CN106380551B - A kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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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
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- 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
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Abstract
The invention discloses a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer and preparation method thereof, pH is 6.0~6.5, and solid content is 45~55%, and raw material is grouped as by the group of following parts by weight：4 hydroxyl butyl vinyl polyoxyethylene ether, 90~130 parts by weight that molecular weight is 2000~5000,6~10 parts by weight of unsaturated monocarboxylic acid, 3~6 parts by weight of unsaturated carboxylate type monomer, unsaturated 1~5 parts by weight of both sexes quaternary alkylphosphonium salt, 0.2~0.8 parts by weight of oxidant, 0.2~1.0 parts by weight of reducing agent, 0.02~0.06 parts by weight of catalyst, 0.2~0.6 parts by weight of chain-transferring agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate amount of deionized water.The side chain distribution of the polycarboxylate water-reducer of the present invention is more uniform, and guarantor is collapsed, and effect is good, and changing to the volume of polycarboxylate water-reducer has excellent hyposensitivity energy.
Description
Technical field
The invention belongs to cement water reducing agent technical fields, and in particular to a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer and
Preparation method.
Background technology
Poly carboxylic acid series water reducer has excellent dispersion performance, concrete can be made to reach preferable stream at low dosage
Dynamic property, is widely used in the engineerings such as highway, bridge, dam, tunnel, skyscraper.With the continuous development of polycarboxylic acids technology, gather
The water-reducing rate of carboxylic acid water reducer is continuously improved, although water-reducing rate improves the dosage that can reduce polycarboxylate water-reducer, reduces cost,
The sensibility for also improving polycarboxylate water-reducer is shown as in the construction process, and the reasonable volume point drop of polycarboxylate water-reducer is a bit
Volume, can cause fresh concrete mobility not enough or loss is too fast, and reasonable volume point carries some volumes, then easily leads to concrete
Isolation, bleeding so that concrete production control difficulty increases, i.e., sensitive to volume.
In addition, a large amount of case history and studies have shown that with the water-reducing agents phase such as naphthalene system, melamine series and amido sulfoacid series
Than poly carboxylic acid series water reducer is more sensitive to the clay content of aggregate, is mainly shown as the diminishing dispersion energy of poly carboxylic acid series water reducer
Power degradation, guarantor's effect of collapsing are poor, lead to maturing strength reduction etc..Although can be obtained by improving water-reducing agent volume
Alleviate, but be easy to cause the problems such as concrete coagulating time overlength is reduced with compressive strength rate, and greatly increases cost.
Invention content
It is an object of the invention to overcome prior art defect, a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer is provided.
Another object of the present invention is to provide the preparation methods of above-mentioned muting sensitive induction reactance chamotte mould polycarboxylate water-reducer.
Technical scheme is as follows：
A kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer, pH be 6.0~6.5, solid content be 45~55%, raw material by
The group of following parts by weight is grouped as：90~130 weight of 4- hydroxyl butyl vinyls polyoxyethylene ether that molecular weight is 2000~5000
Measure part, 6~10 parts by weight of unsaturated monocarboxylic acid, 3~6 parts by weight of unsaturated carboxylate type monomer, unsaturated both sexes quaternary alkylphosphonium salt 1
~5 parts by weight, 0.2~0.8 parts by weight of oxidant, 0.2~1.0 parts by weight of reducing agent, 0.02~0.06 parts by weight of catalyst, chain
0.2~0.6 parts by weight of transfer agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate amount of deionized water,
In, unsaturated both sexes quaternary alkylphosphonium salt be triphenyl phosphorus and allyl bromide, bromoallylene with 1: 1.0~1.5 molar ratio in carbon tetrachloride by as follows
Reaction is made：
In a preferred embodiment of the invention, the preparation method of the unsaturated both sexes quaternary alkylphosphonium salt includes following step
Suddenly：
(1) 1: 1.0~1.5 triphenyl phosphorus and allyl bromide, bromoallylene are weighed in molar ratio；
(2) triphenyl phosphorus and appropriate carbon tetrachloride are mixed, is fully dissolved；
(3) allyl bromide, bromoallylene is added dropwise with the speed of 1/2~5s of drop in the material obtained by step (2), is carried out during being added dropwise
Stirring is reacted simultaneously, and reaction temperature is kept for 40~50 DEG C, and the reaction time is 4~6h, obtains tan precipitate object；
(4) above-mentioned tan precipitate object is recrystallized with acetone, obtains recrystallized product；
(5) above-mentioned recrystallized product is dried in vacuo, obtains the powder of white, the as described unsaturated both sexes quaternary phosphonium
Salt.
