CN106380551A - Low-sensitivity anti-mud polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Low-sensitivity anti-mud polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- CN106380551A CN106380551A CN201610820592.0A CN201610820592A CN106380551A CN 106380551 A CN106380551 A CN 106380551A CN 201610820592 A CN201610820592 A CN 201610820592A CN 106380551 A CN106380551 A CN 106380551A
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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 a low-sensitivity anti-mud polycarboxylic acid water reducing agent and a preparation method thereof. The pH value is 6.0-6.5, and the solid content is 45-55%. The water reducing agent is composed of the following components in parts by weight: 90-130 parts of 4-hydroxybutylvinyl polyoxyvinyl ether with the molecular weight of 2000-5000, 6-10 parts of unsaturated monocarboxylic acid, 3-6 parts of unsaturated carboxylate monomer, 1-5 parts of unsaturated amphoteric quaternary alkylphosphonium salt, 0.2-0.8 part of oxidizer, 0.2-1.0 part of reducer, 0.02-0.06 part of catalyst, 0.2-0.6 part of chain-transfer agent, a right amount of potassium hydroxide water solution, a right amount of sodium hydroxide water solution and a right amount of deionized water. The polycarboxylic acid water reducing agent has the advantages of more uniform side chain distribution and favorable slump retaining effect, and has excellent low sensitivity to the doping amount changes.
Description
Technical field
The invention belongs to cement water reducing agent technical field and in particular to a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer and
Its preparation method.
Background technology
Poly carboxylic acid series water reducer has excellent dispersive property, and concrete can be made under relatively low volume to reach preferable stream
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 improves constantly although water-reducing rate improves the consumption that can reduce polycarboxylate water-reducer, reduces cost, but
Also improve the sensitivity of polycarboxylate water-reducer, show as in work progress, polycarboxylate water-reducer reasonable volume point drops a bit
Volume, can lead to fresh concrete mobility not or loss is too fast, and reasonable volume point carries some volumes, then be easily caused concrete
Isolation, bleeding are so that concrete production controls difficulty to increase, that is, sensitive to volume.
In addition, substantial amounts of case history and research show, with the water reducer phase such as naphthalene system, melamine series and amido sulfoacid series
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 for ratio
Power degradation, to protect effect of collapsing poor, leads to maturing intensity decreases etc..Although can be obtained by improving water reducer volume
Alleviate, but the problems such as be easily caused concrete coagulating time overlength and compressive strength rate and reduce, and greatly increase cost.
Content of the invention
It is an object of the invention to overcoming prior art defect, provide a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer.
Another object of the present invention is to providing the preparation method of above-mentioned hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer.
Technical scheme is as follows：
A kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer, its pH be 6.0～6.5, solid content be 45～55%, its raw material by
The group of following weight portion is grouped into：Molecular weight is 2000～5000 4- hydroxyl butyl vinyl polyoxyethylene ether 90～130 weight
Amount part, unsaturated monocarboxylic acid 6～10 weight portion, unsaturated carboxylate type monomer 3～6 weight portion, unsaturated both sexes quaternary alkylphosphonium salt 1
～5 weight portions, oxidant 0.2～0.8 weight portion, reducing agent 0.2～1.0 weight portion, catalyst 0.02～0.06 weight portion, chain
Transfer agent 0.2～0.6 weight portion, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate amount of deionized water, its
In, it is as follows that unsaturated both sexes quaternary alkylphosphonium salt is that triphenyl phosphorus and allyl bromide, bromoallylene are pressed in carbon tetrachloride with 1: 1.0～1.5 mol ratio
Reaction is obtained：
In a preferred embodiment of the invention, the preparation method of described unsaturation both sexes quaternary alkylphosphonium salt includes walking as follows
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, fully dissolve；
(3) with the speed Deca allyl bromide, bromoallylene of 1/2～5s in the material of step (2) gained, carry out during Deca
Stirring is reacted simultaneously, and reaction temperature keeps 40～50 DEG C, and the response time is 4～6h, obtains tan precipitate thing；
(4) with acetone, recrystallization is carried out to above-mentioned tan precipitate thing, obtain recrystallized product；
(5) above-mentioned recrystallized product is vacuum dried, is obtained the powder of white, as described unsaturation both sexes quaternary phosphonium
Salt.
