CN102504238B - Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof - Google Patents

Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof Download PDF

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CN102504238B
CN102504238B CN201110307442.7A CN201110307442A CN102504238B CN 102504238 B CN102504238 B CN 102504238B CN 201110307442 A CN201110307442 A CN 201110307442A CN 102504238 B CN102504238 B CN 102504238B
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monomer
methyl
comb
acid
formula
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CN102504238A (en
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杨勇
刘加平
冉千平
缪昌文
周栋梁
毛永琳
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Lianyungang Subote New Material Co ltd
Sobute New Materials Co Ltd
Nanjing Bote New Materials Co Ltd
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Sobute New Materials Co Ltd
Jiangsu Bote New Materials Co Ltd
Jiangsu Research Institute of Building Science Co Ltd
Nanjing Bote Building Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641Polyacrylates; Polymethacrylates
    • C04B24/2647Polyacrylates; Polymethacrylates containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40Surface-active agents, dispersants
    • C04B2103/408Dispersants

Abstract

The invention relates to an unsaturated polyether monomer, a comb-like branched copolymer cement dispersant prepared by the monomer, and preparation methods of the monomer and the dispersant. The unsaturated polyether monomer has the general formula (I), wherein R1 is H or -CH3; X is a linking group selected from -CH2-, -CH2CH2-, -OCH2CH2-, -OCH2CH2CH2CH2-; AO is ethylene oxide group and/or propene oxide group; l, m and n are all repeating units of AO; and the sum of l, m and n is an natural number of 10 to 50. The dispersant has the following chemical structure (VI), wherein x, y and z represent mole percentages of three structural units in the copolymer, and the sum of x, y and z is 100%. Preferably, x is 10% to 50%, y is 40% to 80% and z is 0% to 30%. The preparation method of the dispersant is simple and does not need organic solvents or complex esterification. The dispersant is advantageous in low dosage, good dispersibility and small slump loss.

Description

A kind of unsaturated polyester ether monomer, adopt comb-branched copolymer cement dispersants prepared by this monomer and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of comb-branched copolymer cement dispersants, monomer used and gained comb-branched copolymer cement dispersants, belong to technical field of concrete additives.
Background technology
In recent years, development along with comb-shaped copolymer cement dispersant, for the construction of the Infrastructure such as high-speed railway, bridge, water power, urban track traffic and airport provides powerful guarantee, promoted further developing of high-strength concrete and Highrise buildings concrete construction simultaneously.
Comb-shaped copolymer cement dispersant is the high molecular weight water soluble polymer that a class has comb shaped structure, is through free-radical polymerized and prepare gained by unsaturated acid and the large monomer of unsaturated active polyether.Its unsaturated acid using mainly comprises unsaturated carboxylic acid (salt) and unsaturated sulfonic acid (salt), as (methyl) vinylformic acid (salt), toxilic acid (acid anhydride), methylene-succinic acid, (methyl) sodium allyl sulfonate, Sodium styrene sulfonate etc., for dispersion agent main chain provides ionic adsorption site, be adsorbed onto after cement particle surface, ionic group makes mutually to have produced between cement granules electrostatic repulsion; The large monomer of unsaturated polyether mainly comprises (methyl) acrylic ester, toxilic acid polyoxyethylene monoesters and dibasic acid esters, allyl polyethenoxy ether, methacrylic Soxylat A 25-7 of different molecular weight etc., it is as the side chain of cement dispersants, bringing into play sterically hindered repulsion, cement granules is difficult to close to each other, thereby dispersiveness and the stability thereof of cement granules have been improved, concrete water cement ratio be can effectively reduce, concrete mobility and mobility hold facility improved.
As the important component part of comb-shaped copolymer cement dispersant, the large monomer of unsaturated polyether is subject to numerous investigators' favor.The large monomers of unsaturated polyether that adopt the synthetic different structure of the whole bag of tricks have been reported in many research, and for the preparation of comb-shaped copolymer cement dispersant.This type of cement dispersants has improved mobility and the slump retentivity of fresh concrete to a certain extent, but the deficiency existing is, the basic structure of the large monomer of unsaturated polyether is double bond containing single polyoxyalkylene long-chain, after copolymerization, in dispersant molecule, bring into play the limited in one's ability of sterically hindered effect, thereby the higher volume of the general needs of comb-shaped copolymer cement dispersant of the type could effectively improve concrete and newly mix performance.
