously, there is unique both sexes structure, concrete is had the preparation method of better dispersive ability and the high negative and positive both sexes polycarboxylate water-reducer of water-reducing rate; Meanwhile, the present invention also provides a kind of adopt negative and positive both sexes polycarboxylate water-reducer that described method prepares and the application in concrete thereof.
For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method of negative and positive both sexes polycarboxylate water-reducer, comprises the following steps:
(1) the large monomer of chlorination allyl polyethenoxy ether is synthetic: in the four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, add tetrahydrofuran (THF), allyl polyethenoxy ether, 1,6-dichloro hexane, stopper and KOH powder, rising temperature to tetrahydrofuran (THF) refluxes, under reflux conditions react 24 ~ 30h, be cooled to room temperature, remove by filter KOH powder, tetrahydrofuran (THF) is removed in underpressure distillation, obtains the large monomer of chlorination allyl polyethenoxy ether;
(2) the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether is synthetic: quaternary ammonium salinization reactant and stopper are added in there-necked flask, be warming up to 75 ~ 85 ℃, the quaternary ammonium salinization reactant solution of the large monomer of chlorination allyl polyethenoxy ether that slowly dropping step (1) prepares, after dropwising, under 75 ~ 85 ℃ of conditions, continue insulation reaction 24 ~ 36h, unreacted excessive quaternary ammonium salinization reactant is removed in distillation, obtains the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether;
(3) negative and positive both sexes polycarboxylate water-reducer is synthetic: in the four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, the mixed solution that adds the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate that deionized water, molecular weight regulator, step (2) make, be warming up to 85 ~ 95 ℃, drip the aqueous solution of initiator, time for adding is 2 ~ 3h, after dropwising, insulation reaction 2 ~ 4h, be cooled to 50 ~ 45 ℃, regulating pH is 7.0 ~ 8.0, obtains negative and positive both sexes polycarboxylate water-reducer.
In the preparation method of negative and positive both sexes polycarboxylate water-reducer of the present invention, by macromolecular structure, design, through allyl polyethenoxy ether is carried out to modification, synthesized the quaternary carboxylic acid water reducer of positively charged ion end-blocking.The water reducer of synthesized has been introduced negatively charged ion and cationic charge in molecular structure simultaneously.When product of the present invention joins in concrete, anionic polymer main chain is adsorbed on positively charged cement particle surface, the positively charged region of cement granules is neutralized by poly carboxylic acid, the positively charged ion end group of side chain is adsorbed on electronegative cement particle surface, the electronegative region of cement granules is neutralized by poly carboxylic acid, stop the reunion that has suppressed to inhale mutually because of the charges of different polarity cement granules causing, disperse cement granules, improve concrete mobility.Just because of the both sexes structure of its this uniqueness, make it there is unique dispersive ability, water-reducing rate is high, and slump retentivity is good, superior performance.
Preferred implementation as the preparation method of negative and positive both sexes polycarboxylate water-reducer of the present invention, allyl polyethenoxy ether, 1 in described step (1), the mol ratio of 6-dichloro hexane and KOH powder is allyl polyethenoxy ether: 1,6-dichloro hexane: KOH powder=0.5:0.35 ~ 0.4:50 ~ 100, the molar weight of described stopper is 0.02 ~ 0.06% of allyl polyethenoxy ether molar weight.In described step (1), the amount of tetrahydrofuran (THF) is that those skilled in the art add according to demand, generally, when the four-hole boiling flask in described step (1) is 1000ml, the amount of the tetrahydrofuran (THF) adding is 600ml, the add-on of certain described tetrahydrofuran (THF) is not limited to this, and those skilled in the art are choose reasonable according to actual needs.
As the preparation method's of negative and positive both sexes polycarboxylate water-reducer of the present invention preferred implementation, the molecular weight of described allyl polyethenoxy ether is 2500 ~ 5000; Described stopper is Resorcinol.
