CN102531450B - Polyether amine modified polycarboxylate high performance water-reducing agent and preparation method thereof - Google Patents
Polyether amine modified polycarboxylate high performance water-reducing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyether amine modified polycarboxylate high performance water-reducing agent and a preparation method thereof. The water-reducing agent contains 2.0-30.0 percent by weight of polycarboxylate copolymer with weight average molecular weight of 5,000-12,000 derived from carboxyl constitutional unit I, a phosphorus constitutional unit II and amido polyether constitutional unit III; and the preparation method of the water-reducing agent comprises the following steps of: copolymerizing unsaturated carboxylic acid monomer A in aqueous solution of 50-100 DEG C with hypophosphorous acid or salt thereof to obtain phosphorus-containing carboxyl copolymer with molecular weight of 1,000-30,000; and then amidating the phosphorus-containing carboxyl copolymer and polyether amine monomer B at 80-200 DEG C to obtain the water-reducing agent. The polyether amine modified polycarboxylate high performance water-reducing agent still has high concrete water-reducing rate under a low-dosage condition, and also has good concrete slump retention.
Description
Technical field
The invention belongs to technical field of concrete additives, relate to mortar or the reinforcement of concrete superplasticizer, specifically 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 superplastizer, has that volume is low, water-reducing rate is high, the Molecular Structure Design degree of freedom is large, advantages of environment protection, becomes study hotspot and the development priority in 21st century concrete admixture field.
Patent CN 102101906 A have reported the preparation method of a kind of acid amides/imide-type high density polycarboxylate high performance water-reducing agent.This patent is first unsaturated acid anhydride and monobasic hydramine acylation reaction to be obtained acylate by the first step; second step is that pol yalkylene glycol monoalkyl ether, unsaturated acid (acid anhydride) are carried out catalytic esterification; obtain esterification products; the 3rd the step be with acylate, esterification products, sulphonic acids minor comonomer under the effect of initiator and copolymerization conditioning agent; carry out free-radical polymerizedly then copolymerization product pH value being adjusted into 6-7, make poly carboxylic acid series water reducer.Water-reducing rate and the slump retaining of this water reducer are better; the water reducer that can prepare high density (70-80%) reduces transportation cost; but use unsaturated acid anhydride and monobasic hydramine to carry out acylation reaction; very difficult assurance does not have the generation of esterification; and preparation process is comparatively complicated, and technique controlling difficulty is larger.
Patent CN 102181020 A have reported the method for the synthetic high performance water reducing agent of polyocarboxy acid of amidation reactive monomer copolyreaction.This patent is (methyl) Acrylic Acid Monomer and an end to be contained amino methoxy polyoxyethylene base ether prepare a kind of polymerisable monomer by amidate action under catalyst action, again with (methyl) Acrylic Acid Monomer, chain shift monomer under the initiator effect in the aqueous solution after the copolymerization with in the basic solution and the poly carboxylic acid series water reducer of system.Main side chain connects by amido linkage in this water reducer molecular structure, and water-reducing property is excellent, but it is harsh to prepare polymerisable monomer process conditional at amidate action, is difficult to control.
Summary of the invention
The purpose of this invention is to provide a kind of high concrete water-reducing ratio that under the low-dosage condition, still has, have simultaneously polyether amine modified polycarboxylate high performance water-reducing agent of good concrete slump maintenance and preparation method thereof.
Polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, it is to contain following carboxylic acid group's structural units I, following phosphorus based structures unit II, the following co-poly carboxylic acid that is derived from amide group polyether structure unit III of being derived from of being derived from, wherein:
Structural units I is
Wherein: R
1Expression hydrogen, methyl or COOM group, R
2Expression hydrogen, methyl or CH
2COOM group, M represent hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
The structural unit II is
Wherein: M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
The structural unit III is
Wherein: R
3Expression hydrogen, methyl or COOM group, R
4Expression hydrogen, methyl or CH
2The COOM group; R
5Identical or different, expression hydrogen, methyl or ethyl; R
6Alkyl or its mixture of expression hydrogen or 1～18 carbon atom; N represents the adduct number of oxyalkylene group, is the Arbitrary Digit in 1～300;
Described co-poly carboxylic acid has:
The weight of structural units I accounts for 2.0%～30.0% of co-poly carboxylic acid gross weight; With
5000～120000 weight-average molecular weight.
