CN102030496A - Polycarboxylic-acid copolymer dispersant and preparation method thereof - Google Patents
Polycarboxylic-acid copolymer dispersant and preparation method thereof Download PDFInfo
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- CN102030496A CN102030496A CN 201010556514 CN201010556514A CN102030496A CN 102030496 A CN102030496 A CN 102030496A CN 201010556514 CN201010556514 CN 201010556514 CN 201010556514 A CN201010556514 A CN 201010556514A CN 102030496 A CN102030496 A CN 102030496A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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Abstract
The invention discloses a polycarboxylic-acid copolymer dispersant and a preparation method thereof, wherein the dispersant is a polycarboxylic-acid copolymer which contains a structural unit (1), a structural unit (2) and a structural unit (3) and has the weight average molecular weight of 5000-120000, wherein the structural unit (1) is derived from an unsaturated polyether monomer, the structural unit (2) is derived from an unsaturated polyether monomer, and the structural unit (3) with the concentration of 5.0-30.0 percent by weight is derived from an unsaturated carboxylic-acid monomer; and the preparation method of the polycarboxylic-acid copolymer dispersant comprises the step of copolymerizing the unsaturated polyether monomer (A), the unsaturated polyether monomer (B) and the unsaturated carboxylic-acid monomer (C) at the temperature of 20-110 DEG C and in the presence of a chain transfer agent and an initiator to obtain the polycarboxylic-acid copolymer dispersant. Concrete still has high water-reducing rate under the condition of lower blending quantity of the copolymer dispersant of the invention, and meanwhile, the concrete still has better slump and fluidity after the copolymer dispersant of the invention is blended.
Description
Technical field
The invention belongs to technical field of concrete additives, relate to mortar or concrete superplasticizer, specifically relate to a kind of novel high performance water reducing agent of polyocarboxy acid and preparation method thereof.
Background technology
High performance water reducing agent of polyocarboxy acid is called as third generation concrete superplasticizer, has that volume is low, water-reducing rate is high, the Molecular Structure Design degree of freedom is big, advantages of environment protection, becomes the research focus and the development priority in 21st century concrete admixture field.
A kind of preparation method of allyl ester ether monomer and the method for preparing water reducer with this monomer are disclosed in patent CN1412175: at first handle allyl alcohol polyether and its peroxide value is reached below the 5.0meq/kg with sorbing materials such as aluminum oxide, carry out esterification with the aliphatics monocarboxylic acid again and make allyl ester ether monomer.To make weight-average molecular weight under the initiator be 13500 multipolymer making of Diisopropyl azodicarboxylate under 80 ℃ with this refined allyl ester ether monomer and maleic anhydride again, again this multipolymer and alkyl polyalkylene glycol obtained a kind of cement dispersants 100 ℃ of following esterifications.But,, cause the water-reducing property of the cement dispersants that obtains and the slump to keep the performance all can not be satisfactory because the reactive behavior of allyl ester ether monomer is relatively poor.
A kind of thiazolinyl polyglycol ether and unsaturated carboxylic acid copolymerization polycarboxylate dispersant's method is disclosed in patent CN1081615C: carry out copolymerization by thiazolinyl polyglycol ether (as allyl polyglycol or methacrylic polyoxyethylene glycol or 3-methyl-3-butene-1-polyoxyethylene glycol) and unsaturated carboxylic acid (as vinylformic acid or toxilic acid or methacrylic acid) under action of evocating and obtain.But the polycarboxylate dispersant of this invention does not possess good slump hold facility under the condition of high water reducing rate.
A kind of prescription and manufacture method thereof of polycarboxylic acid super-plasticizer are disclosed in patent CN101205127A, at first make the esterification under the condition that catalyzer and stopper exist of poly glycol monomethyl ether and maleic anhydride generate big monomer, make the polycarboxylic acid super-plasticizer that copolymerization under the condition of initiator obtains Xu Fangxing at ammonium persulphate with allyl polyglycol, vinylformic acid, methylpropene sodium sulfonate then.But, because the polymerization activity deficiency of allyl polyglycol, poly glycol monomethyl ether maleic acid ester can remain in institute's synthetic polycarboxylic acid super-plasticizer in a large number, cause the water-reducing rate of gained superplasticizer low, the slump keeps the performance deficiency.