Patent US2004/0204517 has reported that employing vinyl carbinol and methallyl alcohol are initiator, with ethyleneoxide addition, the strand allyl polyethenoxy ether and the methacrylic Soxylat A 25-7 that have synthesized different molecular weight, then carry out free-radical polymerizedly with the toxilic acid of different ratios and Hydroxyethyl acrylate, prepared polycarboxylate water-reducer.During 0.3% left and right that this polycarboxylate water-reducer volume is cement quality, just there is good dispersive ability and slump hold facility.
It is raw material that patent CN100545118 be take the different molecular weight allyl polyglycol of strand and maleic anhydride, methyl acrylate, has synthesized polycarboxylate water-reducer, can make cement paste have good degree of mobilization and degree of mobilization hold facility.
Patent EP1179517, first with methallyl alcohol and reacting ethylene oxide, has prepared the methyl allyl alcohol polyoxyethylene ether of different molecular weight, and then the vinylformic acid with methyl allyl alcohol polyoxyethylene ether and different ratios carries out copolymerization, has synthesized polycarboxylate water-reducer.This water reducer is cement quality at volume 0.18%~0.25% time, have good initial dispersion ability, but the slump hold facility of 30min is limited.
Patent CN101492518 report has synthesized a kind of ethers polycarboxylic acid water reducing agent, and it adopts molecular weight is that 2000~3000 strand allyl polyethenoxy ether and vinylformic acid, Hydroxyethyl acrylate carry out copolyreaction, has prepared ethers polycarboxylic acid water reducing agent.This water reducer volume be cement gross weight 0.5% time, show good slump hold facility.
Summary of the invention
The object of the present invention is to provide a kind of unsaturated polyester ether monomer, adopt comb-branched copolymer cement dispersants prepared by this monomer and preparation method thereof, gained comb-shaped copolymer cement dispersant volume is low, can effectively improve cement dispersiveness and dispersion stabilization thereof.
Following general formula for the chemical structure of unsaturated polyester ether monomer of the present invention (I) represents:
Figure BDA0000097555870000021
R in formula 1for H or-CH 3; X is linking group, for-CH 2-,-CH 2cH 2-,-OCH 2cH 2-,-OCH 2cH 2cH 2cH 2-or aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10~50.
The preparation method of above-mentioned unsaturated polyester ether monomer comprises the steps:
(1) by compound d and the monoethanolamine shown in formula (III), carry out opening, obtain the intermediate e shown in formula (IV);
Figure BDA0000097555870000031
(2) take intermediate e as initiator, under the effect of catalyzer, carry out alkoxylation with the epoxide f shown in formula (V), obtain unsaturated polyester ether monomer a;
Figure BDA0000097555870000032
Described step 1) mol ratio that in, compound d and monoethanolamine carry out opening is preferably 1: 1, preferred concrete operation method is: the compound d shown in formula (III) is added dropwise to lentamente in the monoethanolamine that continues to stir, dropping temperature is 60~80 ℃, time for adding is 4~8h, and dripping the follow-up continuous soaking time of end is 1~4h.
Described step 2) in, epoxide f is the mixture of one or both arbitrary proportions in oxyethane (EO), propylene oxide (PO), its can be separately or with arbitrary proportion mixed polymerization to intermediate molecule, to produce homopolymer, segmented copolymer or the random copolymers of alkoxy polyether, by consumption and the feed way of adjustment ring oxide compound, can prepare the unsaturated branching polyether macromonomer of different molecular weight and structure.
Step 2) in, conventional catalyzer comprises potassium metal (sodium), naphthalene potassium (sodium), potassium hydride KH (sodium), alkyl potassium alcoholate (sodium), potassium hydroxide (sodium) etc.Oxyalkylated catalyst levels is preferably 0.05%~0.2% of products therefrom weight after alkoxylate; Oxyalkylated temperature of reaction is preferably 110~130 ℃; Reaction pressure is preferably 0.2~0.6MPa.