In a preferred embodiment of the invention, the unsaturated monocarboxylic acid is acrylic acid and/or metering system
Acid.
In a preferred embodiment of the invention, the unsaturated carboxylate type monomer is hydroxy-ethyl acrylate, first
In base hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methyl acrylate and methyl methacrylate extremely
Few one kind.
In a preferred embodiment of the invention, the oxidant is hydrogen peroxide, sodium peroxydisulfate and ammonium persulfate
At least one of.
In a preferred embodiment of the invention, the reducing agent is sodium formaldehyde sulphoxylate, Br ü ggolitTM
At least one of FF6 and sodium hypophosphite.
In a preferred embodiment of the invention, the catalyst is ferrous sulfate and/or ferrous nitrate.
In a preferred embodiment of the invention, the chain-transferring agent is thioacetic acid, mercaptopropionic acid and sulfydryl second
At least one of alcohol.
The preparation method of above-mentioned muting sensitive induction reactance chamotte mould polycarboxylate water-reducer, includes the following steps：
(1) each raw material component is weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10~15 parts by weight of deionized water, be used in combination adjust pH to
5.5~6.0, obtain the first solution；It dissolves reduce agent in 10~15 parts by weight of deionized water and obtains the second solution；It will be unsaturated
Carboxylic acid esters monomer, which is dissolved in 6~10 parts by weight of deionized water, obtains third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in going for 80~90 parts by weight
In ionized water, then be sequentially added into 35~55% the first solution, appropriate sodium hydrate aqueous solution, catalyst and oxidant, and
Reaction temperature is adjusted to be reacted to 10~30 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), 0.5~
It is added dropwise in 1.5h, 0.5~1.5h of insulation reaction after completion of dropwise addition；
(5) with the pH value of appropriate sodium hydrate aqueous solution regulating step (4) resulting material to 6.0~6.5 to get to described
Muting sensitive induction reactance chamotte mould polycarboxylate water-reducer.
The beneficial effects of the invention are as follows：
1, muting sensitive induction reactance chamotte mould polycarboxylate water-reducer of the invention, which uses, has high double bond retention rate, the 4- hydroxyl fourths of high activity
Base vinyl polyoxyethylene ether polymeric monomer, compared with allyl polyethenoxy polyethers, isopentene group polyoxyethylene polyethers and methyl alkene
Propyl polyoxyethylene polyethers has higher polymerization activity, and the polycarboxylate water-reducer side chain distribution of synthesis is more uniform, protects effect of collapsing
It is good, there is excellent hyposensitivity energy to the volume variation of polycarboxylate water-reducer.
2, preparation method of the invention introduces unsaturated both sexes quaternary alkylphosphonium salt and unsaturated carboxylate type in the synthesis process
Monomer, the active suction to reduce soil to water-reducing agent for acting as inhibiting or reduce soil of quaternary alkylphosphonium salt cation group side chain
It is attached, so that carboxylic acid ion and polyether lateral chain in molecular structure is played absorption cement respectively and disperses the effect of cement, final body
It is now anti-mud adaptability and hyposensitivity, and carboxylic acid esters group is under alkaline condition, has slowly released the carboxylic of water-reduction
Acid ion has further ensured that the diminishing of poly carboxylic acid series water reducer protects the effect of collapsing.