Japanese Patent JP106890/2003 has announced the manufacture method of a kind of poly-carboxylic-acid cement dispersant and concrete secondary product.It is 100～200 polyethers monomethacrylates or polyether monoacrylates, acrylic or methacrylic acid that this cement dispersants adopts the average addition mole number of oxyalkylene group, contain sulfonic unsaturated monomer copolymerization forms.The poly-carboxylic-acid cement dispersant of being invented has the water-reducing rate height, also can improve early age strength of concrete, but the slump of the poly-carboxylic-acid cement dispersant that should invent keeps poor-performing.
Summary of the invention
The purpose of this invention is to provide a kind of co-poly carboxylic acid dispersion agent that under the condition of high water reducing rate, also has good slump hold facility and preparation method thereof.
Co-poly carboxylic acid dispersion agent of the present invention is to contain the following monomeric structural unit of unsaturated polyether (1) that is derived from, the following monomeric structural unit of unsaturated polyether (2) that is derived from, with the co-poly carboxylic acid of the following structural unit that is derived from unsaturated carboxylic acid monomer (3), wherein:
Structural unit (1) is
Wherein: R
1, R
2, R
3, R
4, R
5Be hydrogen or methyl, and R
1, R
2, R
3, R
4, R
5There are two methyl at most simultaneously; R
6O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; R
7O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; P represents the number of methylene radical, is the integer of 0-2; N, m represent the adduct number of oxyalkylene group, are the integer of 1-300.
Structural unit (2) is
Wherein: R
8Expression hydrogen or methyl; R
9O represents oxyalkylene group of 2-8 carbon atom and composition thereof, and they are homopolymer or random copolymers or segmented copolymer; N represents the average addition mole number of oxyalkylene group, is any number among the 1-180; R
10The alkyl of expression hydrogen or 1-6 carbon atom.
Structural unit (3) is
Wherein: R
11Expression hydrogen, methyl or
Group, R
12Expression hydrogen, methyl or
Group, M are represented hydrogen, monovalence metal, divalent metal, ammonium or organic amino group.
Described co-poly carboxylic acid dispersion agent has: the weight-average molecular weight of the structural unit of 5.0-30.0% weight (3) content and 5000-120000.
A kind of method for preparing co-poly carboxylic acid dispersion agent of the present invention, described method be with comprise following by general formula (4) expression unsaturated polyester ether monomer (A) and by the unsaturated polyester ether monomer (B) of general formula (5) expression and the step of under the condition that 20-110 ℃, chain-transfer agent and initiator exist, carrying out copolymerization, wherein by the unsaturated carboxylic acid monomer (C) of general formula (6) expression:
Monomer (A) is represented with general formula (4):
Wherein: R
1, R
2, R
3, R
4, R
5Be hydrogen or methyl, and R
1, R
2, R
3, R
4, R
5There are two methyl at most simultaneously; R
6O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; R
7O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; P represents the number of methylene radical, is the integer of 0-2; N, m represent the adduct number of oxyalkylene group, are the integer of 1-300.In multipolymer, monomer (A) is wherein a kind of or two kinds, multiple mixing use.
Monomer (B) is represented with general formula (5):
Wherein: R
8Expression hydrogen or methyl; R
9O represents oxyalkylene group of 2-8 carbon atom and composition thereof, and they are homopolymer or random copolymers or segmented copolymer; N represents the average addition mole number of oxyalkylene group, is any number among the 1-180; R
10The alkyl of expression hydrogen or 1-6 carbon atom.In multipolymer, monomer (B) is wherein a kind of or two kinds, multiple mixing use.
Monomer (C) is represented with general formula (6):
In the formula, R
11Expression hydrogen, methyl or
Group, R
12Expression hydrogen, methyl or
Group, M are represented hydrogen, monovalence metal, divalent metal, ammonium or organic amino group.Monomer (C) accounts for the 5.0-30.0% of whole total monomer weights.In multipolymer, monomer (C) is wherein a kind of or two kinds, multiple mixing use.