Step 2) described alkoxylation complete after, the alkalescence of product is stronger, is unfavorable for prolonged storage, as needs prolonged storage, in just need to carrying out and aftertreatment.Post-processing temperature remains between 60~90 ℃, and temperature is too low, and product viscosity is larger, even solidifies, and is difficult to neutralization; Excess Temperature, can cause too much by product to produce.In after aftertreatment adopt organic acid to carry out, organic acid is preferably Glacial acetic acid, oxalic acid, citric acid.
The comb-branched copolymer cement dispersants that adopts above-mentioned unsaturated polyester ether monomer to prepare has following chemical structure:
Figure BDA0000097555870000033
Wherein, x, y, z represents the molecular fraction of three kinds of structural units in multipolymer, x+y+z=100%.As preferred version, x=10%~50%, y=40%~80%, z=0~30%.
General formula for A (VII) represents:
R in formula 1for H or-CH 3; X is linking group, for-CH 2-,-CH 2cH 2-,-OCH 2cH 2-,-OCH 2cH 2cH 2cH 2-or
Figure BDA0000097555870000042
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10~50.
General formula for B (VIII) represents:
Figure BDA0000097555870000043
R in formula 2for hydrogen atom or-COOM; R 3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group.
The weight-average molecular weight of above-mentioned comb-branched copolymer cement dispersants is controlled at 30,000~70, and 000, if molecular weight is too large or too little, all can weaken the dispersion effect to cement.
By monomer a, b, c, in aqueous medium, there is free radicals copolymerization reaction and be prepared from above-mentioned comb-branched copolymer cement dispersants, wherein:
Monomer is general formula (I) expression for a:
Figure BDA0000097555870000044
R in formula 1for H or-CH 3; X is linking group, for-CH 2-,-CH 2cH 2-,-OCH 2cH 2-,-OCH 2cH 2cH 2cH 2-or
Figure BDA0000097555870000045
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10~50.
Monomer is general formula (II) expression for b:
R in formula 2for hydrogen atom or-COOM; R 3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group.
Above-mentioned monomer b contains at least one material in the represented material of general formula (II), is preferably at least one in vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid or their univalent metal salt, divalent metal salt, ammonium salt, organic amine salt.These monomers are used separately or use with the arbitrary proportion form of mixtures of two or more composition, and its hydroxy-acid group provides adsorption site and electrostatic repulsion in cement dispersants.
Monomer c is the 3rd functional monomer, the proportion of composing of adjustable carboxylic group and polyether lateral chain, is selected from any one in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylamide, vinyl acetate.
Through applicant, repeatedly test, the preferred molecular fraction consumption of above-mentioned monomer a, b, c respectively: 10%~50%, 40%~80%, 0~30%.
The initiator of monomer a, b and c copolyreaction is conventional free radical water soluble starter, comprise independent persulphate, the composition of persulphate and hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt, the composition of superoxide and L-AA or metal ion, initiator accounts for 0.5%~5% of monomer a+b+c total mole number, and wherein in composition, both mole ratios are 4~6: 1.
In copolyreaction process, according to the polymerization activity of monomer, can select not add chain-transfer agent, also can select to add water miscible chain-transfer agent to regulate the molecular weight of multipolymer.Aforementioned water-soluble chain transfer agent is preferably mercaptan type chain transfer agent, as at least one or the mixture of its arbitrary proportion in 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, mercaptoethanol, the consumption of chain-transfer agent in polymerization process is 0.2%~3% of monomer a+b+c total mole number.
Monomer weight concentration total in copolyreaction is preferably between 30%~60%, and temperature of reaction is 40~90 ℃, and it is main relevant with used initiator type.Monomer and initiator solution take the mode separately simultaneously dripping to control the homogeneity of multipolymer chain link distribution and the stability of polyreaction.Monomer and initiator solution time for adding are controlled at 1~5 hour.In order to improve the transformation efficiency of monomer, need to drip follow-up continuation of insurance temperature at monomer and initiator, soaking time is preferably 2~6 hours.
