CN110003405A - Comprehensive high-performance polycarboxylic acids diminishing - Google Patents
Comprehensive high-performance polycarboxylic acids diminishing Download PDFInfo
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- CN110003405A CN110003405A CN201910334403.2A CN201910334403A CN110003405A CN 110003405 A CN110003405 A CN 110003405A CN 201910334403 A CN201910334403 A CN 201910334403A CN 110003405 A CN110003405 A CN 110003405A
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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
- 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
- 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
The invention discloses the compositions and preparation method of a kind of comprehensive high-performance polycarboxylic acids diminishing, component including following part: 280-310 parts of vinyl base polyoxyethylene ether, 4-9 parts of sodium hypophosphite, 26-32 parts of acrylic acid, 5-8 parts of alkyl acrylate hydroxy ester, unsaturated 5-7 parts of the gluconolactone monomer of self-control, 0.4-0.6 parts of reducing agent, 2-3.8 parts of oxidant, 1-1.4 parts of chain-transferring agent, 0-2 parts of crosslinking agent, 480-510 parts of water, 30% mass fraction liquid alkaline is appropriate.The present invention uses the large monomer crosslinked synthesis of vinyl polyoxyethylene ether, guarantees higher water-reducing rate while having good function of slump protection.The present invention uses low temperature process and composite initiation system, and reactivity and high conversion rate, reaction temperature do not need to heat at 10-20 DEG C, and the reaction time, production was easier, and cost is lower, more environmentally-friendly energy conservation at 1.5-2 hours.
Description
Technical field
The present invention relates to architectural chemistry building materials field more particularly to a kind of compositions of comprehensive high-performance polycarboxylic acids diminishing
And preparation method.
Background technique
Ligninsulfonate ordinary water-reducing agent of the high performance water reducing agent of polyocarboxy acid as new high performance water-reducing agent, with preceding two generation
Compared with naphthalene series high-efficiency water-reducing agent, have volume is low, water-reducing agent rate is high, function of slump protection is good, favorable dispersibility, workability with it is durable
Property good advantage, there is very high economy to be also able to satisfy environmentally protective, the requirement of energy-saving and emission-reduction simultaneously, in water conservancy, water power, bridge
Have in the developments of the national economy such as the emphasis such as beam, Rail Highway Larger Engineering Projects and civilian common building extensive purposes with
Development space.
With the production of ethers polycarboxylic acid water reducing agent and the rapid growth of application range, ethers polycarboxylic acid water reducing agent is being faced
The various sandstone aggregate in market and cement are in the presence of that adaptability is bad.With the increasing of national environmental protection dynamics, various regions sand
All there is quality of materials not quietly in stone and cement, and sandstone is containing mud and the excessively high situation of content of flocculating.Ethers polycarboxylic acids diminishing
It is more sensitive to admixture dosage that agent encounters this kind of situation usually in concrete and will appear concrete, concrete slump loss
Greatly, easy lag grabs bottom bleeding, the problems such as concrete workability is poor, influence concrete construction unit construction and concrete it is strong
Degree.Now such issues that solution at present general method has following two scheme: the first is to be added largely to protect collapse small powder and mother
Liquid, while the functions small powders such as a series of retarder, water-retaining admixture, anti-mud agent are added, although the method can improve concrete
Workability and workability, reduce the slump-loss of concrete, but additive producer can be sharply increased using this kind of method
Cost, while will cause concrete setting time and later strength problem, bring hidden danger to construction；Second is to reduce to make
With the polycarboxylic acids mother liquor of high water reduction, the ethers polycarboxylic acid water reducing agent and esters water-reducing agent of low diminishing muting sensitive sense, but this are largely used
The complex process of the polycarboxylate water-reducer of class method, the production time is longer, and reaction temperature is higher, aggravated additive producer at
Originally and it is unfavorable for energy conservation and environmental protection.
Now the room temperature technique of current ethers polycarboxylic acid water reducing agent has achieved certain development, but the room temperature of ethers polycarboxylic acids
Production be typically all under conditions of 20-30 DEG C of temperature with polyether macromonomer, unsaturated acrylic monomer, unsaturated esters monomer,
The raw materials such as initiator and chain-transferring agent are added dropwise 3-4 hours, ethers polycarboxylic acid water reducing agent made from heat preservation 1-2 hours, and the method is raw
It is longer to produce the period, and since common ethers polymeric monomer is lower than the reactivity of unsaturated acrylic monomer, causes to be easy when production anti-
Raw unsaturation acrylic monomer autohemagglutination, causes the unstable of product, for this purpose, proposing a kind of group of comprehensive high-performance polycarboxylic acids diminishing
Close object and preparation method.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of groups of comprehensive high-performance polycarboxylic acids diminishing
Close object and preparation method.