A kind of method for preparing the described polyether amine modified polycarboxylate high performance water-reducing agent of claim 1, it comprises the steps:
Step 1: in 50 ℃～100 ℃ the aqueous solution, make by the unsaturated carboxylic acid monomer A of following general formula (4) expression and under the condition that Hypophosporous Acid, 50 or its salt exist, carry out copolymerization, obtain molecular weight and be the carboxylic acid-based copolymer of 1000～30000 phosphorous-containigroups groups; Wherein:
Unsaturated carboxylic acid monomer A is
Wherein: R
7Expression hydrogen, methyl or COOM group, R
8Expression hydrogen, methyl or CH
2COOM group, M represent hydrogen, monovalence metal, divalent metal, ammonium or organic amino group; Work as R
7Expression COOM group or R
8Be expressed as CH
2During the COOM group, between two COOM groups of monomer A, exist with the COOM form or form acid anhydrides;
Step 2: the carboxylic acid-based copolymer of the phosphorous-containigroups groups that step 1 is obtained with carry out amidate action by the polyetheramine monomers B of following general formula (5) expression at 80 ℃～200 ℃, obtain described polyether amine modified polycarboxylate high performance water-reducing agent;
Wherein: R
9Identical or different, expression hydrogen, methyl or ethyl; R
10Alkyl or its mixture of expression hydrogen or 1-18 carbon atom; N represents the adduct number of oxyalkylene group, is the Arbitrary Digit in 1～300;
The consumption of described Hypophosporous Acid, 50 or its salt be in the step 1 unsaturated monomer gross weight 1.0%～10.0%;
The ratio of unsaturated monomer gross weight is 2:1～11:1 in the consumption of described polyetheramine monomers B and the step 1.
Described polyether amine modified polycarboxylate high performance water-reducing agent weight-average molecular weight is 5000～120000.Molecular weight is too low or too high, and the performance of high performance water reducing agent of polyocarboxy acid is all deteriorated.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, measures take polyoxyethylene glycol as standard substance.
There is not special restriction to being used for unsaturated carboxylic acid monomer A of the present invention, as long as it is can be by the monomer of above general formula (4) expression.Monomer A comprises: vinylformic acid, methacrylic acid, methylene-succinic acid, itaconic anhydride, toxilic acid, maleic anhydride, fumaric acid and butenoic acid, and univalent metal salt, divalent metal salt, ammonium salt and organic amine salt.Monomer A is a kind of or its mixture wherein.
There is not special restriction to being used for polyetheramine monomers B of the present invention, as long as it is can be by the monomer of above general formula (5) expression.
When the carboxylic acid-based copolymer of preparation phosphorous-containigroups groups, can also add following monomer component:
Unsaturated polyether comprises vinyl polyether, allyl polyether, methacrylic polyethers, 3-methyl-3-butenyl polyethers;
(methyl) acrylate comprises methyl acrylate, ethyl propenoate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, dimethylaminoethyl acrylate, vinylformic acid diethylin ethyl ester, the polyalkylene glycol acrylate ester, polyalkylene glycol acrylate polypropylene glycol ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, dimethylaminoethyl methacrylate, methacrylic acid diethylin ethyl ester, the methacrylic acid polyethylene glycol, methacrylic acid polyethylene glycol polypropylene glycol ester;
Unsaturated sulfonic acid or its salt comprise sodium allyl sulfonate, methallylsulfonic acid sodium, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic 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, tertiary ethylene carbonate;
Fumarate or maleic acid ester comprise monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, fumaric acid mono—n—butylester, fumaric acid mono methoxy polyethylene glycol ester, fumaric acid mono methoxy polyethylene glycol polypropylene glycol ester, monomethyl maleate, ethyl maleate, toxilic acid list propyl ester, butyl maleate, toxilic acid mono methoxy polyethylene glycol ester, toxilic acid mono methoxy polyethylene glycol polypropylene glycol ester.