After copolyreaction finishes, the principal constituent that can directly serve as cement dispersants is used, and more preferably further uses in alkaline matter and rear use, to strengthen the stability in storage of product.The alkaline matter using comprises oxyhydroxide, oxide compound or the carbonate of monovalence metal and/or divalent metal, ammonium hydroxide, organic amine.The consumption of alkaline matter be take and regulated the pH value of reaction product to be advisable as 7 left and right.
Comb-branched copolymer cement dispersants of the present invention conventional volume is in use 0.08%~0.6% of total gelling material weight, and optimum adding quantity of pulverized is 0.1%~0.25%.Volume is too low, can not be satisfactory to the dispersion effect of cement; Volume is too high, causes waste economically, and dispersion effect does not further increase.Engineering staff can be preferred within the scope of this according to practical situation.
The present invention introduces new unsaturated polyester ether monomer in comb-branched copolymers cement dispersants, in this monomer molecule structure, there are unsaturated activity double key and three branching polyoxyalkylene long-chains, itself and other monomer are carried out to free radical aqueous solution copolymerization to react, there is higher Copolymerization activity, can obtain having the multipolymer of comb-branched structure.Due to the Hydrophilicrto polyether side chain of distributing in this copolymer molecule structure a certain proportion of carboxylic group and branching, the greatly sterically hindered effect between refinforced cement particle during as cement dispersants, the dispersion stabilization of raising cement.The preparation method of dispersion agent of the present invention is simple, production operation is convenient, not with an organic solvent, does not need through loaded down with trivial details esterification, meanwhile, this dispersion agent also has advantages of that volume is low, good dispersity, water-reducing rate are high, little loss of slump, body air content are low.
Embodiment
The preparation of unsaturated polyester ether monomer a
The preparation of unsaturated polyester ether monomer a-1:
73.2g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 60 ℃, under continuously stirring, slowly in flask, continue to drip 136.8g glycidyl allyl ether; time for adding 6h; dropwise rear continuation and stir insulation 4h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 70g and 0.44g sodium Metal 99.5 are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 130 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously 775g oxyethane, keep 130 ℃ of temperature, under the pressure of 0.25MPa, until oxyethane is all reinforced complete, continue constant temperature and stir 30min, then be evacuated to-below 0.08MPa, cool to 90 ℃, discharging, with oxalic acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-1 of 2100 left and right.
The preparation of unsaturated polyester ether monomer a-2:
91.5g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 80 ℃, under continuously stirring, slowly in flask, continue to drip 192g methacrylic glycidyl ether; time for adding 4h; dropwise rear continuation and stir insulation 2h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 151.2g and 0.86g potassium methylate are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 125 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously 730g oxyethane, keep 125 ℃ of temperature, under the pressure of 0.4MPa, until oxyethane is all reinforced complete, continue constant temperature and stir 30min, then be evacuated to-below 0.08MPa, cool to 80 ℃, discharging, with Glacial acetic acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-2 of 1100 left and right.
The preparation of unsaturated polyester ether monomer a-3:
79.3g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 70 ℃, under continuously stirring, slowly in flask, continue to drip 184.6g methyl alkene butylglycidyl ether; time for adding 8h; dropwise rear continuation and stir insulation 3h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 81.2g and 1.32g sodium ethylate are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 110 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously the mixture being formed by 576g oxyethane and 68g propylene oxide, keep 110 ℃ of temperature, under the pressure of 0.6MPa, until the mixture of oxyethane and propylene oxide is all reinforced complete, continue constant temperature and stir 30min, then be evacuated to-below 0.08MPa, cool to 70 ℃, discharging, with citric acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-3 of 1800 left and right.
The preparation of unsaturated polyester ether monomer a-4:
109.8g monoethanolamine is placed in to the four-hole boiling flask with reflux condensing tube, thermometer, nitrogen conduit and agitator; continue to lead to nitrogen protection in reaction flask; flask is placed in to water-bath; then be warming up to 65 ℃, under continuously stirring, slowly in flask, continue to drip 205.2g glycidyl allyl ether; time for adding 7h; dropwise rear continuation and stir insulation 1h, cooling, obtain intermediate.