The composition of comprehensive high-performance polycarboxylic acids diminishing proposed by the present invention, the component including following part: vinyl base
280-310 parts of polyoxyethylene ether, 4-9 parts of sodium hypophosphite, 26-32 parts of acrylic acid, 5-8 parts of alkyl acrylate hydroxy ester, self-control is not
5-7 parts of gluconolactone monomer of saturation, 0.4-0.6 parts of reducing agent, 2-3.8 parts of oxidant, 1-1.4 parts of chain-transferring agent, crosslinking agent
0-2 parts, 480-510 parts of water, 30% mass fraction liquid alkaline is appropriate.
The composition of comprehensive high-performance polycarboxylic acids diminishing, the component including following part: vinyl base polyoxyethylene ether 300
Part, 7 parts of sodium hypophosphite, 28 parts of acrylic acid, 7 parts of alkyl acrylate hydroxy ester, make unsaturated 6 parts of monomer of gluconolactone by oneself, also
0.5 part of former agent, 3.3 parts of oxidant, 1.2 parts of chain-transferring agent, 1 part of crosslinking agent, 500 parts of water, 30% mass fraction liquid alkaline is appropriate.
The preparation method of comprehensive high-performance polycarboxylic acids diminishing, comprising the following steps:
S1: raw material preparation: beaker being placed on high-precision electronic scale, each raw material of required part is weighed using beaker,
Each raw material weighed up again is put into glass container and places spare；
S2: the first mixed solution: by acrylic acid, crosslinking agent described in S1, alkyl acrylate hydroxy ester and unsaturated Portugal is made by oneself
Grape sugar lactone monomer is dissolved in 30-40 parts of water and obtains mixed solution A；
S3: the second mixed solution: reducing agent described in S1 is dissolved in 100-110 parts of water with chain-transferring agent and is mixed
Solution B.
S4: copolyreaction: by vinyl polyoxyethylene ether described in S1, acrylic acid, sodium hypophosphite and ferrous sulfate
In molten addition three-necked flask, three mouthfuls of beakers are put into thermostat water bath, 250-300 parts of water is added and is stirred at 10-15 DEG C
Oxidant described in S1, while the mixed solution B being added dropwise in the mixed solution A and S3 in S2 is added in dissolution after being uniformly dissolved
Solution, solution A are added dropwise 40-60 minutes, and B solution is added dropwise 60-80 minutes, keeps the temperature 0.5 hour after being added dropwise, and be copolymerized anti-
It answers, obtains reactant C；
S5: preparation molding: reactant C described in S4 is placed in beaker, pour into the liquid alkaline of mass fraction 30% into
Row neutralization reaction obtains product D, makes the pH range 6-7 of product D, then water is added into beaker, until obtaining mass fraction
The polycarboxylate water-reducer that collapses is protected for 40% transparent or flaxen high water reduction auxiliary.
Preferably, the alkyl acrylate hydroxy ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate
One of propyl ester and hydroxypropyl acrylate.
Preferably, the reducing agent is ascorbic acid, sodium hydrogensulfite or ferrous sulfate, and the chain-transferring agent is sulfydryl second
Acid, mercaptopropionic acid or mercaptoethanol.
Preferably, the oxidant is hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate, and the crosslinking agent is molecular weight 400
Or 600 polyethyleneglycol diacrylate, the molecular weight of the vinyl polyoxyethylene ether is 3000.
Preferably, the lye is sodium hydroxide, sodium tripolyphosphate or ethanol amine.
Preferably, the unsaturated gluconolactone monomer synthesis of the self-control is that 178 parts of Portugals are added in three-necked flask
Grape sugar lactone, 122 parts of hydroxy-ethyl acrylates or hydroxypropyl acrylate, 0.6 part of hydroquinone, stirring are warming up to 55 DEG C of addition 4-5
98% concentrated sulfuric acid of part is warming up to 60 DEG C and reacts 4 hours, is cooled to 50 DEG C of additions, 75.9 parts of water and obtains admittedly containing the insatiable hunger for being 80%
With gluconolactone monomer.
