CN107446089A - One kind is drawn money on credit chain end group esterification modification polycarboxylate water-reducer and preparation method thereof - Google Patents
One kind is drawn money on credit chain end group esterification modification polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN107446089A CN107446089A CN201710675802.6A CN201710675802A CN107446089A CN 107446089 A CN107446089 A CN 107446089A CN 201710675802 A CN201710675802 A CN 201710675802A CN 107446089 A CN107446089 A CN 107446089A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
Drawn money on credit chain end group esterification modification polycarboxylate water-reducer the invention provides one kind, the polycarboxylate water-reducer is in the presence of initiator and chain-transferring agent, formed by three kinds of monomer copolymerizations, three kinds of monomers are respectively unsaturated monocarboxylic acid, end carboxyl polyether macromonomer and the first polyether macromonomer.The end carboxyl polyether macromonomer is 5~30 parts by weight, the unsaturated monocarboxylic acid is 5~15 parts by weight, first polyether macromonomer is 55~90 parts by weight, and the initiator is the 0.5~4% of total monomer weight, and chain-transferring agent is the 0.1~1% of total monomer weight.The new polycarboxylic acid water reducer of the present invention has good adaptability to the mud that aggregate contains, and preparation technology is simple, and can be used in mixed way in any proportion with conventional polycarboxylate water-reducer.
Description
Technical field
The invention belongs to technical field of concrete additives, and in particular to one kind chain end group esterification modification polycarboxylic acids of drawing money on credit subtracts
Aqua and preparation method thereof.
Background technology
Polycarboxylate water-reducer is used for concrete, meeting to the clay content quite sensitive of sand material, the higher sand material of clay content
Greatly improve the dosage of polycarboxylate water-reducer in concrete, hence it is evident that improve the cost of concrete.In addition it is past to increase water reducer dosage
Toward concrete retarding can be caused, so as to extend the duration.
At present, the main path for improving the anti-mud effect of polycarboxylate water-reducer has three kinds, and the first is by polycarboxylate water-reducer
Compounded with the small-molecule substance of cationic.Second is to polycarboxylate water-reducer molecule using cationic vinyl monomer
Main chain carries out block modified.Such as the Chinese invention patent application of Application No. 201110128635.6, mud blocking agent for concrete and
Its preparation method；Application No. 201610057539.X Chinese invention patent application, a kind of compound polycarboxylate water-reducer are used
Hinder the preparation method of mud agent；The application for a patent for invention of Application No. 201410403384.1, a kind of agent on crack resistance of concrete mud agent and its system
Preparation Method；The Chinese invention patent application of Application No. 201310070383.5, a kind of polymerization with anti-mud or resistance to mud performance
Thing aqueous solution and preparation method thereof；Cationic monomer is employed to participate in polymerization or formed containing cationic surfactant
Mixture.The third is polycarboxylate water-reducer of the synthesis without polyethers long-chain branch.Munich, Germany polytechnical university in terms of this
Professor Plank done more research.2012, Plank synthesized condensation polymer CFS using cyclohexanone, formaldehyde, sulphite.
The same year, Plank are polymerize to obtain a kind of new without polyethers length using methacrylic acid with hydroxy alkyl methacrylate
Side chain PCE.2014, Lei L and Plank etc. were using maleic anhydride, maleic acid mono alkyl ester, 4- hydroxy-butyl vinyl ethers
For raw material, polycarboxylate water-reducer of the synthesis without polyethers long-chain branch.Adsorbance and XRD test results show to use three of the above side
Short-chain branch water reducer prepared by method does not adsorb with montmorillonite intercalation, and the adsorbance in montmorillonite is also far smaller than conventional polycarboxylic acids
Water reducer.
Polycarboxylate water-reducer mostlys come from the montmorillonite in clay to water reducer polyethers long-chain branch to the sensitiveness of mud
Suction-operated.Therefore, it is necessary to by being modified to polyethers long-chain branch, silt montmorillonite is highly resistant to so as to obtain one kind
The new polycarboxylic acid water reducer of suction-operated.
The content of the invention
The present invention provides one kind for solution above-mentioned technical problem and drawn money on credit chain end group esterification modification polycarboxylate water-reducer and its system
Preparation Method.The water reducer reaches by carrying out esterification modification to the terminal hydroxy group of polyethers long-chain branch and is effective against silt montmorillonite suction
Attached effect.