In a preferred embodiment of the invention, described unsaturated monocarboxylic acid is acrylic acid and/or metering system
Acid.
In a preferred embodiment of the invention, described unsaturated carboxylate type monomer is 2-(Acryloyloxy)ethanol, first
In base 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, Hydroxypropyl methacrylate, acrylic acid methyl ester. and methyl methacrylate extremely
Few one kind.
In a preferred embodiment of the invention, described oxidant is hydrogen peroxide, sodium peroxydisulfate and Ammonium persulfate.
In at least one.
In a preferred embodiment of the invention, described reducing agent is sodium formaldehyde sulphoxylate, Br ü ggolitTM
At least one in FF6 and sodium hypophosphite.
In a preferred embodiment of the invention, described catalyst is ferrous sulfate and/or ferrous nitrate.
In a preferred embodiment of the invention, described chain-transferring agent is TGA, mercaptopropionic acid and sulfydryl second
At least one in alcohol.
The preparation method of above-mentioned hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer, comprises the steps：
(1) each raw material components are weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10～15 parts by weight of deionized water, and with adjust pH to
5.5～6.0, obtain the first solution；Dissolve reduce agent in and in 10～15 parts by weight of deionized water, obtain the second solution；By unsaturation
Carboxylic acid esters monomer is dissolved in 6～10 parts by weight of deionized water and obtains the 3rd solution；
(3) 4- hydroxyl butyl vinyl polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in going of 80～90 weight portions
In ionized water, then be sequentially added into 35～55% the first solution, appropriate sodium hydrate aqueous solution, catalyst and oxidant, and
Adjust reaction temperature to be reacted to 10～30 DEG C；
(4) be simultaneously added dropwise the first solution, the second solution and the 3rd solution to the material of step (3) gained, all 0.5～
Completion of dropping in 1.5h, insulation reaction 0.5～1.5h 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, that is, obtain described
Hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer.
The invention has the beneficial effects as follows：
1st, the hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer of the present invention is using having high double bond retention rate, highly active 4- hydroxyl fourth
Base vinyl polyoxyethylene ether polymeric monomer, compared with allyl polyethenoxy polyethers, isopentene group polyoxyethylene polyethers and methyl alkene
Propyl group polyoxyethylene polyethers has higher polymerization activity, and the polycarboxylate water-reducer side chain distribution of synthesis is more uniform, protects effect of collapsing
Good, the volume change to polycarboxylate water-reducer has excellent hyposensitivity energy.
2nd, the preparation method of the present invention introduces unsaturated both sexes quaternary alkylphosphonium salt and unsaturated carboxylate type in building-up process
Monomer, quaternary alkylphosphonium salt cation group side chain act as suppress or reduce soil activity thus reducing the suction to water reducer for the soil
Attached, make the carboxylic acid ion in molecular structure and polyether lateral chain play absorption cement and the effect of dispersion cement, final body respectively
It is now anti-mud adaptability and hyposensitivity, and carboxylic acid esters group is in the basic conditions, has slowly released the carboxylic of water-reduction
Acid ion, has ensured that the diminishing of poly carboxylic acid series water reducer protects the effect of collapsing further.
3rd, the preparation method of the present invention adopts low-temperature oxidation reduction initiating system, and this synthesis technique material dropping time is short,
Production efficiency is high.
Specific embodiment
Below by way of specific embodiment, technical scheme is further detailed and describes.
