CN106380553B - The method that response phase method optimization microwave radiation prepares maleic anhydride analog high efficiency water reducing agent - Google Patents
The method that response phase method optimization microwave radiation prepares maleic anhydride analog high efficiency water reducing agent Download PDFInfo
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- CN106380553B CN106380553B CN201610869618.0A CN201610869618A CN106380553B CN 106380553 B CN106380553 B CN 106380553B CN 201610869618 A CN201610869618 A CN 201610869618A CN 106380553 B CN106380553 B CN 106380553B
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/166—Macromolecular compounds comprising sulfonate or sulfate groups obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
Abstract
The present invention discloses a kind of method that response phase method optimization microwave radiation prepares maleic anhydride analog high efficiency water reducing agent, it be added water and stirred using allyl polyethenoxy ether and methylpropene sodium sulfonate as raw material it is uniformly mixed, reaction temperature is heated under the conditions of microwave radiation, then maleic anhydride and ammonium persulfate reaction a period of time is added in constant temperature, utilize the variable parameter of response phase method setting reaction, it cools down after reaction, adjusts pH to get maleic anhydride analog high efficiency water reducing agent.Present invention research is on the basis of single factor analysis, optimize maleic anhydride analog high efficiency water reducing agent synthesis technology using response phase method, it obtains and is relatively suitable for preparing maleic anhydride analog high efficiency water reducing agent process conditions, it is intended to provide scientific experimentation foundation for exploitation, the popularization of high efficiency water reducing agent.
Description
Technical field
The invention belongs to the preparation fields of water-reducing agent, and in particular to a kind of response phase method optimization microwave radiation prepares maleic acid
The method of anhydride high efficiency water reducing agent.
Background technique
Maleic anhydride contains anhydride group and carbon-carbon double bond, which is conducive to generate conjugation, makes double bond (- C
=C-) easily it is copolymerized with olefin monomer, such as methylpropene sodium sulfonate, acrylic acid, allyl polyethenoxy ether, styrene
Monomer, and the maleic anhydride as cyclic structure, because of carbonyl electrophilic inductive effect in its intramolecule and disubstituted group
Space steric effect makes it be difficult to carry out homopolymerization.So compared with the active olefin for being easy to happen homopolymerization, the low work of maleic anhydride
Property reaction system can be effectively prevent cruelly poly-, realize that reaction condition is easily controllable, simple production process；In addition, maleic anhydride price
It is cheap, product cost is advantageously reduced, convenient for the popularization and application of high efficiency water reducing agent.
Compared with traditional heating, microwave radiation has unique fuel factor and non-thermal effect, can not only realize to reactant
System is quick, is evenly heated, and can realize selectivity heating, and pass through pole according to the dielectric constant difference of medium in reaction system
Change effect, priming reaction group improve polymerization rate.
Responds Surface Methodology is a kind of using functional relation between polynary quadratic regression equation data fitting and response
A kind of statistical method, this method can solve Multivariable, and obtain optimal processing parameter by regression equation analysis.Exist at present
In the exploitation of high efficiency water reducing agent, such as CN201210274917.1, be filtered out using orthogonal experiment method influence index it is significant because
Element simultaneously provides the combination of best factor level, but in the presence of can not find out lacking for the optimal combination of factor and response in whole region
Point, and mostly use linear model, and the problems such as actual conditions are there are deviation, and precision is not high.
Summary of the invention
Present invention aim to address above-mentioned technical problem, a kind of response phase method optimization microwave radiation is provided and prepares maleic acid
The method of anhydride high efficiency water reducing agent is studied on the basis of single factor analysis, is efficiently subtracted using response phase method optimization maleic acid anhydride
Aqua synthesis technology obtains and is relatively suitable for preparing maleic anhydride analog high efficiency water reducing agent process conditions, it is intended to for high efficiency water reducing agent
Offer scientific experimentation foundation is promoted in exploitation.
To realize above-mentioned purpose, the technical solution of the present invention is as follows:
A kind of method that response phase method optimization microwave radiation prepares maleic anhydride analog high efficiency water reducing agent, it is poly- with allyl
It is uniformly mixed that ethylene oxide ether and methylpropene sodium sulfonate are that raw material adds water and stirs, and reaction temperature is heated under the conditions of microwave radiation
Degree, then maleic anhydride and ammonium persulfate reaction a period of time is added in constant temperature, and the variable parameter of reaction is set using response phase method,
It cools down after reaction, adjusts pH to get maleic anhydride analog high efficiency water reducing agent.