In order to solve the above technical problems, technical scheme is as follows：
One kind is drawn money on credit chain end group esterification modification polycarboxylate water-reducer, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit
It is in the presence of initiator and chain-transferring agent, is formed by three kinds of monomer copolymerizations, three kinds of monomers is respectively unsaturated unitary
Carboxylic acid, end carboxyl polyether macromonomer and the first polyether macromonomer, the end carboxyl polyether macromonomer have following structure：
Wherein R1, R2, R3For H or CH3, R4For H or monovalence alkali metal, n=1~100, m=2~10.
In such scheme, n=50, m=2.
In such scheme, the end carboxyl polyether macromonomer is 5~30 parts by weight, the unsaturated monocarboxylic acid is 5~
15 parts by weight, first polyether macromonomer are 55~90 parts by weight, and the initiator is the 0.5~4% of total monomer weight, chain
Transfer agent is the 0.1~1% of total monomer weight.
In such scheme, it is described draw money on credit chain end group esterification modification polycarboxylate water-reducer specific preparation method be：
By the end carboxyl polyether macromonomer of 5~30 parts by weight and 55~90 the first polyether macromonomers of parts by weight, it is dissolved in
In the water of 1.2~1.4 times of parts by weight, reactor is put into, the temperature for controlling reactor is in 20~80 DEG C of water；
The unsaturated monocarboxylic acid monomer of 5~15 parts by weight is dissolved in the water of its 1.1~1.3 times of parts by weight, prepared
Into solution A, initiator and chain-transferring agent are dissolved in the water of its 5~20 times of parts by weight, are configured to B solution；
Solution A and B solution are added dropwise in reactor respectively, the time for adding of solution A and B solution is respectively 3~3.5h,
And 3~4h, 2~3h is then incubated, is cooled to room temperature, alkali lye regulation pH to 6~7 is added, obtains the chain end group ester of drawing money on credit
Change modified polycarboxylic acid water reducer.
In such scheme, the end carboxyl polyether macromonomer is carried out in anhydrous conditions by the second polyether macromonomer with acid anhydrides
Esterification is prepared, and second polyether macromonomer is allyl polyethenoxy ether, methyl allyl polyoxyethylene ether or isoamyl
One or more in alkenyl APEO, the acid anhydrides are malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, heptan
The one or more of dicarboxylic anhydride, phthalic anhydride or maleic anhydride.
In such scheme, the specific preparation method of the end carboxyl polyether macromonomer is：By the molecule of 50~80 mass parts
Measure and be well mixed for 500~5,000 second polyether macromonomers with the dicarboxylic anhydride of 3~10 mass parts, and add 5~10 mass parts
Toluene stirs 1~5 hour at 75~105 DEG C as water entrainer, is evaporated under reduced pressure and removes remaining toluene, be cooled to room temperature, obtain
To end carboxyl polyether macromonomer.
In such scheme, the unsaturated monocarboxylic acid is selected from acrylic acid, methacrylic acid, PAA, metering system
One or more in disulfonate acid, methyl methacrylate or hydroxy-ethyl acrylate.
In such scheme, first polyether macromonomer is selected from allyl polyethenoxy ether, methacrylic polyoxyethylene
One or more in ether or isopentene group APEO.
In such scheme, the initiator is the one or more in ammonium persulfate, sodium peroxydisulfate or hydrogen peroxide.
In such scheme, the chain-transferring agent is in TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids or mercaptoethanol
It is one or more of.
Beneficial effects of the present invention are：Chain end group esterification modification polycarboxylate water-reducer provided by the invention of drawing money on credit, due to ester
The end group of the end carboxyl polyether macromonomer obtained after change becomes electronegative carboxylic group by uncharged oh group, and clay
Particle surface is negatively charged, and the electrostatic repulsion between such polycarboxylate water-reducer molecule and clay will increase, and greatly reduces poly-
The possibility of hydrogen bond is formed between carboxylic acid molecules side chain and mud particles, so as to reduce its combination between mud particles, is had
Obvious resistance mud effect.Also, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit of the present invention is to the mud in aggregate
There is extensive adaptability, influence of the clay content to polycarboxylate water-reducer can be weakened significantly.