Unsaturated both sexes quaternary alkylphosphonium salt in following embodiments is triphenyl phosphorus and allyl bromide, bromoallylene is anti-for 1: 1.2 according to mol ratio
Should be obtained, concrete grammar is as follows：The triphenyl phosphorus of 20g and the carbon tetrachloride of 30g are added in 100mL there-necked flask, magnetic force stirs
Mix, dissolved.Dissolving finishes, Deca (1/2 seconds) 11.07g allyl bromide, bromoallylene, carries out magnetic agitation during Deca, reaction
Temperature keeps 45 DEG C, and reaction will have tan precipitate to separate out after a period of time.After 4h, with acetone, precipitated product is tied again
Crystalline substance, the product of recrystallization is dried 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 components are weighed by following weight portion：4- hydroxyl butyl vinyl polyoxyethylene ether (molecular weight 2000)
110 weight portions, acrylic acid 8 weight portion, 2-(Acryloyloxy)ethanol 6 weight portion, unsaturated both sexes quaternary alkylphosphonium salt 2 weight portion, hydrogen peroxide
0.5 weight portion, Br ü ggolitTMFF60.7 weight portion, ferrous sulfate 0.04 weight portion, TGA 0.35 weight portion, 50%
Potassium hydroxide aqueous solution 4 weight portion of mass concentration, sodium hydrate aqueous solution 5 weight portion of 32% mass concentration, remaining is to go
Ionized water, is adjusted to 50% solid content.
(2) acrylic acid, TGA are dissolved in 15 parts by weight of deionized water, and the potassium hydroxide with 50% mass concentration
Aqueous solution adjusts pH to 5.5～6.0, obtains the first solution；By Br ü ggolitTMFF6 is dissolved in 15 parts by weight of deionized water and obtaining
To the second solution；Unsaturated carboxylate type monomer is dissolved in 10 parts by weight of deionized water and obtains the 3rd solution；
(3) 4- hydroxyl butyl vinyl polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 35% the first solution again, the sodium hydrate aqueous solution of 32% mass concentration, ferrous sulfate and hydrogen peroxide, and
Adjust reaction temperature to 10 DEG C；
(4) be simultaneously added dropwise the first solution, the second solution and the 3rd solution to the material of step (3) gained, three kinds of solution
Completion of dropping all in 1h, is incubated 1.5h after completion of dropwise addition；
(5) insulation terminates, and adjusting pH value with the sodium hydrate aqueous solution of 32% mass concentration is 6.0～6.5, that is, obtain institute
State hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer PCE-1.
Embodiment 2
(1) each raw material components 4- hydroxyl butyl vinyl polyoxyethylene ether (molecular weight 2400) are weighed by following weight portion
110 weight portions, acrylic acid 6 weight portion, hydroxyethyl methylacrylate 3 weight portion, unsaturated both sexes quaternary alkylphosphonium salt 1 weight portion, over cure
Sour sodium 0.6 weight portion, sodium formaldehyde sulphoxylate 0.8 weight portion, ferrous nitrate 0.02 weight portion, mercaptopropionic acid 0.4 weight portion,
Potassium hydroxide aqueous solution 2 weight portion of 50% mass concentration, sodium hydrate aqueous solution 6 weight portion 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, and the potassium hydroxide with 50% mass concentration
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 methylacrylate is dissolved in 10 parts by weight of deionized water and obtains the 3rd solution；
(3) 4- hydroxyl butyl vinyl polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 45% the first solution again, the sodium hydrate aqueous solution of 32% mass concentration, ferrous nitrate and sodium peroxydisulfate, and
Adjust reaction temperature to 15 DEG C；
(4) be simultaneously added dropwise the first solution, the second solution and the 3rd solution to the material of step (3) gained, three kinds of solution
Completion of dropping all in 0.5h, is incubated 1h after completion of dropwise addition；
(5) insulation terminates, and adjusting pH value with the sodium hydrate aqueous solution of 32% mass concentration is 6.0～6.5, that is, obtain institute
State hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer PCE-2.