Preferred implementation as the preparation method of negative and positive both sexes polycarboxylate water-reducer of the present invention, in described step (2), the volume of quaternary ammonium salinization reactant is 200ml:0.02 ~ 0.06mmol with stopper molar weight ratio, in the quaternary ammonium salinization reactant solution of the large monomer of described chlorination allyl polyethenoxy ether, the volume ratio of the molar weight of the large monomer of chlorination allyl polyethenoxy ether and quaternary ammonium salinization reactant is 1mol:300ml, and the mol ratio of described stopper and the large monomer of chlorination allyl polyethenoxy ether is 0.02 ~ 0.06:1.0.
As the preparation method's of negative and positive both sexes polycarboxylate water-reducer of the present invention preferred implementation, the quaternary ammonium salinization reactant in described step (2) is triethylamine, Trimethylamine 99, N, N-dimethyl amine, N, N-diethyl methylamine or pyridine; Stopper is Resorcinol.
Preferred implementation as the preparation method of negative and positive both sexes polycarboxylate water-reducer of the present invention, in described step (3), the mol ratio of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate is 1:1:1.0 ~ 1.5:0.4 ~ 0.8, and the molar weight of molecular weight regulator is 1 ~ 5% of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate integral molar quantity.In described step (3), the amount of deionized water is that those skilled in the art can rationally determine according to actual needs, generally, when in described step (3), the volume of four-hole boiling flask is 1000ml, the deionized water that can add 500ml, the add-on of certain described deionized water is not limited to this, and those skilled in the art are choose reasonable according to actual needs.
As the preparation method's of negative and positive both sexes polycarboxylate water-reducer of the present invention preferred implementation, in described step (3), molecular weight regulator is at least one in 3-thiohydracrylic acid, Thiovanic acid, mercaptoethanol, Virahol; The mass concentration of the aqueous solution of initiator is 10% ~ 20%, and described initiator is Potassium Persulphate, ammonium persulphate or benzoyl peroxide.
As the preparation method's of negative and positive both sexes polycarboxylate water-reducer of the present invention preferred implementation, in described step (3), adopting NaOH that mass concentration is 30% to regulate pH is 7.0 ~ 8.0.
In addition, the present invention also provides a kind of employing negative and positive both sexes polycarboxylate water-reducer that method prepares as mentioned above.Negative and positive both sexes polycarboxylate water-reducer provided by the present invention, peg molecule side chain end group in molecular structure is positively charged ion, cation-adsorption is on electronegative cement particle surface on the one hand, the reunion that inhibition inhales because of the charges of different polarity cement granules causing mutually, on the other hand, positively charged ion can suppress the expansion of earth, make the side-chain of polyelycol of polycarboxylate water-reducer intercalation not occur to connect with earth, thereby reduce the absorption of earth to admixture, improve the tolerance of polycarboxylate water-reducer to earth.When negative and positive both sexes polycarboxylate water-reducer of the present invention joins in cement slurry, the anionic charge of main chain is adsorbed on positively charged cement particle surface, and the positive charge of side chain end group is adsorbed on electronegative cement particle surface, disperses cement granules.When negative and positive both sexes polycarboxylate water-reducer of the present invention is applied in concrete as water reducer, negative and positive both sexes polycarboxylate water-reducer molecular backbone of the present invention is adsorbed on cement particle surface securely, the hydration reaction that can effectively suppress cement, improve its protect plasticity, side chain is enclosed in cement granules surrounding, be adsorbed on electronegative cement particle surface simultaneously, play sterically hindered and dual function electrostatic repulsion, this disperses the mechanism of cement granules completely different from traditional water reducer by electrostatic repulsion, thereby there is better dispersive ability and water-reducing effect, finally make the over-all properties of concrete product obtain qualitative leap.
Finally, the present invention also provides the application of a kind of both sexes of negative and positive as mentioned above polycarboxylate water-reducer in concrete.When negative and positive both sexes polycarboxylate water-reducer of the present invention is used for concrete, compare with existing common polycarboxylate water-reducer, cement slurry is had to better dispersiveness, water-reducing rate improves, positively charged ion due to side chain end group has restraining effect to the absorption of clay simultaneously, thereby has certain resistance to mud guarantor effect of collapsing.