Beneficial effects of the present invention: 1, the present invention uses vinyl polyoxyethylene ether polymeric monomer, reacts under cryogenic
Time greatly reduces than common polycarboxylic acids normal-temperature reaction, improves production efficiency, reduces cost price, energy conservation and environmental protection；
2, the vinyl polyoxyethylene ether polymeric monomer that the present invention uses is than common isopentene group polyoxyethylene ether and methyl alkene
Propyl polyoxyethylene ether has higher reactivity, and the polycarboxylate water-reducer of synthesis has more uniform combed chain knot
Structure, conversion rate of products is higher, and molecular weight more easily controls, to the workability of concrete；
3, comprehensive high-performance polycarboxylic acids water reducing agent of the invention introduces unsaturated glucose esters minor comonomer, to cement
Particle has chelating effect, while the ester groups of institute's band can release carboxylic side-chain in the later period, enables the collapse protection type of cement
It improves.
Detailed description of the invention
Fig. 1 is the experimental data figure in the present invention in experiment one；
Fig. 2 is the experimental data figure in the present invention in experiment two.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment one
The composition of comprehensive high-performance polycarboxylic acids diminishing, the component including following part: ethylene are proposed in the present embodiment
300 parts of base base polyoxyethylene ether, 31 parts of acrylic acid, 6 parts of hydroxy-ethyl acrylate, makes unsaturated glucose by oneself by 7 parts of sodium hypophosphite
4 parts of internal ester monomer, 0.6 part of ascorbic acid, 2 parts of hydrogen peroxide, 1.5 parts of ammonium persulfate, 1.3 parts of mercaptopropionic acid, ferrous sulfate 0.01
Part, 2 parts of the polyethyleneglycol diacrylate of molecular weight 400,500 parts of water, 30% mass fraction sodium hydroxide solution is appropriate.
A kind of preparation method of comprehensive high-performance polycarboxylic acids diminishing is proposed in the present embodiment, comprising the following steps:
S1: raw material preparation: beaker being placed on high-precision electronic scale, each raw material of required part is weighed using beaker,
Each raw material weighed up again is put into glass container and places spare；
S2: the first mixed solution: by acrylic acid, polyethyleneglycol diacrylate described in S1, alkyl acrylate hydroxy ester and
The unsaturated gluconolactone monomer of self-control, which is dissolved in 30 parts of water, obtains mixed solution A；
S3: the second mixed solution: ascorbic acid and mercaptopropionic acid described in S1 are dissolved in 100 parts of water obtain mixing it is molten
Liquid B.
S4: copolyreaction: vinyl polyoxyethylene ether described in S1,3 parts of acrylic acid, sodium hypophosphite and sulfuric acid is sub-
In the molten addition three-necked flask of iron, three mouthfuls of beakers are put into thermostat water bath, setting bath temperature is 8-10 DEG C, is added 250 parts
Water stirring and dissolving, hydrogen peroxide and ammonium persulfate described in S1 are added after being uniformly dissolved, while the mixed solution A in S2 is added dropwise
With the mixed solution B solution in S3, solution A is added dropwise 40 minutes, and B solution is added dropwise 60 minutes, keeps the temperature 0.5 hour after being added dropwise,
Copolyreaction is carried out, reactant C is obtained；
S5: preparation molding: reactant C described in S4 is placed in beaker, the hydroxide of mass fraction 30% is poured into
Sodium solution carries out neutralization reaction and obtains product D, makes the pH range 6-7 of product D, then remaining water is added into beaker, directly
The polycarboxylate water-reducer that collapses is protected to the transparent or flaxen high water reduction auxiliary that mass fraction is 40% is obtained.
In the present embodiment, the alkyl acrylate hydroxy ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, metering system
One of sour hydroxypropyl acrylate and hydroxypropyl acrylate, the reducing agent be ascorbic acid, sodium hydrogensulfite or ferrous sulfate, it is described
Chain-transferring agent is thioacetic acid, mercaptopropionic acid or mercaptoethanol, and the oxidant is hydrogen peroxide, ammonium persulfate or persulfuric acid
Potassium, the crosslinking agent are the polyethyleneglycol diacrylate of molecular weight 400 or 600, the molecule of the vinyl polyoxyethylene ether
Amount is 3000, and the lye is sodium hydroxide, sodium tripolyphosphate or ethanol amine, and the unsaturated gluconolactone monomer of the self-control closes
It is that 178 parts of gluconolactones, 122 parts of hydroxy-ethyl acrylates or hydroxypropyl acrylate are added in three-necked flask at method, 0.6 part
Hydroquinone, stirring are warming up to 55 DEG C of additions, 4 part of 98% concentrated sulfuric acid, are warming up to 60 DEG C and react 4 hours, are cooled to 50 DEG C of additions
75.6 parts of water are to obtain the solid unsaturated gluconolactone monomer containing for 80%.