The above-mentioned synthetic intermediate of 175g and 0.85g potassium hydroxide are placed in to the stainless steel autoclave that 1L is dry, sealed reactor.After reactor is found time, with air in nitrogen replacement still three times, under continuing to stir, be warming up to 120 ℃, heat up simultaneously, after keeping reactor to continue to vacuumize 30min, stop, then slowly pass into continuously 586g oxyethane, keep 120 ℃ of temperature, under the pressure of 0.3MPa, until oxyethane is all reinforced complete, slowly pass into continuously again 45g propylene oxide, keep 120 ℃ of temperature, under the pressure of 0.3MPa, until propylene oxide is all reinforced complete, continuing constant temperature stirs after 30min, be evacuated to-below 0.08MPa, cool to 60 ℃, discharging, with Glacial acetic acid, be neutralized to pH=7 left and right, obtaining molecular weight is the unsaturated polyester ether monomer a-4 of 800 left and right.
The preparation of comb-branched copolymer cement dispersants
The molecular weight of multipolymer described in embodiment and comparative example adopts gel permeation chromatography (GPC) carry out measure and calculation and obtain, and test condition is as described below, take polyoxyethylene glycol as reference material drawing standard curve.
The test condition of GPC is:
Gel column: Shodex SB806+803 two root chromatogram column series connection
Column temperature: 40 ℃
Eluant: 0.1M NaNO 3the aqueous solution
Flow velocity: 1.0ml/min
Sample size: the aqueous solution of 20 μ l 0.5% samples
Detector: Shodex RI-71 type differential refraction detector
Standard curve making standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
The test of comb-shaped copolymer cement dispersant to the dispersing property of cement and slump hold facility, carries out with reference to standard GB/T 8076-2008 " concrete admixture " relevant regulations.
Embodiment 1
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 200g distilled water and 460g unsaturated polyester ether monomer a-1.Reactor is leading under nitrogen protection, the large monomer of stirring and dissolving, and be warming up to 90 ℃, and then 58.6g vinylformic acid, 5.62g acrylamide and 60g water mix and blend are made to uniform monomer solution, it is at the uniform velocity dropped in reactor, time for adding is 4h.Meanwhile, at the uniform velocity drip the initiator solution that 90g contains 2.45g Potassium Persulphate, time for adding is 4.5h.Complete soln dropwises follow-up continuation of insurance temperature 4h, is then cooled to 50 ℃, adds 30% aqueous sodium hydroxide solution that product is neutralized to pH=7 left and right, obtains solid content and be 57.3% transparent liquid, and molecular weight of copolymer is determined as 57,600 through GPC.
Embodiment 2
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 210g distilled water and 320g unsaturated polyester ether monomer a-2.Reactor is leading under nitrogen protection, the large monomer of stirring and dissolving, and be warming up to 80 ℃; then by 22.6g sodium acrylate, 15.6g methylene-succinic acid; 0.89g Thiovanic acid and 100g water mix and blend are made uniform monomer solution, and it is at the uniform velocity dropped in reactor, and time for adding is 4.5h.Meanwhile, drip at the uniform velocity respectively the 110g aqueous solution that contains 4.66g Sodium Persulfate and the 110g aqueous solution that contains 0.48g sodium bisulfite, time for adding is 5h.Complete soln dropwises follow-up continuation of insurance temperature 6h, is then cooled to 50 ℃, adds 20% ammonia soln that product is neutralized to pH=7 left and right, obtains solid content and be 38.6% transparent liquid, and molecular weight of copolymer is determined as 68,400 through GPC.
Embodiment 3
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 200g distilled water, the hydrogen peroxide that 380g unsaturated polyester ether monomer a-3 and 3.96g massfraction are 27.5%.Reactor is leading under nitrogen protection, the large monomer of stirring and dissolving, and be warming up to 45 ℃; then by 34.2g toxilic acid, 24.7g Propylene glycol monoacrylate; 2.06g 3-thiohydracrylic acid and 100g water mix and blend are made uniform monomer solution, and it is at the uniform velocity dropped in reactor, and time for adding is 1h.Meanwhile, at the uniform velocity drip the aqueous solution that 120g contains 1.75g iron vitriol, time for adding is 1.5h.Complete soln dropwises follow-up continuation of insurance temperature 2h, then adds monoethanolamine that product is neutralized to about pH=7, obtains solid content and be 50.8% transparent liquid, and molecular weight of copolymer is determined as 34,200 through GPC.