The preparation method of negative and positive both sexes polycarboxylate water-reducer of the present invention, by macromolecular structure, design, through allyl polyethenoxy ether is carried out to modification, the quaternary polycarboxylate water-reducer that has synthesized positively charged ion end-blocking, this water reducer has been introduced negatively charged ion and cationic charge in molecular structure simultaneously, have unique both sexes structure, described method is simple to operate, is convenient to suitability for industrialized production.The negative and positive both sexes polycarboxylate water-reducer that adopts the method for the invention to prepare, has the following advantages:
(1) insensitive to earth, common polycarboxylate water-reducer is responsive to earth, and while running into earth, the negatively charged ion main chain of polycarboxylate water-reducer molecule is adsorbed on the cement particle surface with positive charge, PEO side chain is inserted in the laminate structure of earth of expansion, and chain intercalation occurs.Mud particles surface is with negative charge, cationic side chain end group in products molecule of the present invention is adsorbed on mud particles surface, suppressing earth expands, make PEO side chain that chain intercalation not occur, solved the sensitive question of existing common polycarboxylate water-reducer to earth, having improved the tolerance of polycarboxylate water-reducer to earth, is the water reducer of resistance to chamotte mould;
(2) dispersing property is good, the PEO side chain of negative and positive both sexes polycarboxylate water-reducer of the present invention is positively charged ion end-blocking, when the negatively charged ion main chain of negative and positive both sexes polycarboxylate water-reducer of the present invention is adsorbed on positively charged cement particle surface, when the positively charged ion end group of side chain is adsorbed on electronegative cement particle surface, therefore the PEO side chain of negative and positive both sexes polycarboxylate water-reducer of the present invention has sterically hindered dual additive effect of inhaling mutually with the charges of different polarity, can effectively stop the reunion of cement granules, improved the dispersiveness to cement granules, it is good cement dispersants, concrete slump retention agent,
(3) water-reducing rate improves, and the water-reducing effect of polycarboxylate water-reducer depends primarily on its space steric effect, and electrostatic repulsion between the positively charged ion end group of negative and positive both sexes polycarboxylate water-reducer side chain of the present invention makes sterically hindered increase, thereby has improved water-reducing rate.
Embodiment
For the object, technical solutions and advantages of the present invention are better described, below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of embodiment of negative and positive both sexes polycarboxylate water-reducer of the present invention, negative and positive both sexes polycarboxylate water-reducer adopts following methods to be prepared from described in the present embodiment:
(1) the large monomer of chlorination allyl polyethenoxy ether is synthetic: in the 1000ml four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, add 600ml tetrahydrofuran (THF), allyl polyethenoxy ether (molecular weight is 2500 ~ 5000), 1,6-dichloro hexane, stopper (Resorcinol) and KOH powder, rising temperature to tetrahydrofuran (THF) refluxes, under reflux conditions react 24 ~ 30h, be cooled to room temperature, remove by filter KOH powder, tetrahydrofuran (THF) is removed in underpressure distillation, obtains the large monomer of chlorination allyl polyethenoxy ether;
(2) the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether is synthetic: triethylamine and stopper (Resorcinol) are added in there-necked flask, be warming up to 75 ~ 85 ℃, the triethylamine solution of the large monomer of chlorination allyl polyethenoxy ether that slowly dropping step (1) prepares, after dropwising, under 75 ~ 85 ℃ of conditions, continue insulation reaction 24 ~ 36h, unreacted excess of triethylamine is removed in distillation, obtains the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether;
(3) negative and positive both sexes polycarboxylate water-reducer is synthetic: agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add 500ml deionized water, 3-thiohydracrylic acid, the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether that step (2) makes, maleic anhydride, the mixed solution of allyl polyethenoxy ether and sodium allyl sulfonate, be warming up to 85 ~ 95 ℃, the aqueous solution that to drip mass concentration be 10%, time for adding is 2 ~ 3h, after dropwising, insulation reaction 2 ~ 4h, be cooled to 50 ~ 45 ℃, adopting the NaOH adjusting pH that mass concentration is 30% is 7.0 ~ 8.0, obtain negative and positive both sexes polycarboxylate water-reducer.