When the carboxylic acid-based copolymer of preparation phosphorous-containigroups groups, can select the water-soluble polymeric reaction initiator, such as ammonium or alkali-metal persulphate, hydrogen peroxide and tertbutyl peroxide.
When implementing amidate action, can or vacuumize to make amidate action more complete by nitrogen gas stream, airflow, Reaction time shorten is raised the efficiency simultaneously.
After amidate action is finished, select as required the solid content of conditioned reaction product or selection not to regulate.When not regulating the solid content of reaction product, can prepare by cooling, pulverizing the high performance water reducing agent of polyocarboxy acid of powder.
After amidate action was finished, pH value or the selection selecting as required to regulate product were not regulated.If select to regulate the pH value, used neutralization reagent is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia or organic amine or their aqueous solution.
In addition, high performance water reducing agent of polyocarboxy acid 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.Polyether amine modified polycarboxylate high performance water-reducing agent of the present invention still has high concrete water-reducing ratio under the low-dosage condition, have simultaneously good concrete slump and keep.
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:
A-1: vinylformic acid
A-2: maleic anhydride
A-3: methacrylic acid
A-4: methylene-succinic acid
B-1: the polyetheramine monomer, structural formula is
, wherein the addition mode of oxyethane and propylene oxide is random copolymerization
B-2: the polyetheramine monomer, structural formula is
, wherein the addition mode of oxyethane and propylene oxide is random copolymerization
B-3: the polyetheramine monomer, structural formula is
C-1: Hydroxyethyl acrylate
The C-2:2-acrylamide-2-methyl propane sulfonic
C-3: methacrylic polyglycol ether (average EO adduct number 54)
Embodiment 1
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 30.0g one hydration sodium hypophosphite, 750.0g water, stir and be warming up to 80 ℃.Drip respectively simultaneously 100.0g ammonium persulfate aqueous solution (be dissolved in 90.0g water obtain by the 10.0g ammonium persulphate), the 120.0g sodium hypophosphite aqueous solution (be dissolved in 90.0g water obtain by 30.0g one hydration sodium hypophosphite) and 1000.0g A-1, time for adding is controlled at respectively 150 minutes, 120 minutes and 150 minutes, temperature of reaction is controlled at 78～82 ℃.After dripping end, 78～82 ℃ of lower insulations about 60 minutes, make polyreaction complete, obtain the carboxylic acid-based copolymer of phosphorous-containigroups groups, be designated as PA-1, it is 3800 that GPC tests its weight-average molecular weight.
The carboxylic acid-based copolymer PA-1 and the 648.25gB-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 180 ℃ and be incubated 3h, the water in the reaction system is reclaimed by condenser and with receiving trap.Then be cooled to about 60 ℃, add the pH value to 7.0 that 138.0g 30%NaOH regulates product, and add the solid content to 40% that 1050.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-1.The weight-average molecular weight of product is 35700, and carboxylic acid group's structural unit accounts for 9.5% of polymer weight.
Embodiment 2
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 40.0g one hydration potassium hypophosphite, 600.0g water, stir and be warming up to 90 ℃.Drip respectively simultaneously 200.0g ammonium persulfate aqueous solution (be dissolved in 180.0g water obtain by the 20.0g ammonium persulphate), the 160.0g potassium hypophosphite aqueous solution (be dissolved in 12.0g water obtain by 40.0g one hydration potassium hypophosphite) and 1000.0g A-3, time for adding is controlled at respectively 180 minutes, 150 minutes and 180 minutes, temperature of reaction is controlled at 88～92 ℃.After dripping end, 88～92 ℃ of lower insulations about 60 minutes, make polyreaction complete, obtain the carboxylic acid-based copolymer of phosphorous-containigroups groups, be designated as PA-2, it is 3100 that GPC tests its weight-average molecular weight.
The carboxylic acid-based copolymer PA-2 and the 586.5gB-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 140 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 140 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 1.5h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 115.0g 30%NaOH regulates product, and add the solid content to 40% that 920g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-2.The weight-average molecular weight of product is 25500, and carboxylic acid group's structural unit accounts for 9.0% of polymer weight.