Embodiment two
The composition of comprehensive high-performance polycarboxylic acids diminishing, the component including following part: ethylene are proposed in the present embodiment
300 parts of base base polyoxyethylene ether, 30.5 parts of acrylic acid, 5 parts of hydroxy-ethyl acrylate, makes unsaturated Portugal by oneself by 8.5 parts of sodium hypophosphite
5 parts of grape sugar lactone monomer, 0.6 part of ascorbic acid, 3 parts of hydrogen peroxide, 1.3 parts of mercaptopropionic acid, 0.01 part of ferrous sulfate, molecular weight
1 part of 400 polyethyleneglycol diacrylate, 498 parts of water, 30% mass fraction sodium hydroxide solution is appropriate.
A kind of preparation method of comprehensive high-performance polycarboxylic acids diminishing is proposed in the present embodiment, comprising the following steps:
S1: raw material preparation: beaker being placed on high-precision electronic scale, each raw material of required part is weighed using beaker,
Each raw material weighed up again is put into glass container and places spare；
S2: the first mixed solution: by acrylic acid, hydroxy-ethyl acrylate described in S1 and unsaturated gluconolactone monomer is made by oneself
It is dissolved in 30 parts of water and obtains mixed solution A；
S3: the second mixed solution: ascorbic acid and mercaptopropionic acid described in S1 are dissolved in 100 parts of water obtain mixing it is molten
Liquid B.
S4: copolyreaction: by vinyl polyoxyethylene ether described in S1,3 parts of acrylic acid, glycol diacrylate
In sodium phosphite and the molten addition three-necked flask of ferrous sulfate, three mouthfuls of beakers are put into thermostat water bath, setting bath temperature is
8-10 DEG C, 250 parts of water stirring and dissolving is added, hydrogen peroxide described in S1 is added after being uniformly dissolved, while being added dropwise mixed in S2
The mixed solution B solution in solution A and S3 is closed, solution A is added dropwise 60 minutes, and B solution is added dropwise 80 minutes, keeps the temperature after being added dropwise
0.5 hour, copolyreaction is carried out, reactant C is obtained；
S5: preparation molding: reactant C described in S4 is placed in beaker, the hydroxide of mass fraction 30% is poured into
Sodium carries out neutralization reaction and obtains product D, makes the pH range 6-7 of product D, then remaining water is added into beaker, until
The polycarboxylate water-reducer that collapses is protected to the transparent or flaxen high water reduction auxiliary that mass fraction is 40%.
In the present embodiment, the alkyl acrylate hydroxy ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, metering system
One of sour hydroxypropyl acrylate and hydroxypropyl acrylate, the reducing agent be ascorbic acid, sodium hydrogensulfite or ferrous sulfate, it is described
Chain-transferring agent is thioacetic acid, mercaptopropionic acid or mercaptoethanol, and the oxidant is hydrogen peroxide, ammonium persulfate or persulfuric acid
Potassium, the crosslinking agent are the polyethyleneglycol diacrylate of molecular weight 400 or 600, the molecule of the vinyl polyoxyethylene ether
Amount is 3000, and the lye is sodium hydroxide, sodium tripolyphosphate or ethanol amine, and the unsaturated gluconolactone monomer of the self-control closes
It is that 178 parts of gluconolactones, 122 parts of hydroxy-ethyl acrylates or hydroxypropyl acrylate are added in three-necked flask at method, 0.6 part
Hydroquinone, stirring are warming up to 55 DEG C of additions, 4 part of 98% concentrated sulfuric acid, are warming up to 60 DEG C and react 4 hours, are cooled to 50 DEG C of additions
75.6 parts of water are to obtain the solid unsaturated gluconolactone monomer containing for 80%.