Embodiment
Below in conjunction with end carboxyl polyether macromonomer of the specific embodiment to the present invention and chain end group ester prepared therefrom of drawing money on credit
The preparation method for changing modified polycarboxylic acid water reducer is described further.Unless limited otherwise, term used herein is ability
The implication that field technique personnel are generally understood that.
Embodiment 1
1st, end carboxyl polyether macromonomer is prepared.
The isopentene group APEO that 7000g molecular weight is 2400 is well mixed with 700g succinic anhydrides, and added
Enter 1000g toluene as water entrainer, stirred 3 hours at 95 DEG C, be evaporated under reduced pressure and remove remaining toluene, be subsequently cooled to room
Temperature, obtain end carboxyl polyether macromonomer.Reaction equation is as follows：
2nd, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit with resistance mud function is prepared.
Dissolve end carboxyl polyether macromonomer and polyether macromonomer.3000g end carboxyls polyether macromonomer and 5500gTPEG are gathered
Ether polymeric monomer is added in reactor, and adds 11900g deionized waters, and keeping temperature is 60 DEG C, stirring, until two kinds of polymeric monomers
It is completely dissolved.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.1000g acrylic acid is dissolved in
In 1100g deionized waters, wiring solution-forming A, 45g ammonium persulfates and 47.5g 3- mercaptopropionic acids are dissolved in 1387.5g deionized waters
In, wiring solution-forming B.
Insulation reaction is added dropwise.Large monomer solution in reactor is kept being sufficiently stirred, keeping temperature is 60 DEG C, by solution
A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3.5 hours, and solution B dripped off in 4 hours.Solution B
After being added dropwise, 3 hours are incubated, is subsequently cooled to room temperature.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain chain end group esterification modification polycarboxylate water-reducer of drawing money on credit.
After tested, chain end group esterification modification polycarboxylate water-reducer weight average molecular weight that what the present embodiment obtained draw money on credit is 53260.
Embodiment 2
1st, end carboxyl polyether macromonomer is prepared.
The isopentene group APEO that 6000g molecular weight is 2400 is well mixed with 500g adipic anhydrides, and added
Enter 700g toluene as water entrainer, 2h is stirred at 90 DEG C, is evaporated under reduced pressure and removes remaining toluene, be cooled to room temperature, obtain
End carboxyl polyether macromonomer.
2nd, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit with resistance mud function is prepared.
Dissolve end carboxyl polyether macromonomer and polyether macromonomer.By 2000g end carboxyls polyether macromonomer and 6000g iso-amylene
Base APEO polymeric monomer is added in reactor, and adds 10400g deionized waters, and keeping temperature is 40 DEG C, stirring, until
Two kinds of polymeric monomers are completely dissolved.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.700g methacrylic acids are dissolved in
In 910g deionized waters, wiring solution-forming A, the 2 mercaptopropionic acid of 87g sodium peroxydisulfates and 60.9g is dissolved in 1479g deionized waters,
Wiring solution-forming B.
Insulation reaction is added dropwise.Large monomer solution in reactor is kept being sufficiently stirred, keeping temperature is 40 DEG C, by solution
A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3 hours, and solution B dripped off in 3.5 hours.Solution B
After being added dropwise, 2 hours are incubated, is subsequently cooled to room temperature.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain chain end group esterification modification polycarboxylate water-reducer of drawing money on credit.
After tested, chain end group esterification modification polycarboxylate water-reducer weight average molecular weight that what the present embodiment obtained draw money on credit is 34550.
Embodiment 3
1st, end carboxyl polyether macromonomer is prepared.
The isopentene group APEO that 5000g molecular weight is 2400 is well mixed with 300g malonic anhydrides, and added
Enter 500g toluene as water entrainer, 1h is stirred at 85 DEG C, is evaporated under reduced pressure and removes remaining toluene, be cooled to room temperature, obtain
End carboxyl polyether macromonomer.
2nd, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit with resistance mud function is prepared.
Dissolve end carboxyl polyether macromonomer and polyether macromonomer.1500g end carboxyl polyether macromonomers, and 7000g is different
Pentenyl APEO polymeric monomer is added in reactor, and adds 10200g deionized waters, and keeping temperature is 20 DEG C, stirring,
Until two kinds of polymeric monomers are completely dissolved.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.500g PAAs are dissolved in
In 600g deionized waters, wiring solution-forming A, the hydrogen peroxide of 380g 50% concentration and 90g TGAs are dissolved in 1400g deionizations
In water, wiring solution-forming B.
