A kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer and preparation method thereofTechnical 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 andPreparation method.
Background technology
Poly carboxylic acid series water reducer has excellent dispersion performance, concrete can be made to reach preferable stream at low dosageDynamic property, is widely used in the engineerings such as highway, bridge, dam, tunnel, skyscraper.With the continuous development of polycarboxylic acids technology, gatherThe 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 bitVolume, can cause fresh concrete mobility not enough or loss is too fast, and reasonable volume point carries some volumes, then easily leads to concreteIsolation, 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 seriesThan 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 reducerPower degradation, guarantor's effect of collapsing are poor, lead to maturing strength reduction etc..Although can be obtained by improving water-reducing agent volumeAlleviate, 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 byThe group of following parts by weight is grouped as：90~130 weight of 4- hydroxyl butyl vinyls polyoxyethylene ether that molecular weight is 2000~5000Measure 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, chain0.2~0.6 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 followsReaction is made：
In a preferred embodiment of the invention, the preparation method of the unsaturated both sexes quaternary alkylphosphonium salt includes following stepSuddenly：
(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 dropwiseStirring 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 phosphoniumSalt.
In a preferred embodiment of the invention, the unsaturated monocarboxylic acid is acrylic acid and/or metering systemAcid.
In a preferred embodiment of the invention, the unsaturated carboxylate type monomer is hydroxy-ethyl acrylate, firstIn base hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methyl acrylate and methyl methacrylate extremelyFew one kind.
In a preferred embodiment of the invention, the oxidant is hydrogen peroxide, sodium peroxydisulfate and ammonium persulfateAt least one of.
In a preferred embodiment of the invention, the reducing agent is sodium formaldehyde sulphoxylate, Br ü ggolitTMAt 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 secondAt 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 to5.5~6.0, 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 unsaturatedCarboxylic 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 weightIn ionized water, then be sequentially added into 35~55% the first solution, appropriate sodium hydrate aqueous solution, catalyst and oxidant, andReaction 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 describedMuting 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 activityBase vinyl polyoxyethylene ether polymeric monomer, compared with allyl polyethenoxy polyethers, isopentene group polyoxyethylene polyethers and methyl alkenePropyl polyoxyethylene polyethers has higher polymerization activity, and the polycarboxylate water-reducer side chain distribution of synthesis is more uniform, protects effect of collapsingIt 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 processMonomer, the active suction to reduce soil to water-reducing agent for acting as inhibiting or reduce soil of quaternary alkylphosphonium salt cation group side chainIt 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 bodyIt is now anti-mud adaptability and hyposensitivity, and carboxylic acid esters group is under alkaline condition, has slowly released the carboxylic of water-reductionAcid 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 stirsIt 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 dropwiseTemperature 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 acetoneThe 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 peroxide0.5 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 goIonized 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 combinationAqueous 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 obtainedTo 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, andReaction 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 solutionIt 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 concentrationState 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 weight110 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 cure0.6 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, remainingFor 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 combinationAqueous solution adjusts pH to 5.5~6.0, obtains the first solution；Sodium formaldehyde sulphoxylate is dissolved in 15 parts by weight of deionized waterObtain 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, andReaction 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 solutionIt 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 concentrationState 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 cure0.4 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, remainingFor 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 combinationChange 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 waterIn 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, andReaction 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 solutionIt 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 concentrationState 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, peroxidating0.7 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 dense5 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 combinationChange 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 obtainedSecond 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, andReaction 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 solutionIt 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 concentrationState 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 andPCE-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 agentVolume, according to GB/T50080-2011《Standard for test methods of properties of ordinary concrete mixture standard》, by fresh concrete divergenceAccomplish 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, sand790kg/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 realityThe 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 bigIn commercially available ethers polycarboxylic acid water reducing agent volume width ratio, illustrate that the muting sensitive sense polycarboxylate water-reducer of embodiment synthesis becomes volumeChange less sensitive.And in the case where aggregate clay content is 1.5%, reach identical divergence, commercially available ethers polycarboxylic acids subtractsAqua 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 synthesisSensitive 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 rangesTo 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 byThe group of following parts by weight is grouped as：90~130 weight of 4- hydroxyl butyl vinyls polyoxyethylene ether that molecular weight is 2000~5000Measure 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, chain0.2~0.6 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 followsReaction 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 dropwiseStirring 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 phosphoniumSalt.
The unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid.The unsaturated carboxylate type monomer is thirdOlefin(e) acid hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methyl acrylate and methyl-propAt least one of e pioic acid methyl ester.The oxidant is at least one of hydrogen peroxide, sodium peroxydisulfate and ammonium persulfate.It is describedReducing agent is sodium formaldehyde sulphoxylate, Br ü ggolitTMAt least one of FF6 and sodium hypophosphite.The catalyst is sulphurSour 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 to5.5~6.0, 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 unsaturatedCarboxylic 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 weightIn ionized water, then be sequentially added into 35~55% the first solution, appropriate sodium hydrate aqueous solution, catalyst and oxidant, andReaction 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 describedMuting 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.