Allyl polyethenoxy ether, 1 in step described in the present embodiment (1), the mol ratio of 6-dichloro hexane and KOH powder is allyl polyethenoxy ether: 1,6-dichloro hexane: KOH powder=0.5:0.35:50, the molar weight of stopper is 0.02% of allyl polyethenoxy ether molar weight; In described step (2), the volume of quaternary ammonium salinization reactant is 200ml:0.02mmol with stopper molar weight ratio, in the quaternary ammonium salinization reactant solution of the large monomer of chlorination allyl polyethenoxy ether, the volume ratio of the molar weight of the large monomer of chlorination allyl polyethenoxy ether and quaternary ammonium salinization reactant is 1mol:300ml, and the mol ratio of stopper and the large monomer of chlorination allyl polyethenoxy ether is 0.02:1.0; In described step (3), the mol ratio of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate is 1:1:1:0.4, and the molar weight of 3-thiohydracrylic acid is 1% of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate integral molar quantity.
Embodiment 2
A kind of embodiment of negative and positive both sexes polycarboxylate water-reducer of the present invention, negative and positive both sexes polycarboxylate water-reducer adopts following methods to be prepared from described in the present embodiment:
(1) the large monomer of chlorination allyl polyethenoxy ether is synthetic: in the 1000ml four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, add 600ml tetrahydrofuran (THF), allyl polyethenoxy ether (molecular weight is 2500 ~ 5000), 1,6-dichloro hexane, stopper (Resorcinol) and KOH powder, rising temperature to tetrahydrofuran (THF) refluxes, under reflux conditions react 24 ~ 30h, be cooled to room temperature, remove by filter KOH powder, tetrahydrofuran (THF) is removed in underpressure distillation, obtains the large monomer of chlorination allyl polyethenoxy ether;
(2) the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether is synthetic: Trimethylamine 99 and stopper (Resorcinol) are added in there-necked flask, be warming up to 75 ~ 85 ℃, the trimethylamine solution of the large monomer of chlorination allyl polyethenoxy ether that slowly dropping step (1) prepares, after dropwising, under 75 ~ 85 ℃ of conditions, continue insulation reaction 24 ~ 36h, unreacted excessive Trimethylamine 99 is removed in distillation, obtains the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether;
(3) negative and positive both sexes polycarboxylate water-reducer is synthetic: agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add 500ml deionized water, Thiovanic acid, the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether that step (2) makes, maleic anhydride, the mixed solution of allyl polyethenoxy ether and sodium allyl sulfonate, be warming up to 85 ~ 95 ℃, the aqueous solution of the ammonium persulphate that dropping mass concentration is 20%, time for adding is 2 ~ 3h, after dropwising, insulation reaction 2 ~ 4h, be cooled to 50 ~ 45 ℃, adopting the NaOH adjusting pH that mass concentration is 30% is 7.0 ~ 8.0, obtain negative and positive both sexes polycarboxylate water-reducer.
Allyl polyethenoxy ether, 1 in step described in the present embodiment (1), the mol ratio of 6-dichloro hexane and KOH powder is allyl polyethenoxy ether: 1,6-dichloro hexane: KOH powder=0.5:0.4:100, the molar weight of stopper is 0.04% of allyl polyethenoxy ether molar weight; In described step (2), the volume of quaternary ammonium salinization reactant is 200ml:0.06mmol with stopper molar weight ratio, in the quaternary ammonium salinization reactant solution of the large monomer of chlorination allyl polyethenoxy ether, the volume ratio of the molar weight of the large monomer of chlorination allyl polyethenoxy ether and quaternary ammonium salinization reactant is 1mol:300ml, and the mol ratio of stopper and the large monomer of chlorination allyl polyethenoxy ether is 0.02:1.0; In described step (3), the mol ratio of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate is 1:1:1.5:0.8, and the molar weight of Thiovanic acid is 5% of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate integral molar quantity.