There is not special restriction to being used for unsaturated polyester ether monomer of the present invention (A), as long as it is can be by the monomer of above general formula (4) expression.Monomer (A) is by 1 mole unsaturated glyceryl ether (3-allyloxy-1 for example, 2-propylene glycol, 3-(2-methyl allyloxy)-1,2-propylene glycol, 3-(2-methyl isophthalic acid-alkene butoxy)-1,2-propylene glycol, 3-(2-methyl-2-alkene butoxy)-1,2-propylene glycol, 3-(3,3-dimethyl allyloxy)-1, the 2-propylene glycol) carry out addition with oxirane (containing 2 to 18 carbon atoms) and obtain, the oxirane number of addition on each hydroxyl is 1-300.
There is not special restriction to being used for unsaturated polyester ether monomer of the present invention (B), as long as it is can be by the monomer of above general formula (5) expression.The method that obtains monomer (B) has two kinds: a kind of is that to adopt crylic acid hydroxy ester or methacrylic acid hydroxyl ester be that the individual oxirane addition of 2-8 obtains with carbonatoms, the method of addition comprises homopolymerization, random copolymerization and block copolymerization, and crylic acid hydroxy ester commonly used or methacrylic acid hydroxyl ester have Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester; Another kind is to be obtained by alkoxyl group polyalkylene glycol ethers and acrylic or methacrylic acid estersization, described alkoxyl group polyalkylene glycol ethers is to be that 2-8 oxirane addition obtains by Fatty Alcohol(C12-C14 and C12-C18) such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, propyl carbinol, isopropylcarbinol, 1-amylalcohol and 1-hexanol and carbonatoms, and the method for addition comprises homopolymerization, random copolymerization and block copolymerization.
The object lesson of monomer (C) comprises following monomer: vinylformic acid, methacrylic acid, methylene-succinic acid and toxilic acid, and univalent metal salt, divalent metal salt, ammonium salt and organic amine salt.
If desired, can also add following monomer component:
(methyl) acrylate comprises methyl acrylate, ethyl propenoate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, dimethylaminoethyl acrylate, vinylformic acid diethylin ethyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, dimethylaminoethyl methacrylate, methacrylic acid diethylin ethyl ester.
Unsaturated sulfonic acid or its salt comprise sodium allyl sulfonate, methallylsulfonic acid sodium, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic acid or its salt, vinylformic acid sulphur ethyl ester, methacrylic acid sulphur ethyl ester.
Unsaturated amides comprises acrylamide, Methacrylamide, n-methylolacrylamide, N,N-DMAA.
Vinyl ester comprises vinyl acetate, propionate.
Chain-transfer agent of the present invention is a kind of or its mixture in mercaptoethanol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, the Dodecyl Mercaptan, and the consumption of chain-transfer agent is 0.2%～8.0% of a total monomer weight.
Initiator of the present invention comprises thermal decomposition initiating and redox initiator, and thermal decomposition initiating is one or several the mixture in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide and the tertbutyl peroxide; Redox initiator is to adopt thermal decomposition initiating and the common composition of reductive agent, wherein thermal decomposition initiating is one or several mixing in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide and the tertbutyl peroxide, and reductive agent is one or several mixing in sodium bisulfite, Potassium hydrogen sulfite, Sodium Pyrosulfite, rongalite, Hypophosporous Acid, 50, sodium hypophosphite, potassium hypophosphite, ferrous salt and the vitamins C.When enforcement was of the present invention, the thermal decomposition initiating consumption that joins in the reaction mixture system was 0.2%～10.0% of a total monomer weight, and the reductive agent consumption that joins in the reaction mixture system is 0%～8.0% of a total monomer weight.
Described co-poly carboxylic acid dispersion agent weight-average molecular weight is 5000～120000.Molecular weight is too low or too high, the equal deterioration of the performance of co-poly carboxylic acid admixture.U.S. Waters 1515 HPLC SYSTEM high performance liquid chromatographs are adopted in the test of weight-average molecular weight, configuration Ultrahydrogel
TMWater-soluable gel post, Waters 2414 differential refraction detectors are with 0.1mol/L NaNO
3The aqueous solution is moving phase, is that standard substance are measured with the polyoxyethylene glycol.