Embodiment 3
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 200.0g A-2,20.0g one hydration sodium hypophosphite, 800.0g water, stir and be warming up to 80 ℃.Drip respectively simultaneously 100.0g ammonium persulfate aqueous solution (be dissolved in 90.0g water obtain by the 10.0g ammonium persulphate), the 80.0g sodium hypophosphite aqueous solution (be dissolved in 60.0g water obtain by 20.0g one hydration sodium hypophosphite) and 800.0g A-1, time for adding is controlled at respectively 210 minutes, 150 minutes and 210 minutes, temperature of reaction is controlled at 78～82 ℃.After dripping end, 78～82 ℃ of lower insulations about 60 minutes, make polyreaction complete, obtain the carboxylic acid-based copolymer of phosphorous-containigroups groups, be designated as PA-3, it is 2900 that GPC tests its weight-average molecular weight.
The carboxylic acid-based copolymer PA-3 and the 742.9gB-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 2h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 150.0g 30%NaOH regulates product, and add the solid content to 40% that 1120.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-3.The weight-average molecular weight of product is 29500, and carboxylic acid group's structural unit accounts for 9.7% of polymer weight.
Embodiment 4
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 400.0g A-4,20.0g one hydration sodium hypophosphite, 800.0g water, stir and be warming up to 52 ℃.Drip respectively simultaneously 100.0g sodium persulfate aqueous solution (be dissolved in 90.0g water obtain by the 10.0g Sodium Persulfate), the 80.0g sodium hypophosphite aqueous solution (be dissolved in 60.0g water obtain by 20.0g one hydration sodium hypophosphite) and 600.0g A-1, time for adding is controlled at respectively 180 minutes, 150 minutes and 180 minutes, temperature of reaction is controlled at 50～54 ℃.After dripping end, 50～54 ℃ of lower insulations about 60 minutes, make polyreaction complete, obtain the carboxylic acid-based copolymer of phosphorous-containigroups groups, be designated as PA-4, it is 4400 that GPC tests its weight-average molecular weight.
The carboxylic acid-based copolymer PA-4 and the 703.8gB-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 100 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 100 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 4h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 140.0g 30%NaOH regulates product, and add the solid content to 40% that 1080.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-4.The weight-average molecular weight of product is 42400, and carboxylic acid group's structural unit accounts for 9.7% of polymer weight.
Embodiment 5
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 30.0g one hydration sodium hypophosphite, 400.0g water, stir and be warming up to 80 ℃.Drip respectively simultaneously 100.0g sodium persulfate aqueous solution (be dissolved in 90.0g water obtain by the 10.0g Sodium Persulfate), 1470.0g Acrylic Acid Monomer solution (be dissolved in the 450.0g water and obtain by 20.0g one hydration sodium hypophosphite, 800.0g A-1,200.0g C-1), Sodium Persulfate solution and Acrylic Acid Monomer solution time for adding all are controlled at 180 minutes, and temperature of reaction is controlled at 78～82 ℃.After dripping end, 78～82 ℃ of lower insulations about 60 minutes, make polyreaction complete, obtain the carboxylic acid-based copolymer of phosphorous-containigroups groups, be designated as PA-5, it is 3400 that GPC tests its weight-average molecular weight.
The carboxylic acid-based copolymer PA-5 and the 547.4gB-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 160 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 160 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 1h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 110.0g 30%NaOH regulates product, and add the solid content to 40% that 880.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-5.The weight-average molecular weight of product is 26400, and carboxylic acid group's structural unit accounts for 9.2% of polymer weight.
Embodiment 6
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 50.0g Hypophosporous Acid, 50,300.0g water, stir and be warming up to 60 ℃.Drip respectively simultaneously 100.0g ammonium persulfate aqueous solution (be dissolved in 90.0g water obtain by the 10.0g ammonium persulphate), 1550.0g Acrylic Acid Monomer solution (be dissolved in 500.0g water obtain by 50.0g Hypophosporous Acid, 50,720.0g A-1,280.0g C-2), ammonium persulfate solution and Acrylic Acid Monomer solution time for adding all are controlled at 180 minutes, and temperature of reaction is controlled at 58～62 ℃.After dripping end, 58～62 ℃ of lower insulations about 60 minutes, make polyreaction complete, obtain the carboxylic acid-based copolymer of phosphorous-containigroups groups, be designated as PA-6, it is 2500 that GPC tests its weight-average molecular weight.