Embodiment 3
A kind of embodiment of negative and positive both sexes polycarboxylate water-reducer of the present invention, negative and positive both sexes polycarboxylate water-reducer adopts following methods to be prepared from described in the present embodiment:
(1) the large monomer of chlorination allyl polyethenoxy ether is synthetic: in the 1000ml four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, add 600ml tetrahydrofuran (THF), allyl polyethenoxy ether (molecular weight is 2500 ~ 5000), 1,6-dichloro hexane, stopper (Resorcinol) and KOH powder, rising temperature to tetrahydrofuran (THF) refluxes, under reflux conditions react 24 ~ 30h, be cooled to room temperature, remove by filter KOH powder, tetrahydrofuran (THF) is removed in underpressure distillation, obtains the large monomer of chlorination allyl polyethenoxy ether;
(2) the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether is synthetic: by N, N-dimethyl amine and stopper (Resorcinol) add in there-necked flask, be warming up to 75 ~ 85 ℃, the N of the large monomer of chlorination allyl polyethenoxy ether that slowly dropping step (1) prepares, N-dimethyl amine solution, after dropwising, under 75 ~ 85 ℃ of conditions, continue insulation reaction 24 ~ 36h, unreacted excessive N is removed in distillation, N-dimethyl amine, obtains the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether;
(3) negative and positive both sexes polycarboxylate water-reducer is synthetic: agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add 500ml deionized water, mercaptoethanol, the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether that step (2) makes, maleic anhydride, the mixed solution of allyl polyethenoxy ether and sodium allyl sulfonate, be warming up to 85 ~ 95 ℃, the aqueous solution of the benzoyl peroxide that dropping mass concentration is 15%, time for adding is 2 ~ 3h, after dropwising, insulation reaction 2 ~ 4h, be cooled to 50 ~ 45 ℃, adopting the NaOH adjusting pH that mass concentration is 30% is 7.0 ~ 8.0, obtain negative and positive both sexes polycarboxylate water-reducer.
Allyl polyethenoxy ether, 1 in step described in the present embodiment (1), the mol ratio of 6-dichloro hexane and KOH powder is allyl polyethenoxy ether: 1,6-dichloro hexane: KOH powder=0.5:0.36:60, the molar weight of stopper is 0.06% of allyl polyethenoxy ether molar weight; In described step (2), the volume of quaternary ammonium salinization reactant is 200ml:0.04mmol with stopper molar weight ratio, in the quaternary ammonium salinization reactant solution of the large monomer of chlorination allyl polyethenoxy ether, the volume ratio of the molar weight of the large monomer of chlorination allyl polyethenoxy ether and quaternary ammonium salinization reactant is 1mol:300ml, and the mol ratio of stopper and the large monomer of chlorination allyl polyethenoxy ether is 0.06:1.0; In described step (3), the mol ratio of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate is 1:1:1.2:0.5, and the molar weight of mercaptoethanol is 2% of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate integral molar quantity.
Embodiment 4
A kind of embodiment of negative and positive both sexes polycarboxylate water-reducer of the present invention, negative and positive both sexes polycarboxylate water-reducer adopts following methods to be prepared from described in the present embodiment:
(1) the large monomer of chlorination allyl polyethenoxy ether is synthetic: in the 1000ml four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, add 600ml tetrahydrofuran (THF), allyl polyethenoxy ether (molecular weight is 2500 ~ 5000), 1,6-dichloro hexane, stopper (Resorcinol) and KOH powder, rising temperature to tetrahydrofuran (THF) refluxes, under reflux conditions react 24 ~ 30h, be cooled to room temperature, remove by filter KOH powder, tetrahydrofuran (THF) is removed in underpressure distillation, obtains the large monomer of chlorination allyl polyethenoxy ether;
(2) the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether is synthetic: pyridine and stopper (Resorcinol) are added in there-necked flask, be warming up to 75 ~ 85 ℃, the pyridine of the large monomer of chlorination allyl polyethenoxy ether that slowly dropping step (1) prepares, after dropwising, under 75 ~ 85 ℃ of conditions, continue insulation reaction 24 ~ 36h, unreacted excess pyridine is removed in distillation, obtains the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether;
(3) negative and positive both sexes polycarboxylate water-reducer is synthetic: agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add 500ml deionized water, Virahol, the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether that step (2) makes, maleic anhydride, the mixed solution of allyl polyethenoxy ether and sodium allyl sulfonate, be warming up to 85 ~ 95 ℃, the aqueous solution of the Potassium Persulphate that dropping mass concentration is 18%, time for adding is 2 ~ 3h, after dropwising, insulation reaction 2 ~ 4h, be cooled to 50 ~ 45 ℃, adopting the NaOH adjusting pH that mass concentration is 30% is 7.0 ~ 8.0, obtain negative and positive both sexes polycarboxylate water-reducer.