After copolyreaction was finished, pH value or the selection selecting as required to regulate product were not regulated.If the choosing folding is regulated the pH value, used neutralization reagent is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia or organic amine or their aqueous solution.
In addition, co-poly carboxylic acid dispersion agent of the present invention can be used from mortar or the concrete with known cement water reducing agent, setting accelerator, hardening accelerator, retardant, air entrapment agent, defoamer, tackifier, economization agent one.Multipolymer of the present invention still has high concrete water-reducing ratio under lower volume condition, still have concrete slump and degree of mobilization preferably after being mixed with copolymer dispersant of the present invention simultaneously.
Embodiment
The present invention is further described by following examples, but the present invention is not produced any restriction.
Listed abbreviation below having used in an embodiment:
B-1: methacrylic acid macrogol ester (making average EO adduct number 45 by hydroxyethyl methylacrylate and oxyethane addition)
B-2: methoxy poly (ethylene glycol) acrylate (average EO adduct number 22)
C-1: vinylformic acid
C-2: toxilic acid
C-3: methacrylic acid
D-1: Hydroxyethyl acrylate
D-2:2-acrylamide-2-methyl propane sulfonic acid
Synthesis example 1
In the reactor of 2L, drop into 3-allyloxy-1,2-propylene glycol 132.0g, catalyzer sodium methylate 2.0g,, stir and be warming up to 105 ℃～115 ℃ after the reactor displacement with nitrogen, vacuumize water and methyl alcohol, the pressure that vacuumizes reaches more than the negative 0.09MPa, and the pumpdown time is 30 minutes.After stopping to vacuumize the back, add a small amount of oxyethane to reactor pressure from the reactor top and rise to about 0.10MPa; Treat that still pushes back backwardness, continue to feed at a slow speed oxyethane again, the speed that feeds oxyethane to be keeping reacting kettle inner pressure between 0.30MPa～0.40MPa, and makes temperature of reaction maintain 105 ℃～115 ℃ by regulating water coolant, and the weight that accumulative total adds oxyethane is 1760g.After treating that oxyethane all adds, 105 ℃～115 ℃ continue insulation reaction and no longer descend to reacting kettle inner pressure more than 30 minutes till, be cooled to 50 ℃～60 ℃ dischargings, obtain the unsaturated polyester ether monomer, be designated as A-1.
Synthesis example 2
In the reactor of 2L, drop into the 3-(2-methyl allyloxy)-1,2-propylene glycol 73.0g, catalyzer sodium methylate 1.0g, with nitrogen with after the reactor displacement, stirring is warming up to 130 ℃～140 ℃, vacuumize water and methyl alcohol, the pressure that vacuumizes reaches more than the negative 0.09MPa, and the pumpdown time is 30 minutes.After stopping to vacuumize the back, add a small amount of oxyethane to reactor pressure from the reactor top and rise to about 0.10MPa; Treat that still pushes back backwardness, continue to feed at a slow speed oxyethane again, the speed that feeds oxyethane to be keeping reacting kettle inner pressure between 0.30MPa～0.40MPa, and makes temperature of reaction maintain 130 ℃～140 ℃ by regulating water coolant, and the weight that accumulative total adds oxyethane is 1760g.After treating that oxyethane all adds, 130 ℃～140 ℃ continue insulation reaction and no longer descend to reacting kettle inner pressure more than 30 minutes till, be cooled to 50 ℃～60 ℃ dischargings, obtain the unsaturated polyester ether monomer, be designated as A-2.