The carboxylic acid-based copolymer PA-6 and the 488.75gB-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 130 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 130 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 2h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 100.0g 30%NaOH regulates product, and add the solid content to 40% that 790.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-6.The weight-average molecular weight of product is 17800, and carboxylic acid group's structural unit accounts for 9.1% of polymer weight.
Embodiment 7
In the four-hole boiling flask of the 2000ml that disposes agitator, thermometer, Dropping feeder, add 100.0g A-2,600.0g C-3,10.0g one hydration sodium hypophosphite and 760.0g water, stir and be warming up to 80 ℃.Drip respectively simultaneously 150.0g ammonium persulfate aqueous solution (be dissolved in 135.0g water obtain by the 15.0g Sodium Persulfate), the 80.0g sodium hypophosphite aqueous solution (be dissolved in 60.0g water obtain by 20.0g one hydration sodium hypophosphite) and 300.0g A-1, time for adding is controlled at respectively 180 minutes, 150 minutes and 180 minutes, temperature of reaction is controlled at 78～82 ℃.After dripping end, 78～82 ℃ of lower insulations about 60 minutes, make polyreaction complete, obtain the carboxylic acid-based copolymer of phosphorous-containigroups groups, be designated as PA-7, it is 15200 that GPC tests its weight-average molecular weight.
The carboxylic acid-based copolymer PA-7 and the 312.8g B-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 130 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 130 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 2h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 60.0g 30%NaOH regulates product, and add the solid content to 40% that 560.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-7.The weight-average molecular weight of product is 70600, and carboxylic acid group's structural unit accounts for 8.0% of polymer weight.
Embodiment 8
The carboxylic acid-based copolymer PA-1 and the 449.65g B-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 2h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 152.0g 30%NaOH regulates product, and add the solid content to 40% that 680.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-8.The weight-average molecular weight of product is 20800, and carboxylic acid group's structural unit accounts for 15.2% of polymer weight.
Embodiment 9
The carboxylic acid-based copolymer PA-1 and the 1094.8g B-1 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 2h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 110.0g 30%NaOH regulates product, and add the solid content to 40% that 1690.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-9.The weight-average molecular weight of product is 49900, and carboxylic acid group's structural unit accounts for 5.0% of polymer weight.
Embodiment 10
The carboxylic acid-based copolymer PA-4 and the 372.6g B-2 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 2h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 145.0g 30%NaOH regulates product, and add the solid content to 40% that 570.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-10.The weight-average molecular weight of product is 19700, and carboxylic acid group's structural unit accounts for 16.6% of polymer weight.
Embodiment 11
The carboxylic acid-based copolymer PA-4 and the 676.44g B-3 that add the 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask that disposes agitator, thermometer, condenser and vacuum receiving device, progressively be warming up to 120 ℃ and be incubated 1h, the water in the reaction system is reclaimed by condenser and with receiving trap; Then keep about 120 ℃ of temperature of reaction, open vacuum, the relative vacuum degree in the reaction system is progressively risen to-0.08MPa, keep this vacuum tightness until react completely, about 2h of time.Then be cooled to about 60 ℃, add the pH value to 7.0 that 145.0g 30%NaOH regulates product, and add the solid content to 40% that 1030.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-11.The weight-average molecular weight of product is 35800, and carboxylic acid group's structural unit accounts for 10.1% of polymer weight.
Embodiment 12
To disposing agitator, thermometer, N
2Add carboxylic acid-based copolymer PA-4,351.9g B-1 and the 186.3g B-2 of 200.0g phosphorous-containigroups groups in the 2000ml four-hole boiling flask of access device, condenser and receiving trap, in reaction system, continue slowly to pass into N
2, progressively be warming up to 120 ℃, the water in the reaction system is reclaimed, until react completely about 3h of time by condenser and with receiving trap.Then be cooled to about 60 ℃, add the pH value to 7.0 that 145.0g 30%NaOH regulates product, and add the solid content to 40% that 820.0g water is regulated product, obtain polyether amine modified polycarboxylate high performance water-reducing agent of the present invention, be designated as NPA-12.The weight-average molecular weight of product is 28700, and carboxylic acid group's structural unit accounts for 12.2% of polymer weight.