Embodiment three
The composition of comprehensive high-performance polycarboxylic acids diminishing, the component including following part: ethylene are proposed in the present embodiment
300 parts of base base polyoxyethylene ether, 8 parts of sodium hypophosphite, 31.5 parts of acrylic acid, 5 parts of hydroxyethyl methacrylate, self-control is unsaturated
5 parts of gluconolactone monomer, 0.6 part of ascorbic acid, 3 parts of hydrogen peroxide, 1 part of potassium peroxydisulfate, 1.1 parts of thioacetic acid, ferrous sulfate
0.01 part, 1 part of the polyethyleneglycol diacrylate of molecular weight 200,498 parts of water, 30% mass fraction sodium hydroxide solution is appropriate.
A kind of preparation method of comprehensive high-performance polycarboxylic acids diminishing is proposed in the present embodiment, comprising the following steps:
S1: raw material preparation: beaker being placed on high-precision electronic scale, each raw material of required part is weighed using beaker,
Each raw material weighed up again is put into glass container and places spare；
S2: the first mixed solution: by acrylic acid, hydroxyethyl methacrylate described in S1 and unsaturated gluconolactone is made by oneself
Monomer is dissolved in 30 parts of water and obtains mixed solution A；
S3: the second mixed solution: ascorbic acid and thioacetic acid described in S1 are dissolved in 100 parts of water obtain mixing it is molten
Liquid B.
S4: copolyreaction: by vinyl polyoxyethylene ether described in S1,4 parts of acrylic acid, glycol diacrylate,
In sodium hypophosphite and the molten addition three-necked flask of ferrous sulfate, three mouthfuls of beakers are put into thermostat water bath, bath temperature is set
It is 8-10 DEG C, 250 parts of water stirring and dissolving is added, hydrogen peroxide and potassium peroxydisulfate described in S1 is added after being uniformly dissolved, simultaneously
The mixed solution B solution in the mixed solution A and S3 in S2 is added dropwise, solution A is added dropwise 50 minutes, and B solution is added dropwise 60 minutes, is added dropwise
After keep the temperature 0.5 hour, carry out copolyreaction, obtain reactant C；
S5: preparation molding: reactant C described in S4 is placed in beaker, the hydroxide of mass fraction 30% is poured into
Sodium carries out neutralization reaction and obtains product D, makes the pH range 6-7 of product D, then remaining water is added into beaker, until
The polycarboxylate water-reducer that collapses is protected to the transparent or flaxen high water reduction auxiliary that mass fraction is 40%.
In the present embodiment, the alkyl acrylate hydroxy ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, metering system
One of sour hydroxypropyl acrylate and hydroxypropyl acrylate, the reducing agent be ascorbic acid, sodium hydrogensulfite or ferrous sulfate, it is described
Chain-transferring agent is thioacetic acid, mercaptopropionic acid or mercaptoethanol, and the oxidant is hydrogen peroxide, ammonium persulfate or persulfuric acid
Potassium, the crosslinking agent are the polyethyleneglycol diacrylate of molecular weight 400 or 600, the molecule of the vinyl polyoxyethylene ether
Amount is 3000, and the lye is sodium hydroxide, sodium tripolyphosphate or ethanol amine, and the unsaturated gluconolactone monomer of the self-control closes
It is that 178 parts of gluconolactones, 122 parts of hydroxy-ethyl acrylates or hydroxypropyl acrylate are added in three-necked flask at method, 0.6 part
Hydroquinone, stirring are warming up to 55 DEG C of additions, 4 part of 98% concentrated sulfuric acid, are warming up to 60 DEG C and react 4 hours, are cooled to 50 DEG C of additions
75.6 parts of water are to obtain the solid unsaturated gluconolactone monomer containing for 80%.
Example IV
The composition of comprehensive high-performance polycarboxylic acids diminishing, the component including following part: ethylene are proposed in the present embodiment
300 parts of base base polyoxyethylene ether, 30.5 parts of acrylic acid, 7 parts of hydroxy propyl methacrylate, makes insatiable hunger by oneself by 7.5 parts of sodium hypophosphite
With 5 parts of gluconolactone monomer, 0.5 part of ascorbic acid, 0.15 part of sodium hydrogensulfite, 3 parts of hydrogen peroxide, 1.1 parts of mercaptopropionic acid, sulphur
Sour 0.01 part ferrous, 2 parts of the polyethyleneglycol diacrylate of molecular weight 200,500 parts of water, 30% mass fraction sodium hydroxide is molten
Appropriate liquid.