Synthesis example 3
In the reactor of 2L, drop into the 3-(2-methyl allyloxy)-1,2-propylene glycol 73.0g, catalyzer sodium amide 2.0g, with nitrogen with after the reactor displacement, stirring is warming up to 140 ℃～150 ℃, vacuumize water and ammonia, the pressure that vacuumizes reaches more than the negative 0.09MPa, and the pumpdown time is 30 minutes.After stopping to vacuumize the back, add the mixture (mol ratio of oxyethane and propylene oxide is 95:5) of a small amount of oxyethane and propylene oxide from the reactor top, rise to about 0.10MPa to reactor pressure; Treat that still pushes back backwardness, the mixture that continues to feed at a slow speed oxyethane and propylene oxide (mass ratio of oxyethane and propylene oxide is 95:5), the speed that feeds epoxy mixture is to keep reacting kettle inner pressure between 0.30MPa～0.40MPa, and make temperature of reaction maintain 140 ℃～150 ℃ by regulating water coolant, the weight that accumulative total adds the oxyethane propylene oxide is 1800g.After treating that epoxy mixture all adds, 140 ℃～150 ℃ continue insulation reaction and no longer descend to reacting kettle inner pressure more than 30 minutes till, be cooled to 50 ℃～60 ℃ dischargings, obtain the unsaturated polyester ether monomer, be designated as A-3.
Embodiment 1
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 160.0g A-1,598.0g water, stir and be warming up to 80 ℃.Drip 100.0g ammonium persulfate aqueous solution (be dissolved in 90.0g water obtain by the 10.0g ammonium persulphate) and 965.0g monomer solution (being dissolved in 320.0g water by 544.0g B-2,96.0g C-1,5.0g 3-thiohydracrylic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 177.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-1 of the present invention, its solid content is 42.1%, and weight-average molecular weight is 35200.
Embodiment 2
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 400.0g A-2,698.0g water, stir and be warming up to 80 ℃.Drip 150.0g ammonium persulfate aqueous solution (be dissolved in 135.0g water obtain by the 15.0g ammonium persulphate) and 604.0g monomer solution (being dissolved in 200.0g water by 320.0g B-1,80.0g C-1,4.0g Thiovanic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 148.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-2 of the present invention, its solid content is 42.0%, and weight-average molecular weight is 38600.
Embodiment 3
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add the hydrogen peroxide of 240.0g A-3,544.0g water, 20.0g 30% concentration, stir and be warming up to 65 ℃.Drip the 80.0g vitamins C aqueous solution (be dissolved in the 72.0g water and obtain) and 840.0g monomer solution (be dissolved in 280.0g water obtain by 440.0g B-1,40.0g C-1,80.0g C-3) simultaneously by 3.0g vitamins C, 5.0g 3-thiohydracrylic acid, the dropping time was controlled at respectively 210 minutes and 180 minutes, and temperature of reaction is controlled at 63～67 ℃.After dripping end, be incubated 30 minutes down, make polyreaction complete at 63～67 ℃.After insulation finishes, be cooled to the 276.0g of adding below the 50 ℃ 30%KOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-3 of the present invention, its solid content is 43.2%, and weight-average molecular weight is 41100.
Embodiment 4
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add the hydrogen peroxide of 360.0g A-2,722.0g water, 20.0g 30% concentration, stir and be warming up to 65 ℃.Drip the 90.0g vitamins C aqueous solution (be dissolved in 81.0g water obtain by 4.0g vitamins C, 5.0g 2 mercaptopropionic acid) and 660.0g monomer solution (be dissolved in 220.0g water obtain by 360.0g B-1,80.0g C-1) simultaneously, the dropping time was controlled at respectively 210 minutes and 180 minutes, and temperature of reaction is controlled at 63～67 ℃.After dripping end, be incubated 30 minutes down, make polyreaction complete at 63～67 ℃.After insulation finishes, be cooled to the 148.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-4 of the present invention, its solid content is 41.6%, and weight-average molecular weight is 39500.
Embodiment 5
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 480.0g A-3,764.0g water, stir and be warming up to 80 ℃.Drip 100.0g ammonium persulfate aqueous solution (be dissolved in 90.0g water obtain by the 10.0g ammonium persulphate) and 482.0g monomer solution (being dissolved in 160.0g water by 256.0g B-1,64.0g C-2,2.0g 2 mercaptopropionic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 174.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-5 of the present invention, its solid content is 41.9%, and weight-average molecular weight is 18200.
Embodiment 6
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 512.0g A-2,805.0g water, stir and be warming up to 80 ℃.Drip 120.0g ammonium persulfate aqueous solution (be dissolved in 108.0g water obtain by the 12.0g ammonium persulphate) and 437.0g monomer solution (being dissolved in 144.0g water by 200.0g B-2,68.0g C-1,20.0g D-1,5.0g 3-thiohydracrylic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 126.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-6 of the present invention, its solid content is 41.7%, and weight-average molecular weight is 29400.