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, 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 the indexs such as water-reducing rate, air content, slump hold facility, and test result sees Table 2.
Table 1 test concrete mix
| Starting material | Cement | River sand | The 5-10mm stone | The 10-20mm stone |
| Proportioning, Kg/m 3 | 360 | 805 | 410 | 615 |
Table 2 high performance water reducing agent of polyocarboxy acid the performance test results
Annotate :/expression concrete does not have divergence
Test result from table 2, polyether amine modified polycarboxylate high performance water-reducing agent of the present invention still has high concrete water-reducing ratio under the low-dosage condition, still have preferably concrete slump and degree of mobilization after being mixed with simultaneously a hour of high performance water reducing agent of polyocarboxy acid of the present invention.
Claims (2)
1. polyether amine modified polycarboxylate high performance water-reducing agent it is characterized in that containing following carboxylic acid group's structural units I, following phosphorus based structures unit II, the following co-poly carboxylic acid that is derived from amide group polyether structure unit III of being derived from of being derived from, wherein:
Structural units I is
Wherein: R
1Expression hydrogen, methyl or COOM group, R
2Expression hydrogen, methyl or CH
2COOM group, M represent hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
The structural unit II is
Wherein: M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
The structural unit III is
Wherein: R
3Expression hydrogen, methyl or COOM group, R
4Expression hydrogen, methyl or CH
2The COOM group; R
5Identical or different, expression hydrogen, methyl or ethyl; R
6The alkyl of expression hydrogen or 1～18 carbon atom; N represents the adduct number of oxyalkylene group, is the Arbitrary Digit in 1～300;
Described co-poly carboxylic acid has:
The weight of structural units I accounts for 2.0%～30.0% of co-poly carboxylic acid gross weight; With
5000～120000 weight-average molecular weight.
2. a method for preparing the described polyether amine modified polycarboxylate high performance water-reducing agent of claim 1 is characterized in that it comprises the steps:
Step 1: in 50 ℃～100 ℃ the aqueous solution, make by the unsaturated carboxylic acid monomer A of following general formula (4) expression and under the condition that Hypophosporous Acid, 50 or its salt exist, carry out copolymerization, obtain molecular weight and be the carboxylic acid-based copolymer of 1000～30000 phosphorous-containigroups groups; Wherein:
Unsaturated carboxylic acid monomer A is
Wherein: R
7Expression hydrogen, methyl or COOM group, R
8Expression hydrogen, methyl or CH
2COOM group, M represent hydrogen, monovalence metal, divalent metal, ammonium or organic amino group; Work as R
7Expression COOM group or R
8Be expressed as CH
2During the COOM group, between two COOM groups of monomer A, exist with the COOM form or form acid anhydrides;
Step 2: the carboxylic acid-based copolymer of the phosphorous-containigroups groups that step 1 is obtained with carry out amidate action by the polyetheramine monomers B of following general formula (5) expression at 80 ℃～200 ℃, obtain described polyether amine modified polycarboxylate high performance water-reducing agent;
Wherein: R
9Identical or different, expression hydrogen, methyl or ethyl; R
10The alkyl of expression hydrogen or 1-18 carbon atom; N represents the adduct number of oxyalkylene group, is the Arbitrary Digit in 1～300;
The consumption of described Hypophosporous Acid, 50 or its salt be in the step 1 unsaturated monomer gross weight 1.0%～10.0%;
The ratio of unsaturated monomer gross weight is 2: 1～11: 1 in the consumption of described polyetheramine monomers B and the step 1.
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| CN107337789B (en) * | 2016-12-30 | 2020-08-07 | 江苏苏博特新材料股份有限公司 | Preparation method and application of micromolecular phosphate dispersant |
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| CN101215119A (en) * | 2007-12-28 | 2008-07-09 | 淘正化工（上海）有限公司 | High-performance polycarboxylic acids water reducing agent prepared by one-step method |
| CN102173642B (en) * | 2011-02-25 | 2013-01-02 | 南京瑞迪高新技术公司 | Polyetheramine carboxylate high-efficiency water-reducing agent |
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