Insulation reaction is added dropwise.Large monomer solution in reactor is kept being sufficiently stirred, keeping temperature is 20 DEG C, by solution
A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3 hours, and solution B dripped off in 3.5 hours.Solution B
After being added dropwise, 2 hours are incubated.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain chain end group esterification modification polycarboxylate water-reducer of drawing money on credit.
After tested, the weight average molecular weight of what the present embodiment obtained draw money on credit chain end group esterification modification polycarboxylate water-reducer is
21710。
Embodiment 4
1st, end carboxyl polyether macromonomer is prepared.
The isopentene group APEO that 8000g molecular weight is 2400 is well mixed with 900g phthalic anhydrides,
And 500g toluene is added as water entrainer, 4h is stirred at 100 DEG C, is evaporated under reduced pressure and removes remaining toluene, be cooled to room temperature,
Obtain end carboxyl polyether macromonomer.
2nd, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit with resistance mud function is prepared.
Dissolve end carboxyl polyether macromonomer and polyether macromonomer.By 1000g end carboxyls polyether macromonomer and 8000g isoamyls
Alkenyl APEO polymeric monomer is added in reactor, and adds 12600g deionized waters, and keeping temperature is 80 DEG C, stirring, directly
It is completely dissolved to two kinds of polymeric monomers.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.By 1200g methyl methacrylates
It is dissolved in 1560g deionized waters, wiring solution-forming A, 204g sodium peroxydisulfates and 30.6g mercaptoethanols is dissolved in 1173g deionized waters
In, wiring solution-forming B.
Insulation reaction is added dropwise.Large monomer solution in reactor is kept being sufficiently stirred, keeping temperature is 60 DEG C, by solution
A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3.5 hours, and solution B dripped off in 4 hours.Solution B
After being added dropwise, 3 hours are incubated, is subsequently cooled to room temperature.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain chain end group esterification modification polycarboxylate water-reducer of drawing money on credit.
After tested, the weight average molecular weight of what the present embodiment obtained draw money on credit chain end group esterification modification polycarboxylate water-reducer is
68640。
Embodiment 5
1st, end carboxyl polyether macromonomer is prepared.
The isopentene group APEO that 7000g molecular weight is 2400 is well mixed with 1000g malonic anhydrides, and added
Enter 1000g toluene as water entrainer, stir 5h at 105 DEG C, be cooled to room temperature, obtain end carboxyl polyether macromonomer.
2nd, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit with resistance mud function is prepared.
Dissolve end carboxyl polyether macromonomer and polyether macromonomer.By 500g end carboxyl polyether macromonomers, and 9000g isoamyls
Alkenyl APEO polymeric monomer is added in reactor, and adds 13300g deionized waters, and keeping temperature is 50 DEG C, stirring, directly
It is completely dissolved to two kinds of polymeric monomers.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.1500g hydroxy-ethyl acrylates is molten
In 1800g deionized waters, wiring solution-forming A, 110g ammonium persulfates and 11g TGAs are dissolved in 1210g deionized waters, matched somebody with somebody
Into solution B.
Insulation reaction is added dropwise.Large monomer solution in reactor is kept being sufficiently stirred, keeping temperature is 50 DEG C, by solution
A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3 hours, and solution B dripped off in 3.5 hours.Solution B
After being added dropwise, 3 hours are incubated, is subsequently cooled to room temperature.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain chain end group esterification modification polycarboxylate water-reducer of drawing money on credit.
After tested, the weight average molecular weight of what the present embodiment obtained draw money on credit chain end group esterification modification polycarboxylate water-reducer is
76850。
Embodiment 6
1st, end carboxyl polyether macromonomer is prepared.
The methyl allyl polyoxyethylene ether that 7000g molecular weight is 2400 is well mixed with 700g adipic anhydrides, and
1000g toluene is added as water entrainer, is stirred 3 hours at 95 DEG C, is evaporated under reduced pressure and removes unnecessary toluene, be cooled to room
Temperature, obtain end carboxyl polyether macromonomer.
2nd, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit with resistance mud function is prepared.