A kind of preparation method of comprehensive high-performance polycarboxylic acids diminishing is proposed in the present embodiment, comprising the following steps:
S1: raw material preparation: beaker being placed on high-precision electronic scale, each raw material of required part is weighed using beaker,
Each raw material weighed up again is put into glass container and places spare；
S2: the first mixed solution: by acrylic acid, hydroxy propyl methacrylate described in S1 and unsaturated gluconolactone is made by oneself
Monomer is dissolved in 30 parts of water and obtains mixed solution A；
S3: the second mixed solution: ascorbic acid, sodium hydrogensulfite described in S1 and thioacetic acid are dissolved in 100 parts of water
In obtain mixed solution B.
S4: copolyreaction: vinyl polyoxyethylene ether described in S1,3 parts of acrylic acid, sodium hypophosphite and sulfuric acid is sub-
In the molten addition three-necked flask of iron, three mouthfuls of beakers are put into thermostat water bath, setting bath temperature is 8-10 DEG C, is added 250 parts
Water stirring and dissolving, hydrogen peroxide described in S1 is added after being uniformly dissolved, while being added dropwise mixed in the mixed solution A and S3 in S2
Solution B solution is closed, solution A is added dropwise 50 minutes, and B solution is added dropwise 60 minutes, keeps the temperature 0.5 hour after being added dropwise, and be copolymerized anti-
It answers, obtains reactant C；
S5: preparation molding: reactant C described in S4 is placed in beaker, the hydroxide of mass fraction 30% is poured into
Sodium carries out neutralization reaction and obtains product D, makes the pH range 6-7 of product D, then remaining water is added into beaker, until
The polycarboxylate water-reducer that collapses is protected to the transparent or flaxen high water reduction auxiliary that mass fraction is 40%.
In the present embodiment, the alkyl acrylate hydroxy ester is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, metering system
One of sour hydroxypropyl acrylate and hydroxypropyl acrylate, the reducing agent be ascorbic acid, sodium hydrogensulfite or ferrous sulfate, it is described
Chain-transferring agent is thioacetic acid, mercaptopropionic acid or mercaptoethanol, and the oxidant is hydrogen peroxide, ammonium persulfate or persulfuric acid
Potassium, the crosslinking agent are the polyethyleneglycol diacrylate of molecular weight 400 or 600, the molecule of the vinyl polyoxyethylene ether
Amount is 3000, and the lye is sodium hydroxide, sodium tripolyphosphate or ethanol amine, and the unsaturated gluconolactone monomer of the self-control closes
It is that 178 parts of gluconolactones, 122 parts of hydroxy-ethyl acrylates or hydroxypropyl acrylate are added in three-necked flask at method, 0.6 part
Hydroquinone, stirring are warming up to 55 DEG C of additions, 4 part of 98% concentrated sulfuric acid, are warming up to 60 DEG C and react 4 hours, are cooled to 50 DEG C of additions
75.6 parts of water are to obtain the solid unsaturated gluconolactone monomer containing for 80%.
Experimental comparison:
Experiment one: example 1-4 is synthesized into obtained polycarboxylate water-reducer sample, using reference cement, according to GB
8076-2008 " concrete admixture ", surveys its concrete water-reducing ratio, the slump, Slump Time losing of Large and workability etc., mixes
Solidifying soil match ratio are as follows: cement 360kg/m3, sand 800kg/m3, stone 1050kg/m3, slump control is in 210 ± 10mm, gained
As a result as shown in Figure 1；
Experiment two: synthesizing obtained polycarboxylate water-reducer sample for example 1-4, using flammule cement, high victory cement, draws
Three kinds of cement of method base cement carry out concrete experiments to test the adaptability of water-reducing agent and cement.Concrete mix are as follows: cement
360kg/m3, sand 800kg/m3, stone 1050kg/m3, in 210 ± 10mm, acquired results are as shown in Figure 2 for slump control；
Experiment conclusion: example 1-4's the experiment results show that polycarboxylate water-reducer of the invention have it is preferable comprehensive
Can, there is good function of slump protection and cement adaptability in the case where keeping certain water-reducing rate.