3, preparation method of the invention uses low-temperature oxidation reduction initiating system, and the synthesis technology material dropping time is short,
Production efficiency is high.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode.
It is 1: 1.2 anti-that unsaturated both sexes quaternary alkylphosphonium salt in following embodiments, which is triphenyl phosphorus and allyl bromide, bromoallylene according to molar ratio,
It should be made, the specific method is as follows：The triphenyl phosphorus of 20g and the carbon tetrachloride of 30g are added in 100mL three-necked flasks, magnetic force stirs
It mixes, is dissolved.Dissolving finishes, and (1 drop/2 seconds) 11.07g allyl bromide, bromoallylenes are added dropwise, magnetic agitation, reaction are carried out during being added dropwise
Temperature is kept for 45 DEG C, will have tan precipitate precipitation after reacting a period of time.After 4h, precipitated product is tied again with acetone
The product of crystalline substance, recrystallization is dry in 80 DEG C of vacuum drying ovens, finally obtains the powder of white, as unsaturated both sexes quaternary alkylphosphonium salt.
Embodiment 1
(1) each raw material component is weighed by following parts by weight：4- hydroxyl butyl vinyl polyoxyethylene ethers (molecular weight 2000)
110 parts by weight, 8 parts by weight of acrylic acid, 6 parts by weight of hydroxy-ethyl acrylate, unsaturated 2 parts by weight of both sexes quaternary alkylphosphonium salt, hydrogen peroxide
0.5 parts by weight, Br ü ggolitTMFF60.7 parts by weight, 0.04 parts by weight of ferrous sulfate, 0.35 parts by weight of thioacetic acid, 50%
4 parts by weight of potassium hydroxide aqueous solution of mass concentration, 5 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining is to go
Ionized water is adjusted to 50% solid content.
(2) acrylic acid, thioacetic acid are dissolved in 15 parts by weight of deionized water, the potassium hydroxide of 50% mass concentration is used in combination
Aqueous solution adjusts pH to 5.5~6.0, obtains the first solution；By Br ü ggolitTMFF6, which is dissolved in 15 parts by weight of deionized water, to be obtained
To the second solution；Unsaturated carboxylate type monomer is dissolved in 10 parts by weight of deionized water and obtains third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 35% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, ferrous sulfate and hydrogen peroxide again, and
Reaction temperature is adjusted to 10 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), three kinds of solution
It is added dropwise in 1h, 1.5h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~6.5 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
State muting sensitive induction reactance chamotte mould polycarboxylate water-reducer PCE-1.
Embodiment 2
(1) each raw material component 4- hydroxyl butyl vinyl polyoxyethylene ethers (molecular weight 2400) are weighed by following parts by weight
110 parts by weight, 6 parts by weight of acrylic acid, 3 parts by weight of hydroxyethyl methacrylate, unsaturated 1 parts by weight of both sexes quaternary alkylphosphonium salt, over cure
0.6 parts by weight of sour sodium, 0.8 parts by weight of sodium formaldehyde sulphoxylate, 0.02 parts by weight of ferrous nitrate, 0.4 parts by weight of mercaptopropionic acid,
2 parts by weight of potassium hydroxide aqueous solution of 50% mass concentration, 6 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining
For deionized water, it is adjusted to 50% solid content.
(2) acrylic acid, mercaptopropionic acid are dissolved in 15 parts by weight of deionized water, the potassium hydroxide of 50% mass concentration is used in combination
Aqueous solution adjusts pH to 5.5~6.0, obtains the first solution；Sodium formaldehyde sulphoxylate is dissolved in 15 parts by weight of deionized water
Obtain the second solution；Hydroxyethyl methacrylate is dissolved in 10 parts by weight of deionized water and obtains third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 45% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, ferrous nitrate and sodium peroxydisulfate again, and
Reaction temperature is adjusted to 15 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), three kinds of solution
It is added dropwise in 0.5h, 1h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~6.5 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
State muting sensitive induction reactance chamotte mould polycarboxylate water-reducer PCE-2.