As further technical solution, the variable parameter of response phase method setting reaction described above, by following secondary
Multinomial regression equation:
Y=320.00+0.83A+2.33B+4.92C-0.42D-1.50AB-3.25AC-4.75AD-4. 50CD-
10.93A2–5.93B2-8.31C2+1.44D2；
In formula: response Y is flowing degree of net paste of cement, unit mm；A is methylpropene sodium sulfonate and allyl polyethenoxy
The molar ratio of ether；B is the molar ratio of maleic anhydride and allyl polyethenoxy ether；C is reaction time, unit min；D is reaction
Temperature, unit DEG C.
As further technical solution, the molar ratio of methylpropene sodium sulfonate and allyl polyethenoxy ether described above
For 0.4-0.6, the molar ratio of the maleic anhydride and allyl polyethenoxy ether is 2.5-3.5, and the reaction time is 25-
35min, the reaction temperature are 80-90 DEG C.
As further technical solution, the molar ratio of methylpropene sodium sulfonate and allyl polyethenoxy ether described above
It is 0.52, the molar ratio of the maleic anhydride and allyl polyethenoxy ether is 3.10, and the reaction time is 33min, described
Reaction temperature is 80 DEG C.
As further technical solution, the volume of ammonium persulfate described above is allyl polyethenoxy ether and methyl-prop
The 1.5%-2.5% of alkene sodium sulfonate gross mass.
As further technical solution, the power of microwave radiation described above is 250W-350W.
As further technical solution, it is to be adjusted to reaction solution pH after cooling with aqueous slkali that the above, which adjusts pH,
7-8。
As further technical solution, aqueous slkali described above is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
As further technical solution, the mass fraction of sodium hydroxide described above is 20%-40%.
Compared with prior art, the invention has the benefit that
(1) response phase method of the present invention be suitable for solve nonlinear transportation relevant issues, it enumerate experimental design,
Modeling, testing model well-formedness, seek optimum combination condition etc.；Pass through the regression fit and response surface, contour to process
Drafting, it is convenient to find out the response corresponding to each factor level；And the response optimal value of prediction is found out based on this
And the experiment condition of response.Compared with orthogonal test, advantage is:, can be continuously right in experimental condition searching process
Each level of test is analyzed, and resulting prediction model is that continuously, and orthogonal test can only be to examination isolated one by one
It tests and is a little analyzed；Response phase method considers test random error, at the same response phase method by complicated unknown function relationship small
It is fitted in region with simple primary or quadratic polynomial model, it is effective hand of solving practical problems that calculating is easier
Section.
(2) present invention establishes the secondary multinomial regression equation model of flowing degree of net paste of cement and dependent variable, use
8.0 software of Design-Expert, with five changed factors, only with four levels, compared with Orthogonal Method, with a small amount of test group
It can obtain a result, and obtained optimum condition is not the value of setting but within the scope of setting condition.Pass through
Using response phase method to the molar ratio of methylpropene sodium sulfonate and allyl polyethenoxy ether, maleic anhydride and allyl polyoxy second
Molar ratio, reaction time and the reaction temperature of alkene ether optimize, the condition optimized are as follows: methylpropene sodium sulfonate and allyl
The molar ratio of base polyoxyethylene ether is 0.52, and the molar ratio of maleic anhydride and allyl polyethenoxy ether is 3.10, the reaction time
For 33min, reaction temperature is 80 DEG C, and obtained product flowing degree of net paste of cement is 325.24mm, is efficiently subtracted for maleic acid anhydride
Aqua industrialized production provides a scientific basis.
(3) the method for the present invention is accurate and reliable.For the validity for verifying model, efficient diminishing is prepared using the method for the present invention
Agent, and carry out properties of product test.It is water in water-reducing agent solid volume with the ratio of mud for 0.29 by practical 3 parallel testings
Under the conditions of the 0.5% of shale amount, flowing degree of net paste of cement average value is 326mm, coincide substantially with theoretical expectation values, shows to be based on
Response phase method optimum synthesis technique is accurate and reliable.