Allyl polyethenoxy ether, 1 in step described in the present embodiment (1), the mol ratio of 6-dichloro hexane and KOH powder is allyl polyethenoxy ether: 1,6-dichloro hexane: KOH powder=0.5:0.38:80, the molar weight of stopper is 0.05% of allyl polyethenoxy ether molar weight; In described step (2), the volume of quaternary ammonium salinization reactant is 200ml:0.05mmol with stopper molar weight ratio, in the quaternary ammonium salinization reactant solution of the large monomer of chlorination allyl polyethenoxy ether, the volume ratio of the molar weight of the large monomer of chlorination allyl polyethenoxy ether and quaternary ammonium salinization reactant is 1mol:300ml, and the mol ratio of stopper and the large monomer of chlorination allyl polyethenoxy ether is 0.04:1.0; In described step (3), the mol ratio of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate is 1:1:1.4:0.6, and the molar weight of Virahol is 4% of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate integral molar quantity.
Embodiment 5
The application test of negative and positive both sexes polycarboxylate water-reducer of the present invention in concrete
Test sample is the concrete that contains cement, flyash, breeze, river sand, water, polycarboxylate water-reducer, and in described concrete, the mass ratio of each composition is:
Cement: flyash: breeze: river sand: water: polycarboxylate water-reducer=200:90:60:800:1080:165:7.
Test is divided into invention group and control group, the negative and positive both sexes polycarboxylate water-reducer that invention group adopts the method for the invention to prepare, and control group adopts the existing polycarboxylate water-reducer without positively charged ion end group, is directly purchased from market.
Respectively the concrete performance of invention group and control group is detected, result is:
(1) invention group is compared with control group, although the volume of polycarboxylate water-reducer is identical, the water-reducing rate of invention group water reducer is compared with control group and improved 5 ~ 8%, 2h Slump Time losing of Large rate reduction by 15 ~ 25%.
(2) to the concrete of high silt content (silt content is 5%), invention group is compared with control group, although the volume of polycarboxylate water-reducer is identical, the water-reducing rate of invention group water reducer is compared with control group and improved 10 ~ 15%, 2h Slump Time losing of Large rate reduction by 20 ~ 30%.
From the present embodiment result, the negative and positive both sexes polycarboxylate water-reducer that adopts the method for the invention to prepare, overcome the sensitive question of existing common polycarboxylate water-reducer to earth, improved the tolerance of polycarboxylate water-reducer to earth, it is the water reducer of resistance to chamotte mould, and effective raising of obtaining of water-reducing rate, slump retentivity is good, and performance is more superior.