Embodiment 3
(1) each raw material component is weighed by following parts by weight：4- hydroxyl butyl vinyl polyoxyethylene ethers (molecular weight 4000)
100 parts by weight, 7 parts by weight of methacrylic acid, 4 parts by weight of hydroxypropyl acrylate, unsaturated 3 parts by weight of both sexes quaternary alkylphosphonium salt, over cure
0.4 parts by weight of sour ammonium, Br ü ggolitTM0.7 parts by weight of FF6,0.06 parts by weight of ferrous nitrate, 0.5 parts by weight of mercaptoethanol,
3 parts by weight of potassium hydroxide aqueous solution of 50% mass concentration, 4 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining
For deionized water, it is adjusted to 50% solid content.
(2) methacrylic acid, mercaptoethanol are dissolved in 15 parts by weight of deionized water, the hydrogen-oxygen of 50% mass concentration is used in combination
Change aqueous solutions of potassium and adjust pH to 5.5~6.0, obtains the first solution；By Br ü ggolitTMFF6 is dissolved in 15 parts by weight of deionized water
In obtain the second solution；Hydroxypropyl acrylate is dissolved in 10 parts by weight of deionized water and obtains third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 40% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, ferrous nitrate and ammonium persulfate again, and
Reaction temperature is adjusted to 20 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), three kinds of solution
It is added dropwise in 0.75h, 0.5h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~6.5 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
State muting sensitive induction reactance chamotte mould polycarboxylate water-reducer PCE-3.
Embodiment 4
(1) each raw material component is weighed by following parts by weight：4- hydroxyl butyl vinyl polyoxyethylene ethers (molecular weight 5000)
100 parts by weight, 9 parts by weight of methacrylic acid, 5 parts by weight of methyl acrylate, unsaturated 4 parts by weight of both sexes quaternary alkylphosphonium salt, peroxidating
0.7 parts by weight of hydrogen, 1.0 parts by weight of sodium hypophosphite, 0.05 parts by weight of ferrous sulfate, 0.6 parts by weight of mercaptopropionic acid, 50% mass are dense
5 parts by weight of potassium hydroxide aqueous solution of degree, 5 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining is deionized water,
It is adjusted to 50% solid content.
(2) methacrylic acid, mercaptopropionic acid are dissolved in 15 parts by weight of deionized water, the hydrogen-oxygen of 50% mass concentration is used in combination
Change aqueous solutions of potassium and adjust pH to 5.5~6.0, obtains the first solution；Sodium hypophosphite is dissolved in 15 parts by weight of deionized water and is obtained
Second solution；Methyl acrylate is dissolved in 10 parts by weight of deionized water and obtains third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 55% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, ferrous sulfate and hydrogen peroxide again, and
Reaction temperature is adjusted to 30 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), three kinds of solution
It is added dropwise in 1h, 0.75h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~6.5 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
State muting sensitive induction reactance chamotte mould polycarboxylate water-reducer PCE-4.
Embodiment 5
Examples 1 to 4 is synthesized muting sensitive induction reactance chamotte mould polycarboxylate water-reducer (PCE-1, PCE-2, PCE-3 and
PCE-4 it) carries out different addition quantity concrete performance with commercially available ethers polycarboxylic acid water reducing agent (PCE-0) and compares, by adjusting water-reducing agent
Volume, according to GB/T50080-2011《Standard for test methods of properties of ordinary concrete mixture standard》, by fresh concrete divergence
Accomplish 400 ± 10mm (volume a%) and 550 ± 10mm (volume b%) respectively, calculate its volume width ratio γ (γ=
B/a), γ is bigger, illustrates that water-reducing agent is more insensitive, and adaptability is better.