Claims (8)
1. the composition of comprehensive high-performance polycarboxylic acids diminishing, which is characterized in that the component including following part: vinyl base polyoxy
280-310 parts of vinethene, 4-9 parts of sodium hypophosphite, 26-32 parts of acrylic acid, 5-8 parts of alkyl acrylate hydroxy ester, self-control is unsaturated
5-7 parts of gluconolactone monomer, 0.4-0.6 parts of reducing agent, 2-3.8 parts of oxidant, 1-1.4 parts of chain-transferring agent, crosslinking agent 0-2
Part, 480-510 parts of water, 30% mass fraction liquid alkaline is appropriate.
2. the composition of comprehensive high-performance polycarboxylic acids diminishing according to claim 1, which is characterized in that including following part
Component: 300 parts of vinyl base polyoxyethylene ether, 7 parts of sodium hypophosphite, 28 parts of acrylic acid, 7 parts of alkyl acrylate hydroxy ester, from
Unsaturated 6 parts of monomer of the gluconolactone of system, 0.5 part of reducing agent, 3.3 parts of oxidant, 1.2 parts of chain-transferring agent, 1 part of crosslinking agent, water
500 parts, 30% mass fraction liquid alkaline is appropriate.
3. the preparation method of comprehensive high-performance polycarboxylic acids diminishing, which comprises the following steps:
S1: raw material preparation: beaker is placed on high-precision electronic scale, each raw material of required part is weighed using beaker, then is claimed
Good each raw material is put into glass container and places spare；
S2: the first mixed solution: by acrylic acid, crosslinking agent described in S1, alkyl acrylate hydroxy ester and unsaturated glucose is made by oneself
Internal ester monomer is dissolved in 30-40 parts of water and obtains mixed solution A；
S3: the second mixed solution: reducing agent described in S1 and chain-transferring agent are dissolved in 100-110 parts of water and obtain mixed solution
B。
S4: copolyreaction: by vinyl polyoxyethylene ether described in S1, acrylic acid, sodium hypophosphite and ferrous sulfate it is molten plus
Enter in three-necked flask, three mouthfuls of beakers are put into thermostat water bath, the water of 250-300 parts of addition stirring and dissolving at 10-15 DEG C,
Oxidant described in S1, while the mixed solution B solution being added dropwise in the mixed solution A and S3 in S2, A are added after being uniformly dissolved
Solution is added dropwise 40-60 minutes, and B solution is added dropwise 60-80 minutes, keeps the temperature 0.5 hour after being added dropwise, and carries out copolyreaction, obtains
Reactant C；
S5: preparation molding: reactant C described in S4 is placed in beaker, is poured into the liquid alkaline progress of mass fraction 30%
Product D is obtained with reaction, makes the pH range 6-7 of product D, then adds water into beaker, is up to obtaining mass fraction
40% transparent or flaxen high water reduction auxiliary protects the polycarboxylate water-reducer that collapses.
4. the composition of comprehensive high-performance polycarboxylic acids diminishing according to claim 1 or 2, which is characterized in that described third
Olefin(e) acid alkane hydroxy ester is in hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate and hydroxypropyl acrylate
One kind.
5. the composition of comprehensive high-performance polycarboxylic acids diminishing according to claim 1 or 2, which is characterized in that described to go back
Former agent is ascorbic acid, sodium hydrogensulfite or ferrous sulfate, and the chain-transferring agent is thioacetic acid, mercaptopropionic acid or sulfydryl second
Alcohol.
6. the composition of comprehensive high-performance polycarboxylic acids diminishing according to claim 1 or 2, which is characterized in that the oxygen
Agent is hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate, and the crosslinking agent is two propylene of polyethylene glycol of molecular weight 400 or 600
Acid esters, the molecular weight of the vinyl polyoxyethylene ether are 3000.
7. the composition of comprehensive high-performance polycarboxylic acids diminishing according to claim 1 or 2, which is characterized in that the alkali
Liquid is sodium hydroxide, sodium tripolyphosphate or ethanol amine.
8. the composition of comprehensive high-performance polycarboxylic acids diminishing according to claim 1 or 2, which is characterized in that it is described from
Making unsaturated gluconolactone monomer synthesis is that 178 parts of gluconolactones, 122 parts of acrylic acid hydroxyls are added in three-necked flask
Ethyl ester or hydroxypropyl acrylate, 0.6 part of hydroquinone, stirring are warming up to 55 DEG C of 98% concentrated sulfuric acids of addition 4-5 part, are warming up to 60 DEG C
Reaction 4 hours is cooled to 50 DEG C of additions, 75.9 parts of water and obtains the solid unsaturated gluconolactone monomer containing for 80%.
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