Embodiment 4
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add 200g distilled water and 420g unsaturated polyester ether monomer a-4.Reactor is under logical nitrogen protection; the large monomer of stirring and dissolving; and be warming up to 70 ℃; then by 77.3g toxilic acid disodium, 7.54g Hydroxyethyl acrylate, 15.1g sodium allyl sulfonate; 0.27g mercaptoethanol and 70g water mix and blend are made uniform monomer solution; it is at the uniform velocity dropped in reactor, and time for adding is 2h.Meanwhile, at the uniform velocity drip 76g and contain 4.28g ammonium persulfate solution, time for adding is 2.5h.After complete soln dropwises, be warming up to 90 ℃ and continue insulation 5h, be then cooled to 50 ℃, add saturated calcium hydroxide aqueous solution that product is neutralized to pH=7 left and right, obtain solid content and be 59.4% transparent liquid, molecular weight of copolymer is determined as 52,600 through GPC.
Embodiment 5
In the 1L glass reactor of thermometer, agitator, dropping funnel and nitrogen conduit is housed, add the hydrogen peroxide that 300g distilled water and 240g unsaturated polyester ether monomer a-1 and 1.74g massfraction are 27.5%.Reactor is under logical nitrogen protection; the large monomer of stirring and dissolving; and be warming up to 65 ℃; then by 29.2g sodium acrylate, 18.2g toxilic acid; 6.58g sodium itaconate; 2.85g methyl acrylate and 210g water mix and blend are made uniform monomer solution, and it is at the uniform velocity dropped in reactor, and time for adding is 3h.Meanwhile, at the uniform velocity drip the aqueous solution that 180g contains 0.42g L-AA, time for adding is 3.5h.Complete soln dropwises follow-up continuation of insurance temperature 4h, is then cooled to 50 ℃, in add 30% potassium hydroxide aqueous solution that product is neutralized to pH=7 left and right, obtain solid content and be 30.5% transparent liquid, molecular weight of copolymer is determined as 46,100 through GPC.
Comparative example 1
By the 460g unsaturated polyester ether monomer a-1 adding in embodiment 1, replace to that to add 482g molecular weight be the common strand allyl polyethenoxy ether of 2200 left and right, other synthesis condition is constant, obtains solid content and be 59.5% transparent liquid, molecular weight of copolymer is 51,200 through GPC test.
Comparative example 2
By the 320g unsaturated polyester ether monomer a-2 adding in embodiment 2, change that to add 320g molecular weight be the common methacrylic Soxylat A 25-7 of 1800 left and right into, other synthesis condition is constant, obtains solid content and be 38.5% transparent liquid, molecular weight of copolymer is 78,300 through GPC test.
Comb-shaped copolymer cement dispersant synthetic in Evaluation operation example 1~5 and comparative example 1~2, to the dispersing property of cement and slump hold facility, is carried out with reference to standard GB/T 8076-2008 " concrete admixture " relevant regulations.Test is carried out under 25 ℃ of environment, and test cement adopts little Ye field, the south of the River 52.5 P.II cement, fixing water consumption, and adjusting dispersant dosage, to make the initial slump of fresh concrete be 21.0 ± 1cm, adopting identical defoamer adjustment concrete 's air-containing is 3% left and right.The volume of copolymer cement dispersant is with solid component meter, and to take the weight of cement be benchmark to volume simultaneously.Test-results sees the following form:
Table 1. comb-branched copolymer cement dispersants of the present invention for the Performance Ratio of fresh concrete
Figure BDA0000097555870000101
From result shown in table 1, can find out, compare with the concrete sample of comparative example 2 cement dispersants with use comparative example 1, use the concrete sample of the cement dispersants of the present invention of embodiment 1~5 all can make concrete obtain the specific slump and divergence with less incorporation, demonstrate the good performance that cement is disperseed.In addition, use the concrete sample of the cement dispersants of the present invention of embodiment 1~5 after 60 minutes, all to show the less slump and divergence loss, illustrate that this sample has good cement dispersiveness and dispersed hold facility.