Using Fujian good fortune cement (P.O 42.5R), concrete mix is：Cement 260kg/m3, flyash 80kg/m3, sand
790kg/m3, stone 1140kg/m3, water 170kg/m3, aggregate clay content is 1.5%, and acquired results are as shown in table 1：
1 embodiment performance comparison of table
It can be seen that from the above, its volume width ratio of commercially available ethers polycarboxylic acid water reducing agent γ is 1.41, and passes through reality
The muting sensitive sense polycarboxylate water-reducer of example synthesis is applied, volume width ratio γ is respectively 1.65,1.73,1.68 and 1.77, is intended to big
In commercially available ethers polycarboxylic acid water reducing agent volume width ratio, illustrate that the muting sensitive sense polycarboxylate water-reducer of embodiment synthesis becomes volume
Change less sensitive.And in the case where aggregate clay content is 1.5%, reach identical divergence, commercially available ethers polycarboxylic acids subtracts
Aqua volume is substantially higher compared with the polycarboxylate water-reducer volume that embodiment synthesizes, and is protected to collapse and wanted poor, illustrates the low of embodiment synthesis
Sensitive polycarboxylate water-reducer is preferable to adaptability for materials, and anti-mud effect is good.
Those of ordinary skill in the art remain able to it is found that when technical scheme of the present invention changes in following ranges
To same as the previously described embodiments or similar technique effect, protection scope of the present invention is still fallen within：
A kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer, pH be 6.0~6.5, solid content be 45~55%, raw material by
The group of following parts by weight is grouped as：90~130 weight of 4- hydroxyl butyl vinyls polyoxyethylene ether that molecular weight is 2000~5000
Measure part, 6~10 parts by weight of unsaturated monocarboxylic acid, 3~6 parts by weight of unsaturated carboxylate type monomer, unsaturated both sexes quaternary alkylphosphonium salt 1
~5 parts by weight, 0.2~0.8 parts by weight of oxidant, 0.2~1.0 parts by weight of reducing agent, 0.02~0.06 parts by weight of catalyst, chain
0.2~0.6 parts by weight of transfer agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate amount of deionized water,
In, unsaturated both sexes quaternary alkylphosphonium salt be triphenyl phosphorus and allyl bromide, bromoallylene with 1: 1.0~1.5 molar ratio in carbon tetrachloride by as follows
Reaction is made：
The preparation method of the unsaturation both sexes quaternary alkylphosphonium salt includes the following steps：
(1) 1: 1.0~1.5 triphenyl phosphorus and allyl bromide, bromoallylene are weighed in molar ratio；
(2) triphenyl phosphorus and appropriate carbon tetrachloride are mixed, is fully dissolved；
(3) allyl bromide, bromoallylene is added dropwise with the speed of 1/2~5s of drop in the material obtained by step (2), is carried out during being added dropwise
Stirring is reacted simultaneously, and reaction temperature is kept for 40~50 DEG C, and the reaction time is 4~6h, obtains tan precipitate object；
(4) above-mentioned tan precipitate object is recrystallized with acetone, obtains recrystallized product；
(5) above-mentioned recrystallized product is dried in vacuo, obtains the powder of white, the as described unsaturated both sexes quaternary phosphonium
Salt.
The unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid.The unsaturated carboxylate type monomer is third
Olefin(e) acid hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methyl acrylate and methyl-prop
At least one of e pioic acid methyl ester.The oxidant is at least one of hydrogen peroxide, sodium peroxydisulfate and ammonium persulfate.It is described
Reducing agent is sodium formaldehyde sulphoxylate, Br ü ggolitTMAt least one of FF6 and sodium hypophosphite.The catalyst is sulphur
Sour ferrous and/or ferrous nitrate.The chain-transferring agent is at least one of thioacetic acid, mercaptopropionic acid and mercaptoethanol.