Last institute should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although the present invention is explained in detail with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a preparation method for negative and positive both sexes polycarboxylate water-reducer, is characterized in that, comprises the following steps:
(1) the large monomer of chlorination allyl polyethenoxy ether is synthetic: in the four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, add tetrahydrofuran (THF), allyl polyethenoxy ether, 1,6-dichloro hexane, stopper and KOH powder, rising temperature to tetrahydrofuran (THF) refluxes, under reflux conditions react 24 ~ 30h, be cooled to room temperature, remove by filter KOH powder, tetrahydrofuran (THF) is removed in underpressure distillation, obtains the large monomer of chlorination allyl polyethenoxy ether;
(2) the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether is synthetic: quaternary ammonium salinization reactant and stopper are added in there-necked flask, be warming up to 75 ~ 85 ℃, the quaternary ammonium salinization reactant solution of the large monomer of chlorination allyl polyethenoxy ether that slowly dropping step (1) prepares, after dropwising, under 75 ~ 85 ℃ of conditions, continue insulation reaction 24 ~ 36h, unreacted excessive quaternary ammonium salinization reactant is removed in distillation, obtains the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether;
(3) negative and positive both sexes polycarboxylate water-reducer is synthetic: in the four-hole boiling flask of agitator, thermometer and reflux condensing tube is housed, the mixed solution that adds the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate that deionized water, molecular weight regulator, step (2) make, be warming up to 85 ~ 95 ℃, drip the aqueous solution of initiator, time for adding is 2 ~ 3h, after dropwising, insulation reaction 2 ~ 4h, be cooled to 50 ~ 45 ℃, regulating pH is 7.0 ~ 8.0, obtains negative and positive both sexes polycarboxylate water-reducer.
2. the preparation method of negative and positive both sexes polycarboxylate water-reducer as claimed in claim 1, it is characterized in that, allyl polyethenoxy ether, 1 in described step (1), the mol ratio of 6-dichloro hexane and KOH powder is allyl polyethenoxy ether: 1,6-dichloro hexane: KOH powder=0.5:0.35 ~ 0.4:50 ~ 100, the molar weight of described stopper is 0.02 ~ 0.06% of allyl polyethenoxy ether molar weight.
3. the preparation method of negative and positive both sexes polycarboxylate water-reducer as claimed in claim 1 or 2, is characterized in that, the molecular weight of described allyl polyethenoxy ether is 2500 ~ 5000; Described stopper is Resorcinol.
4. the preparation method of negative and positive both sexes polycarboxylate water-reducer as claimed in claim 1, it is characterized in that, in described step (2), the volume of quaternary ammonium salinization reactant is 200ml:0.02 ~ 0.06mmol with stopper molar weight ratio, in the quaternary ammonium salinization reactant solution of the large monomer of described chlorination allyl polyethenoxy ether, the volume ratio of the molar weight of the large monomer of chlorination allyl polyethenoxy ether and quaternary ammonium salinization reactant is 1mol:300ml, and the mol ratio of described stopper and the large monomer of chlorination allyl polyethenoxy ether is 0.02 ~ 0.06:1.0.
5. the preparation method of the negative and positive both sexes polycarboxylate water-reducer as described in claim 1 or 4, is characterized in that, the quaternary ammonium salinization reactant in described step (2) is triethylamine, Trimethylamine 99, N, N-dimethyl amine, N, N-diethyl methylamine or pyridine; Stopper is Resorcinol.
6. the preparation method of negative and positive both sexes polycarboxylate water-reducer as claimed in claim 1, it is characterized in that, in described step (3), the mol ratio of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate is 1:1:1.0 ~ 1.5:0.4 ~ 0.8, and the molar weight of molecular weight regulator is 1 ~ 5% of the large monomer of cation quaternary ammonium salt allyl polyethenoxy ether, maleic anhydride, allyl polyethenoxy ether and sodium allyl sulfonate integral molar quantity.
7. the preparation method of negative and positive both sexes polycarboxylate water-reducer as claimed in claim 1, is characterized in that, in described step (3), molecular weight regulator is at least one in 3-thiohydracrylic acid, Thiovanic acid, mercaptoethanol, Virahol; The mass concentration of the aqueous solution of initiator is 10% ~ 20%, and described initiator is Potassium Persulphate, ammonium persulphate or benzoyl peroxide.
8. the preparation method of negative and positive both sexes polycarboxylate water-reducer as claimed in claim 1, is characterized in that, in described step (3), adopting the NaOH adjusting pH that mass concentration is 30% is 7.0 ~ 8.0.
An employing as arbitrary in claim 1 ~ 8 as described in the negative and positive both sexes polycarboxylate water-reducer for preparing of method.
10. the application of negative and positive both sexes polycarboxylate water-reducer in concrete as claimed in claim 9.
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