Embodiment 3
(1) each raw material components are weighed by following weight portion：4- hydroxyl butyl vinyl polyoxyethylene ether (molecular weight 4000)
100 weight portions, methacrylic acid 7 weight portion, Hydroxypropyl acrylate 4 weight portion, unsaturated both sexes quaternary alkylphosphonium salt 3 weight portion, over cure
Sour ammonium 0.4 weight portion, Br ü ggolitTMFF6 0.7 weight portion, ferrous nitrate 0.06 weight portion, mercaptoethanol 0.5 weight portion,
Potassium hydroxide aqueous solution 3 weight portion of 50% mass concentration, sodium hydrate aqueous solution 4 weight portion 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, and the hydrogen-oxygen with 50% mass concentration
Change aqueous solutions of potassium and adjust pH to 5.5～6.0, obtain 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 the 3rd solution；
(3) 4- hydroxyl butyl vinyl polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 40% the first solution again, the sodium hydrate aqueous solution of 32% mass concentration, ferrous nitrate and Ammonium persulfate., and
Adjust reaction temperature to 20 DEG C；
(4) be simultaneously added dropwise the first solution, the second solution and the 3rd solution to the material of step (3) gained, three kinds of solution
Completion of dropping all in 0.75h, is incubated 0.5h after completion of dropwise addition；
(5) insulation terminates, and adjusting pH value with the sodium hydrate aqueous solution of 32% mass concentration is 6.0～6.5, that is, obtain institute
State hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer PCE-3.
Embodiment 4
(1) each raw material components are weighed by following weight portion：4- hydroxyl butyl vinyl polyoxyethylene ether (molecular weight 5000)
100 weight portions, methacrylic acid 9 weight portion, acrylic acid methyl ester. 5 weight portion, unsaturated both sexes quaternary alkylphosphonium salt 4 weight portion, peroxidating
Hydrogen 0.7 weight portion, sodium hypophosphite 1.0 weight portion, ferrous sulfate 0.05 weight portion, mercaptopropionic acid 0.6 weight portion, 50% mass are dense
Potassium hydroxide aqueous solution 5 weight portion of degree, sodium hydrate aqueous solution 5 weight portion 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, and the hydrogen-oxygen with 50% mass concentration
Change aqueous solutions of potassium and adjust pH to 5.5～6.0, obtain the first solution；Sodium hypophosphite is dissolved in 15 parts by weight of deionized water and obtains
Second solution；Acrylic acid methyl ester. is dissolved in 10 parts by weight of deionized water and obtains the 3rd solution；
(3) 4- hydroxyl butyl vinyl polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 55% the first solution again, the sodium hydrate aqueous solution of 32% mass concentration, ferrous sulfate and hydrogen peroxide, and
Adjust reaction temperature to 30 DEG C；
(4) be simultaneously added dropwise the first solution, the second solution and the 3rd solution to the material of step (3) gained, three kinds of solution
Completion of dropping all in 1h, is incubated 0.75h after completion of dropwise addition；
(5) insulation terminates, and adjusting pH value with the sodium hydrate aqueous solution of 32% mass concentration is 6.0～6.5, that is, obtain institute
State hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer PCE-4.
Embodiment 5
By embodiment 1～4 synthesis obtain hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer (PCE-1, PCE-2, PCE-3 and
PCE-4) carry out different addition quantity concrete performance and compare with commercially available ethers polycarboxylic acid water reducing agent (PCE-0), by adjusting water reducer
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 be a%) and 550 ± 10mm (volume is b%) respectively, calculate its volume width ratio γ (γ=
B/a), γ is bigger, illustrates that water reducer 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：
Table 1 embodiment performance comparison
Can be seen that from the above, its volume width ratio γ of commercially available ethers polycarboxylic acid water reducing agent is 1.41, and passes through reality
Apply the hypoallergenic sense polycarboxylate water-reducer of example synthesis, volume width ratio γ is respectively 1.65,1.73,1.68 and 1.77, be intended to big
In commercially available ethers polycarboxylic acid water reducing agent volume width ratio, illustrate that the hypoallergenic sense polycarboxylate water-reducer of embodiment synthesis becomes to volume
Change less sensitive.And in the case that aggregate clay content is 1.5%, reach identical divergence, commercially available ethers polycarboxylic acids subtract
Water preparation volume is substantially higher compared with the polycarboxylate water-reducer volume that embodiment synthesizes, and protect collapse poor, illustrate embodiment synthesize low
Sensitive polycarboxylate water-reducer is preferable to adaptability for materials, and anti-mud effect is good.