The preparation method of above-mentioned muting sensitive induction reactance chamotte mould polycarboxylate water-reducer, includes the following steps：
(1) each raw material component is weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10~15 parts by weight of deionized water, be used in combination adjust pH to
5.5~6.0, obtain the first solution；It dissolves reduce agent in 10~15 parts by weight of deionized water and obtains the second solution；It will be unsaturated
Carboxylic acid esters monomer, which is dissolved in 6~10 parts by weight of deionized water, obtains third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in going for 80~90 parts by weight
In ionized water, then be sequentially added into 35~55% the first solution, appropriate sodium hydrate aqueous solution, catalyst and oxidant, and
Reaction temperature is adjusted to be reacted to 10~30 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), 0.5~
It is added dropwise in 1.5h, 0.5~1.5h of insulation reaction after completion of dropwise addition；
(5) with the pH value of appropriate sodium hydrate aqueous solution regulating step (4) resulting material to 6.0~6.5 to get to described
Muting sensitive induction reactance chamotte mould polycarboxylate water-reducer.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (9)
1. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer, it is characterised in that：Its pH be 6.0~6.5, solid content be 45~
55%, raw material is grouped as by the group of following parts by weight：The 4- hydroxyl butyl vinyl polyoxyethylene that molecular weight is 2000~5000
90~130 parts by weight of base ether, 6~10 parts by weight of unsaturated monocarboxylic acid, 3~6 parts by weight of unsaturated carboxylate type monomer, insatiable hunger
With 1~5 parts by weight of both sexes quaternary alkylphosphonium salt, 0.2~0.8 parts by weight of oxidant, 0.2~1.0 parts by weight of reducing agent, catalyst 0.02~
0.06 parts by weight, 0.2~0.6 parts by weight of chain-transferring agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate
Deionized water, wherein unsaturated both sexes quaternary alkylphosphonium salt is triphenyl phosphorus and allyl bromide, bromoallylene with 1:1.0~1.5 molar ratio is in tetrachloro
Change in carbon and is made by following reaction：
2. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in claim 1, it is characterised in that：The unsaturation both sexes
The preparation method of quaternary alkylphosphonium salt includes the following steps：
(1) in molar ratio 1:1.0~1.5 weigh triphenyl phosphorus and allyl bromide, bromoallylene；
(2) triphenyl phosphorus and appropriate carbon tetrachloride are mixed, is fully dissolved；
(3) allyl bromide, bromoallylene is added dropwise with the speed of 1/2~5s of drop in the material obtained by step (2), is carried out simultaneously during being added dropwise
Stirring is reacted, and reaction temperature is kept for 40~50 DEG C, and the reaction time is 4~6h, obtains tan precipitate object；
(4) above-mentioned tan precipitate object is recrystallized with acetone, obtains recrystallized product；
(5) above-mentioned recrystallized product is dried in vacuo, obtains the powder of white, the as described unsaturated both sexes quaternary alkylphosphonium salt.
3. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in claim 1, it is characterised in that：The unsaturation unitary
Carboxylic acid is acrylic acid and/or methacrylic acid.
4. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in claim 1, it is characterised in that：The unsaturated carboxylic acid
Esters monomer is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylic acid
At least one of methyl esters and methyl methacrylate.
5. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in claim 1, it is characterised in that：The oxidant was
At least one of hydrogen oxide, sodium peroxydisulfate and ammonium persulfate.
6. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in claim 1, it is characterised in that：The reducing agent is first
Aldehyde closes at least one of sodium bisulphite, Bruggolite FF6 and sodium hypophosphite.
7. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in claim 1, it is characterised in that：The catalyst is sulphur
Sour ferrous and/or ferrous nitrate.
8. a kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in claim 1, it is characterised in that：The chain-transferring agent is
At least one of thioacetic acid, mercaptopropionic acid and mercaptoethanol.