Claims (11)

1. a comb-branched copolymer cement dispersants, is characterized in that having following chemical structure:
Figure FDA0000371903280000011
Wherein, x, y, z represents the molecular fraction of three kinds of structural units in multipolymer, x+y+z=100%, x=10%~50%, y=40%~80%, z=0~30%;
General formula for A (VII) represents:
Figure FDA0000371903280000012
R in formula 1for H or-CH 3; X is-CH 2-,-CH 2cH 2-,-OCH 2cH 2-,-OCH 2cH 2cH 2cH 2-or
Figure FDA0000371903280000013
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10~50;
General formula for B (VIII) represents:
Figure FDA0000371903280000014
R in formula 2for hydrogen atom or-COOM; R 3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group;
C is the structural unit after any one polymerization in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylamide, vinyl acetate.
2. comb-branched copolymer cement dispersants as claimed in claim 1, is characterized in that the weight-average molecular weight of described comb-branched copolymer cement dispersants is controlled at 30,000~70,000.
3. the preparation method of comb-branched copolymer cement dispersants described in claim 1 or 2, is characterized in that, by monomer a, b, c, free radicals copolymerization reaction occurs in aqueous medium, wherein
Monomer a represents with logical formula I:
Figure FDA0000371903280000021
R in formula 1for H or-CH 3; X is-CH 2-,-CH 2cH 2-,-OCH 2cH 2-,-OCH 2cH 2cH 2cH 2-or
Figure FDA0000371903280000022
aO is oxyethylene group and/or oxypropylene group; L, m, n are the number of repeat unit of AO, the natural number of l+m+n=10~50;
Monomer b represents with logical formula II:
R in formula 2for hydrogen atom or-COOM; R 3for hydrogen atom or methyl; M represents hydrogen atom, alkalimetal ion, alkaline-earth metal ion, ammonium ion or organic amine group;
Monomer c is the 3rd functional monomer, is selected from any one in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) sodium allyl sulfonate, (methyl) acrylamide, vinyl acetate.
4. method as claimed in claim 3, is characterized in that monomer a, b, the shared molecular fraction of c are respectively 10%~50%, 40%~80%, 0~30%.
5. method as claimed in claim 3, is characterized in that monomer b is at least one material containing in the logical represented material of formula II.
6. method as claimed in claim 5, is characterized in that monomer b is selected from least one in vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or their univalent metal salt, divalent metal salt, ammonium salt, organic amine salt.
7. method as claimed in claim 3, the initiator that it is characterized in that monomer a, b and c copolyreaction is selected from independent persulphate, the composition of persulphate and hydrosulphite, sulphite, thiosulphate, pyrosulfite or ferrous salt, the composition of superoxide and L-AA or metal ion, initiator accounts for 0.5%~5% of monomer a+b+c total mole number, and wherein in composition, both mole ratios are 4~6:1.
8. method as claimed in claim 3, it is characterized in that adding water miscible chain-transfer agent to regulate the molecular weight of multipolymer in copolyreaction process, aforementioned water-soluble chain transfer agent is mercaptan type chain transfer agent, and the consumption of chain-transfer agent in polymerization process is 0.2%~3% of monomer a+b+c total mole number.
9. method as claimed in claim 8, is characterized in that described mercaptan type chain transfer agent is selected from least one or the mixture of its arbitrary proportion in 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-mercaprol, 3-mercaprol, Thiovanic acid, mercaptoethanol.
10. method as claimed in claim 3, is characterized in that monomer weight concentration total in copolyreaction is between 30%~60%, and temperature of reaction is 40~90 ℃.
11. methods as claimed in claim 3, it is characterized in that mode that monomer and initiator solution are taked separately to drip simultaneously controls homogeneity that multipolymer chain link distributes and the stability of polyreaction, monomer and initiator solution time for adding are controlled at 1~5 hour, and monomer and initiator solution drip follow-up continuation of insurance temperature 2~6 hours.
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