Embodiment 7
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 320.0g A-3,687.0g water, stir and be warming up to 80 ℃.Drip 120.0g ammonium persulfate aqueous solution (be dissolved in 108.0g water obtain by the 12.0g ammonium persulphate) and 725.0g monomer solution (being dissolved in 240.0g water by 344.0g B-2,96.0g C-3,40.0g D-2,5.0g 3-thiohydracrylic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 148.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-7 of the present invention, its solid content is 41.9%, and weight-average molecular weight is 38300.
Embodiment 8
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 320.0g A-2,640.0g water, stir and be warming up to 80 ℃.Drip 120.0g ammonium persulfate aqueous solution (be dissolved in 108.0g water obtain by the 12.0g ammonium persulphate) and 723.0g monomer solution (being dissolved in 240.0g water by 392.0g B-1,48.0g C-1,40.0g C-2,3.0g 3-thiohydracrylic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 197.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain co-poly carboxylic acid dispersion agent PC-8 of the present invention, its solid content is 42.2%, and weight-average molecular weight is 24700.
Comparative example 1
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 527.0g water, stir and be warming up to 80 ℃.Drip 120.0g ammonium persulfate aqueous solution (be dissolved in 108.0g water obtain by the 12.0g ammonium persulphate) and 1205g monomer solution (being dissolved in 400.0g water by 704.0g B-1,96.0g C-3,5.0g 3-thiohydracrylic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 148.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain the co-poly carboxylic acid dispersion agent SPC-1 of comparative example, its solid content is 41.9%, and weight-average molecular weight is 36100.
Comparative example 2
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 527.0g water, stir and be warming up to 80 ℃.Drip 120.0g ammonium persulfate aqueous solution (be dissolved in 108.0g water obtain by the 12.0g ammonium persulphate) and 1205g monomer solution (being dissolved in 400.0g water by 680.0g B-1,80.0g C-1,5.0g 3-thiohydracrylic acid obtains) simultaneously, the dropping time was controlled at respectively 150 minutes and 120 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, be incubated about 60 minutes down, make polyreaction complete at 78～82 ℃.After insulation finishes, be cooled to the 148.0g of adding below the 50 ℃ 30%NaOH aqueous solution, obtain the co-poly carboxylic acid dispersion agent SPC-2 of comparative example, its solid content is 41.9%, and weight-average molecular weight is 31300.
Application examples
According to high-performance water reducing agent test request in GB8076-2008 " concrete admixture " standard, adopting the reference cement of Beijing Xingfa Cement Co., Ltd's production, the river sand of silt content 0.8% fineness modulus 2.6, the nominal particle diameter 5-10mm and the 10-20mm continuous grading rubble of silt content 0.2% is material, concrete mix according to table 1 regulation has been tested indexs such as water-reducing rate, air content, slump hold facility, and test result sees 2.
Annotate :/expression concrete does not have divergence
From the test result of table 2, multipolymer of the present invention still has high concrete water-reducing ratio under lower volume condition, still has concrete slump and degree of mobilization preferably after being mixed with a hour of co-poly carboxylic acid dispersion agent of the present invention simultaneously.
Claims (5)
1. co-poly carboxylic acid dispersion agent, it is characterized in that containing the following monomeric structural unit of unsaturated polyether (1), the following co-poly carboxylic acid that is derived from monomeric structural unit of unsaturated polyether (2) and the following structural unit that is derived from unsaturated carboxylic acid monomer (3) of being derived from, wherein:
Structural unit (1) is
Wherein: R
1, R
2, R
3, R
4, R
5Be hydrogen or methyl, and R
1, R
2, R
3, R
4, R
5There are two methyl at most simultaneously; R
6O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; R
7O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; P represents the number of methylene radical, is the integer of 0-2; N, m represent the adduct number of oxyalkylene group, are the integer of 1-300;
Structural unit (2) is
Wherein: R
8Expression hydrogen or methyl; R
9O represents oxyalkylene group of 2-8 carbon atom and composition thereof; N represents the average addition mole number of oxyalkylene group, is any number among the 1-180; R
10The alkyl of expression hydrogen or 1-6 carbon atom;
Structural unit (3) is
Wherein: R
11Expression hydrogen, methyl or
Group, R
12Expression hydrogen, methyl or
Group, M are represented hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
Described co-poly carboxylic acid dispersion agent has: the weight-average molecular weight of the structural unit of 5.0-30.0% weight (3) content and 5000-120000.