9. a kind of preparation side of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer as described in any claim in claim 1 to 8
Method, it is characterised in that：Include the following steps：
(1) each raw material component is weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10~15 parts by weight of deionized water, potassium hydroxide aqueous solution is used in combination
PH to 5.5~6.0 is adjusted, the first solution is obtained；It dissolves reduce agent in 10~15 parts by weight of deionized water and obtains the second solution；
Unsaturated carboxylate type monomer is dissolved in 6~10 parts by weight of deionized water and obtains third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in the deionization of 80~90 parts by weight
In water, then be sequentially added into 35~55% the first solution, appropriate sodium hydrate aqueous solution, catalyst and oxidant, and adjust
Reaction temperature is reacted to 10~30 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), in 0.5~1.5h
It is inside added dropwise, 0.5~1.5h of insulation reaction after completion of dropwise addition；
(5) with the pH value of appropriate sodium hydrate aqueous solution regulating step (4) resulting material to 6.0~6.5 to get to the muting sensitive
Induction reactance chamotte mould polycarboxylate water-reducer.
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| CN107200817B (en) * | 2017-07-07 | 2019-07-19 | 科之杰新材料集团有限公司 | A kind of preparation method of stable type concrete slump controlling agent |
| CN107556442A (en) * | 2017-09-30 | 2018-01-09 | 江苏兆佳建材科技有限公司 | A kind of comprehensive polycarboxylate water-reducer of muting sensitive sense |
| CN108147700B (en) * | 2017-12-28 | 2020-12-29 | 科之杰新材料集团有限公司 | Preparation method of shrinkage-reducing viscosity-reducing polycarboxylic acid plasticizer |
| CN110066133A (en) * | 2019-04-04 | 2019-07-30 | 南京瑞固聚合物有限公司 | The dedicated polycarboxylate water-reducer of prefabricated components concrete and its preparation process |
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| CN104609756A (en) * | 2014-12-31 | 2015-05-13 | 中建商品混凝土有限公司 | Cationic concrete mud inhibiting agent and preparation method thereof |
| CN104628969A (en) * | 2015-01-30 | 2015-05-20 | 江苏奥莱特新材料有限公司 | Preparation method of slow-release solid polycarboxylic acid water reducing agent |
| CN105037648A (en) * | 2015-08-25 | 2015-11-11 | 科之杰新材料集团有限公司 | Slump-retaining water-reducing polycarboxylic acid water reducing agent and low-temperature quick preparation method thereof |
| CN105294967A (en) * | 2015-10-20 | 2016-02-03 | 江苏苏博特新材料股份有限公司 | Anti-clay naphthalene water reducing agent and preparation method thereof |
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| KR20110073507A (en) * | 2008-09-11 | 2011-06-29 | 가부시키가이샤 닛폰 쇼쿠바이 | Multibranched polyalkylene glycol polymer and manufacturing method thereof, and cement admixture |
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| CN104609756A (en) * | 2014-12-31 | 2015-05-13 | 中建商品混凝土有限公司 | Cationic concrete mud inhibiting agent and preparation method thereof |
| CN104628969A (en) * | 2015-01-30 | 2015-05-20 | 江苏奥莱特新材料有限公司 | Preparation method of slow-release solid polycarboxylic acid water reducing agent |
| CN105037648A (en) * | 2015-08-25 | 2015-11-11 | 科之杰新材料集团有限公司 | Slump-retaining water-reducing polycarboxylic acid water reducing agent and low-temperature quick preparation method thereof |
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Address after: 361000 Fujian province Xiamen torch hi tech Zone (Xiangan) Industrial Zone neian Road No. 169 Co-patentee after: Kezhijie New Material Group Fujian Co., Ltd Patentee after: KZJ NEW MATERIALS GROUP Co.,Ltd. Address before: 361000 Fujian province Xiamen torch hi tech Zone (Xiangan) Industrial Zone neian Road No. 169 Co-patentee before: FUJIAN KEZHIJIE NEW MATERIALS Co.,Ltd. Patentee before: KZJ NEW MATERIALS GROUP Co.,Ltd. |