Dissolve end carboxyl polyether macromonomer and polyether macromonomer.By 3000g end carboxyls polyether macromonomer and 5500g methyl alkene
Propyl group APEO polymeric monomer is added in reactor, and adds 11900g deionized waters, and keeping temperature is 60 DEG C, stirring, directly
It is completely dissolved to two kinds of polymeric monomers.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.1000g acrylic acid is dissolved in
In 1100g deionized waters, wiring solution-forming A, 45g ammonium persulfates and 47.5g 3- mercaptopropionic acids are dissolved in 1387.5g deionized waters
In, wiring solution-forming B.
Insulation reaction is added dropwise.Large monomer solution in reactor is kept being sufficiently stirred, keeping temperature is 60 DEG C, by solution
A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3.5 hours, and solution B dripped off in 4 hours.Solution B
After being added dropwise, 3 hours are incubated, is subsequently cooled to room temperature.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain chain end group esterification modification polycarboxylate water-reducer of drawing money on credit.
After tested, the weight average molecular weight of what the present embodiment obtained draw money on credit chain end group esterification modification polycarboxylate water-reducer is
52100。
Embodiment 7
1st, end carboxyl polyether macromonomer is prepared.
The allyl polyethenoxy ether that 7000g molecular weight is 2400 is well mixed with 700g adipic anhydrides, and added
1000g toluene stirs 3 hours at 95 DEG C as water entrainer, is cooled to room temperature, obtains end carboxyl polyether macromonomer.
2nd, the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit with resistance mud function is prepared.
Dissolve end carboxyl polyether macromonomer and polyether macromonomer.By 3000g end carboxyls polyether macromonomer and 5500g pi-allyls
APEO polymeric monomer is added in reactor, and adds 11900g deionized waters, and keeping temperature is 60 DEG C, stirring, until two
Kind polymeric monomer is completely dissolved.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.1000g acrylic acid is dissolved in
In 1100g deionized waters, wiring solution-forming A, 45g ammonium persulfates and 47.5g 3- mercaptopropionic acids are dissolved in 1387.5g deionized waters
In, wiring solution-forming B.
Insulation reaction is added dropwise.Large monomer solution in reactor is kept being sufficiently stirred, keeping temperature is 60 DEG C, by solution
A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3.5 hours, and solution B dripped off in 4 hours.Solution B
After being added dropwise, 3 hours are incubated, is subsequently cooled to room temperature.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain chain end group esterification modification polycarboxylate water-reducer of drawing money on credit.
After tested, chain end group esterification modification polycarboxylate water-reducer weight average molecular weight that what the present embodiment obtained draw money on credit is 56230.
Comparative example
Prepare polycarboxylate water-reducer.
Dissolve polyether macromonomer.The isopentene group APEO polyether macromonomer that 8500g molecular weight is 2400 is added
In reactor, and 11900g deionized waters are added, keeping temperature is 60 DEG C, stirring, until polyether macromonomer is completely dissolved.
Prepare unsaturated monocarboxylic acid monomer solution and initiator, chain-transferring agent solution.1000g acrylic acid is dissolved in
In 1100g deionized waters, wiring solution-forming A, 45g ammonium persulfates and 47.5g 3- mercaptopropionic acids are dissolved in 1387.5g deionized waters
In, wiring solution-forming B.
Insulation reaction is added dropwise.Polyether macromonomer solution in reactor is kept being sufficiently stirred, keeping temperature is 60 DEG C, will
Solution A and solution B are at the uniform velocity added drop-wise in reactor respectively, and wherein solution A dripped off in 3.5 hours, and solution B dripped off in 4 hours.It is molten
After liquid B is added dropwise, 3 hours are incubated, is subsequently cooled to room temperature.
PH value is adjusted.It is 6 that sodium hydroxide solution to the reacting solution pH value that mass fraction is 30% is added into reactor
~7, obtain polycarboxylate water-reducer.
After tested, the weight average molecular weight for the polycarboxylate water-reducer that this comparative example obtains is 56200.
Experimental example
Chain end group esterification modification polycarboxylate water-reducer provided by the invention of drawing money on credit, without compounding polycarboxylate water-reducer again,
Both it can be used separately as water reducer, while there is good resistance mud effect.
In order to detect the effect of the chain end group esterification modification polycarboxylate water-reducer of drawing money on credit of the present invention, from kaolin and swelling
Soil is spiked into cement as clay component, simulates the clay content under reality, carries out each implementation under the solid volume of equal folding
The flowing degree of net paste of cement and concrete test of example and comparative example.Experiment is according to GB/8077-2012《Concrete admixture is homogeneous
Property test method》With JGJ52-2006《Regular concrete sand, stone quality and test method standard》Carry out.