Those of ordinary skill in the art understand, when technical scheme changes in following ranges, remain able to
To same as the previously described embodiments or close technique effect, still fall within protection scope of the present invention：
A kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer, its pH be 6.0～6.5, solid content be 45～55%, its raw material by
The group of following weight portion is grouped into：Molecular weight is 2000～5000 4- hydroxyl butyl vinyl polyoxyethylene ether 90～130 weight
Amount part, unsaturated monocarboxylic acid 6～10 weight portion, unsaturated carboxylate type monomer 3～6 weight portion, unsaturated both sexes quaternary alkylphosphonium salt 1
～5 weight portions, oxidant 0.2～0.8 weight portion, reducing agent 0.2～1.0 weight portion, catalyst 0.02～0.06 weight portion, chain
Transfer agent 0.2～0.6 weight portion, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate amount of deionized water, its
In, it is as follows that unsaturated both sexes quaternary alkylphosphonium salt is that triphenyl phosphorus and allyl bromide, bromoallylene are pressed in carbon tetrachloride with 1: 1.0～1.5 mol ratio
Reaction is obtained：
The preparation method of described unsaturation both sexes quaternary alkylphosphonium salt comprises the 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, fully dissolve；
(3) with the speed Deca allyl bromide, bromoallylene of 1/2～5s in the material of step (2) gained, carry out during Deca
Stirring is reacted simultaneously, and reaction temperature keeps 40～50 DEG C, and the response time is 4～6h, obtains tan precipitate thing；
(4) with acetone, recrystallization is carried out to above-mentioned tan precipitate thing, obtain recrystallized product；
(5) above-mentioned recrystallized product is vacuum dried, is obtained the powder of white, as described unsaturation both sexes quaternary phosphonium
Salt.
Described unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid.Described unsaturated carboxylate type monomer is third
Olefin(e) acid hydroxyl ethyl ester, hydroxyethyl methylacrylate, Hydroxypropyl acrylate, Hydroxypropyl methacrylate, acrylic acid methyl ester. and methyl-prop
At least one in e pioic acid methyl ester.Described oxidant is at least one in hydrogen peroxide, sodium peroxydisulfate and Ammonium persulfate..Described
Reducing agent is sodium formaldehyde sulphoxylate, Br ü ggolitTMAt least one in FF6 and sodium hypophosphite.Described catalyst is sulfur
Acid ferrous iron and/or ferrous nitrate.Described chain-transferring agent is at least one in TGA, mercaptopropionic acid and mercaptoethanol.
The preparation method of above-mentioned hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer, comprises the steps：
(1) each raw material components are weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10～15 parts by weight of deionized water, and with adjust pH to
5.5～6.0, obtain the first solution；Dissolve reduce agent in and in 10～15 parts by weight of deionized water, obtain the second solution；By unsaturation
Carboxylic acid esters monomer is dissolved in 6～10 parts by weight of deionized water and obtains the 3rd solution；
(3) 4- hydroxyl butyl vinyl polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in going of 80～90 weight portions
In ionized water, then be sequentially added into 35～55% the first solution, appropriate sodium hydrate aqueous solution, catalyst and oxidant, and
Adjust reaction temperature to be reacted to 10～30 DEG C；
(4) be simultaneously added dropwise the first solution, the second solution and the 3rd solution to the material of step (3) gained, all 0.5～
Completion of dropping in 1.5h, insulation reaction 0.5～1.5h 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, that is, obtain described
Hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer.