2. method for preparing the described co-poly carboxylic acid dispersion agent of claim 1, described method be with comprise following by general formula (4) expression unsaturated polyester ether monomer (A) and by the unsaturated polyester ether monomer (B) of general formula (5) expression and the step of under the condition that 20-110 ℃, chain-transfer agent and initiator exist, carrying out copolymerization, wherein by the unsaturated carboxylic acid monomer (C) of general formula (6) expression:
Monomer (A) is represented with general formula (4):
Wherein: R
1, R
2, R
3, R
4, R
5Be hydrogen or methyl, and R
1, R
2, R
3, R
4, R
5There are two methyl at most simultaneously; R
6O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; R
7O is identical or different, and expression has the oxyalkylene group of 2-18 carbon atom; P represents the number of methylene radical, is the integer of 0-2; N, m represent the adduct number of oxyalkylene group, are the integer of 1-300;
In multipolymer, monomer (A) is wherein a kind of or two kinds, multiple mixing use;
Monomer (B) is represented with general formula (5):
Wherein: R
8Expression hydrogen or methyl; R
9O represents oxyalkylene group of 2-8 carbon atom and composition thereof, and they are homopolymer or random copolymers or segmented copolymer; N represents the average addition mole number of oxyalkylene group, is any number among the 1-180; R
10The alkyl of expression hydrogen or 1-6 carbon atom; In multipolymer, monomer (B) is wherein a kind of or two kinds, multiple mixing use;
Monomer (C) is represented with general formula (6):
In the formula, R
11Expression hydrogen, methyl or
Group, R
12Expression hydrogen, methyl or
Group, M are represented hydrogen, monovalence metal, divalent metal, ammonium or organic amino group; Monomer (C) accounts for the 5.0-30.0% of whole total monomer weights;
In multipolymer, monomer (C) is wherein a kind of or two kinds, multiple mixing use.
3. the method for preparing the co-poly carboxylic acid dispersion agent according to claim 2, it is characterized in that described chain-transfer agent is a kind of or its mixture in mercaptoethanol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, the Dodecyl Mercaptan, the consumption of chain-transfer agent is 0.2%～8.0% of a total monomer weight.
4. the method for preparing the co-poly carboxylic acid dispersion agent according to claim 2, it is characterized in that described initiator comprises thermal decomposition initiating and redox initiator, thermal decomposition initiating is one or several the mixture in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide and the tertbutyl peroxide; Redox initiator is to adopt thermal decomposition initiating and the common composition of reductive agent, wherein thermal decomposition initiating is one or several mixing in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide and the tertbutyl peroxide, and reductive agent is one or several mixing in sodium bisulfite, Potassium hydrogen sulfite, Sodium Pyrosulfite, rongalite, Hypophosporous Acid, 50, sodium hypophosphite, potassium hypophosphite, ferrous salt and the vitamins C.
5. the method for preparing the co-poly carboxylic acid dispersion agent according to claim 4 is characterized in that described thermal decomposition initiating consumption is 0.2%～10.0% of a total monomer weight, and the reductive agent consumption is 0%～8.0% of a total monomer weight.
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| CN102659338A (en) * | 2012-04-20 | 2012-09-12 | 株洲加美乐素建材有限公司 | Polycarboxylic water reducer applicable to manufactured sand and preparation method of polycarboxylic water reducer |
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| CN111268935A (en) * | 2019-11-22 | 2020-06-12 | 中交二航武汉港湾新材料有限公司 | Additive for ultra-high performance concrete and preparation method thereof |
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| CN111825788B (en) * | 2020-07-28 | 2022-05-20 | 北京普斯维斯石油技术有限责任公司 | High-temperature retarder for well cementation and preparation method thereof |
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