1. flowing degree of net paste of cement is tested.
Reference cement PO42.5 is selected, mixes kaolin and bentonite outside, volume is respectively the 5% and 3% of cement quality, so
Afterwards by draw money on credit chain end group esterification modification polycarboxylate water-reducer and the polycarboxylate water-reducer of comparative example of embodiment 1 to embodiment 7,
According to the folding addition of amount 0.25% admittedly, flowing degree of net paste of cement test is carried out, test result is shown in Table 1.
The flowing degree of net paste of cement test result of table 1
2nd, concrete test.
Concrete test, in aggregate respectively it is interior mix 5% and 3% kaolin and bentonite, cement selection reference cement, subtract
The solid volume of aqua folding is 2.5%, and result of the test is shown in Table 2.
The concrete test result of table 2
From the point of view of the test result of above-mentioned experimental example, the chain end group esterification modification polycarboxylic acids diminishing of drawing money on credit of the invention prepared
Agent, for common polycarboxylate water-reducer, there is good resistance mud effect.
Chain end group esterification modification polycarboxylate water-reducer and preparation method thereof provided by the present invention of drawing money on credit is carried out above
It is discussed in detail, the explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
- The chain end group esterification modification polycarboxylate water-reducer 1. one kind is drawn money on credit, it is characterised in that：The chain end group esterification modification of drawing money on credit gathers Carboxylic acid water reducer is in the presence of initiator and chain-transferring agent, is formed by three kinds of monomer copolymerizations, and three kinds of monomers are respectively Unsaturated monocarboxylic acid, end carboxyl polyether macromonomer and the first polyether macromonomer, the end carboxyl polyether macromonomer have as follows Structure：Wherein R1, R2, R3For H or CH3, R4For H or monovalence alkali metal, n=1~100, m=2~10.
- 2. chain end group esterification modification polycarboxylate water-reducer according to claim 1 of drawing money on credit, it is characterised in that：N=50, m= 2。
- 3. chain end group esterification modification polycarboxylate water-reducer according to claim 1 of drawing money on credit, it is characterised in that：The end carboxyl Polyether macromonomer is 5~30 parts by weight, and the unsaturated monocarboxylic acid is 5~15 parts by weight, and first polyether macromonomer is 55~90 parts by weight, the initiator are the 0.5~4% of total monomer weight, and chain-transferring agent is the 0.1~1% of total monomer weight.
- 4. chain end group esterification modification polycarboxylate water-reducer according to claim 3 of drawing money on credit, it is characterised in that：The long-chain branch The specific preparation method of end group esterification modification polycarboxylate water-reducer is：By the end carboxyl polyether macromonomer of 5~30 parts by weight and 55~90 the first polyether macromonomers of parts by weight, it is dissolved in 1.2~ In the water of 1.4 times of parts by weight, reactor is put into, the temperature for controlling reactor is in 20~80 DEG C of water；The unsaturated monocarboxylic acid monomer of 5~15 parts by weight is dissolved in the water of its 1.1~1.3 times of parts by weight, it is molten to be configured to A Liquid, initiator and chain-transferring agent are dissolved in the water of its 5~20 times of parts by weight, are configured to B solution；Solution A and B solution are added dropwise in reactor respectively, the time for adding of solution A and B solution is respectively 3~3.5h, and 3~4h, 2~3h is then incubated, is cooled to room temperature, add alkali lye regulation pH to 6~7, obtained the chain end group esterification of drawing money on credit and change Property polycarboxylate water-reducer.
- 5. chain end group esterification modification polycarboxylate water-reducer according to claim 1 of drawing money on credit, it is characterised in that：The end carboxyl Polyether macromonomer carries out esterification with acid anhydrides by the second polyether macromonomer and is prepared in anhydrous conditions, the big list of the second polyethers Body is the one or more in allyl polyethenoxy ether, methyl allyl polyoxyethylene ether or isopentene group APEO, The acid anhydrides is malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic acid acid anhydride, phthalic anhydride or maleic two The one or more of acid anhydrides.