The above, only presently preferred embodiments of the present invention, therefore the scope of present invention enforcement can not be limited according to this, that is,
The equivalence changes made according to the scope of the claims of the present invention and description and modification, all should still belong in the range of the present invention covers.
Claims (9)
1. a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：Its pH be 6.0～6.5, solid content be 45～
55%, its raw material is grouped into by the group of following weight portion：Molecular weight is 2000～5000 4- hydroxyl butyl vinyl polyoxyethylene
Base ether 90～130 weight portion, unsaturated monocarboxylic acid 6～10 weight portion, unsaturated carboxylate type monomer 3～6 weight portion, insatiable hunger
With both sexes quaternary alkylphosphonium salt 1～5 weight portion, oxidant 0.2～0.8 weight portion, reducing agent 0.2～1.0 weight portion, catalyst 0.02～
0.06 weight portion, chain-transferring agent 0.2～0.6 weight portion, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate
Deionized water, wherein, unsaturated both sexes quaternary alkylphosphonium salt be triphenyl phosphorus and allyl bromide, bromoallylene with 1: 1.0～1.5 mol ratio in tetrachloro
Change in carbon and be obtained by following reaction：
2. as claimed in claim 1 a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：The both sexes of described unsaturation
The preparation method of quaternary alkylphosphonium salt comprises the 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, fully dissolve；
(3) with the speed Deca allyl bromide, bromoallylene of 1/2～5s in the material of step (2) gained, carry out simultaneously during Deca
Stirring is reacted, and reaction temperature keeps 40～50 DEG C, and the response time is 4～6h, obtains tan precipitate thing；
(4) with acetone, recrystallization is carried out to above-mentioned tan precipitate thing, obtain recrystallized product；
(5) above-mentioned recrystallized product is vacuum dried, is obtained the powder of white, as described unsaturation both sexes quaternary alkylphosphonium salt.
3. as claimed in claim 1 a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：Described unsaturation unitary
Carboxylic acid is acrylic acid and/or methacrylic acid.
4. as claimed in claim 1 a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：Described unsaturated carboxylic acid
Esters monomer is 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate, Hydroxypropyl methacrylate, acrylic acid
At least one in methyl ester and methyl methacrylate.
5. as claimed in claim 1 a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：Described oxidant was
At least one in hydrogen oxide, sodium peroxydisulfate and Ammonium persulfate..
6. as claimed in claim 1 a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：Described reducing agent is first
Aldehyde closes sodium bisulphite, Br ü ggolitTMAt least one in FF6 and sodium hypophosphite.
7. as claimed in claim 1 a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：Described catalyst is sulfur
Acid ferrous iron and/or ferrous nitrate.
8. as claimed in claim 1 a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer it is characterised in that：Described chain-transferring agent is
At least one in TGA, mercaptopropionic acid and mercaptoethanol.
9. the preparation side of a kind of hypoallergenic induction reactance chamotte mould polycarboxylate water-reducer as described in any claim in claim 1 to 8
Method it is characterised in that：Comprise the steps：
(1) each raw material components are weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10～15 parts by weight of deionized water, and with adjust pH to 5.5～
6.0, obtain the first solution；Dissolve reduce agent in and in 10～15 parts by weight of deionized water, obtain the second solution；By unsaturated carboxylic acid
Esters monomer is dissolved in 6～10 parts by weight of deionized water and obtains the 3rd solution；
(3) 4- hydroxyl butyl vinyl polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in the deionization of 80～90 weight portions
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) be simultaneously added dropwise the first solution, the second solution and the 3rd solution to the material of step (3) gained, all in 0.5～1.5h
Interior completion of dropping, insulation reaction 0.5～1.5h 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, that is, obtain described hypoallergenic
Induction reactance chamotte mould polycarboxylate water-reducer.
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| 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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