- 6. chain end group esterification modification polycarboxylate water-reducer according to claim 5 of drawing money on credit, it is characterised in that：The end carboxyl The specific preparation method of polyether macromonomer is：It is 500~5,000 second polyether macromonomers and 3 by the molecular weight of 50~80 mass parts The dicarboxylic anhydride of~10 mass parts is well mixed, and the toluene for adding 5~10 mass parts stirs as water entrainer at 75~105 DEG C Mix 1~5 hour, be evaporated under reduced pressure and remove remaining toluene, be cooled to room temperature, obtain end carboxyl polyether macromonomer.
- 7. chain end group esterification modification polycarboxylate water-reducer according to claim 1 of drawing money on credit, it is characterised in that：The unsaturation Monocarboxylic acid is selected from acrylic acid, methacrylic acid, PAA, methacrylic sulfonic acids sodium, methyl methacrylate or propylene One or more in sour hydroxyl ethyl ester.
- 8. chain end group esterification modification polycarboxylate water-reducer according to claim 1 of drawing money on credit, it is characterised in that：Described first is poly- The one kind of ether polymeric monomer in allyl polyethenoxy ether, methyl allyl polyoxyethylene ether or isopentene group APEO It is or several.
- 9. chain end group esterification modification polycarboxylate water-reducer according to claim 1 of drawing money on credit, it is characterised in that：The initiator For the one or more in ammonium persulfate, sodium peroxydisulfate or hydrogen peroxide.
- 10. chain end group esterification modification polycarboxylate water-reducer according to claim 1 of drawing money on credit, it is characterised in that：The chain turns Shifting agent is the one or more in TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids or mercaptoethanol.
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| CN108283911A (en) * | 2018-01-24 | 2018-07-17 | 咸阳师范学院 | Oil emulsion high molecular surfactant and preparation method thereof |
| CN108948283A (en) * | 2018-05-31 | 2018-12-07 | 靖西市秀美边城农业科技有限公司 | A kind of phthalic anhydride modified polycarboxylic acid water-reducing agent and preparation method thereof |
| CN109694446A (en) * | 2018-12-14 | 2019-04-30 | 上海台界化工有限公司 | A kind of synthetic method of solid polycarboxylic acid water reducing agent |
| CN111154048A (en) * | 2020-01-07 | 2020-05-15 | 湖北凯祥新技术有限公司 | Long-branch-chain-end hydroxyl-grafted sugar molecule mud-resistant polycarboxylate superplasticizer and application thereof |
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| CN108283911A (en) * | 2018-01-24 | 2018-07-17 | 咸阳师范学院 | Oil emulsion high molecular surfactant and preparation method thereof |
| CN108948283A (en) * | 2018-05-31 | 2018-12-07 | 靖西市秀美边城农业科技有限公司 | A kind of phthalic anhydride modified polycarboxylic acid water-reducing agent and preparation method thereof |
| CN108948283B (en) * | 2018-05-31 | 2020-10-30 | 台州中知英健机械自动化有限公司 | Phthalic anhydride modified polycarboxylate superplasticizer and preparation method thereof |
| CN109694446A (en) * | 2018-12-14 | 2019-04-30 | 上海台界化工有限公司 | A kind of synthetic method of solid polycarboxylic acid water reducing agent |
| CN109694446B (en) * | 2018-12-14 | 2021-03-30 | 上海台界化工有限公司 | Synthesis method of solid polycarboxylate superplasticizer |
| CN111154048A (en) * | 2020-01-07 | 2020-05-15 | 湖北凯祥新技术有限公司 | Long-branch-chain-end hydroxyl-grafted sugar molecule mud-resistant polycarboxylate superplasticizer and application thereof |
| CN111234131A (en) * | 2020-03-25 | 2020-06-05 | 陕西科技大学 | Gluconolactone-based polycarboxylic acid water reducing agent and preparation method thereof |
| CN111234130A (en) * | 2020-03-25 | 2020-06-05 | 陕西科技大学 | Michelic acid modified polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
| CN111234131B (en) * | 2020-03-25 | 2023-08-08 | 山东易和建材科技有限公司 | Glucolactone-based polycarboxylate water reducer and preparation method thereof |
| CN111234130B (en) * | 2020-03-25 | 2023-08-29 | 安新县金运化工原料有限公司 | Mi's acid modified polycarboxylic acid high-efficiency water reducer and preparation method thereof |
| CN112707668A (en) * | 2020-09-15 | 2021-04-27 | 科之杰新材料集团有限公司 | Modified polyol acrylate, shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
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