(4) product of the present invention has good dispersion retentivity.In the present invention, when product volume is 0.15%, just
Beginning flowing degree of net paste of cement is 287mm, and as the initial flowing degree of net paste of cement of volume increase is gradually increased and is tended towards stability,
The corresponding initial flowing degree of net paste of cement of middle volume 0.5% reaches 328mm；In addition, as the testing time extends, four kinds of different diminishings
Flowing degree of net paste of cement under agent volume is declined slightly, and wherein volume is corresponding to 0.15%, 0.30%, 0.50%, 0.70%
60min flowing degree of net paste of cement gradual loss rate be respectively 5.9%, 4.5%, 5.2% and 4.9%, illustrate the efficient diminishing
Agent has good dispersion retentivity, is suitable for concrete long-distance transportation, construction.
(5) product of the present invention has preferable practical application value.The present invention is probing into maleic anhydride analog high efficiency water reducing agent
On the basis of dispersion performance, experiment investigation water-reducing agent application performance.When water-reducing agent solid volume is the 0.3% of cement quality,
Its corresponding water reducing ratio of cement mortar shows that the high efficiency water reducing agent prepared under the process conditions can meet high property well up to 35.4%
Energy concrete application requirement, has preferable practical application value.
(6) microwave radiation of the present invention effectively increases process efficiency, and energy conservation and environmental protection, easy to operate, easy to control.
Detailed description of the invention
Fig. 1 is methylpropene sodium sulfonate of the present invention and influence of the allyl polyethenoxy ether mole to flowing degree of net paste of cement
Figure；
Fig. 2 is the influence diagram of maleic anhydride of the present invention and allyl polyethenoxy ether molar ratio to flowing degree of net paste of cement；
Fig. 3 is influence diagram of the ammonium persulfate dosage of the present invention to flowing degree of net paste of cement；
Fig. 4 is influence diagram of the reaction temperature of the present invention to flowing degree of net paste of cement；
Fig. 5 is influence diagram of the reaction time of the invention to flowing degree of net paste of cement；
Fig. 6 is the molar ratio and maleic anhydride and allyl of methylpropene sodium sulfonate of the present invention and allyl polyethenoxy ether
Response surface figure of the reciprocation of the molar ratio of polyoxyethylene ether to flowing degree of net paste of cement；
Fig. 7 is to interact work in methylpropene sodium sulfonate of the present invention and the molar ratio of allyl polyethenoxy ether and reaction time
With the response surface figure to flowing degree of net paste of cement；
Fig. 8 is that methylpropene sodium sulfonate of the present invention and the molar ratio of allyl polyethenoxy ether and reaction temperature interact work
With the response surface figure to flowing degree of net paste of cement；
Fig. 9 is maleic anhydride of the present invention and the molar ratio of allyl polyethenoxy ether and the reciprocation in reaction time to water
The response surface figure of cement paste fluidity；
Figure 10 is the molar ratio of maleic anhydride of the present invention and allyl polyethenoxy ether and the reciprocation pair of reaction temperature
The response surface figure of flowing degree of net paste of cement；
Figure 11 is the response surface figure of reaction temperature of the present invention and the reciprocation in reaction time to flowing degree of net paste of cement；
Figure 12 is flowing degree of net paste of cement gradual loss figure under maleic anhydride analog high efficiency water reducing agent different addition quantity of the present invention.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to
The range that embodiment indicates.
Embodiment 1:
A kind of method that response phase method optimization microwave radiation prepares maleic anhydride analog high efficiency water reducing agent, it is poly- with allyl
It is uniformly mixed that ethylene oxide ether and methylpropene sodium sulfonate are that raw material adds water and stirs, and reaction temperature is heated under the conditions of microwave radiation
Degree, then maleic anhydride and ammonium persulfate reaction a period of time is added in constant temperature, and the variable parameter of reaction is set using response phase method,
It cools down after reaction, adjusts pH to get maleic anhydride analog high efficiency water reducing agent.Specifically includes the following steps:
1, the preparation of sample
A certain amount of allyl polyethenoxy ether and methylpropene sodium sulfonate are accurately weighed, tetra- mouthfuls of clean 500mL is put into
In reaction flask, it is put into microwave reactor, and installs reflux condensing tube, thermometer, blender, water 50mL is added after sealing, and
Mixture solution is stirred evenly.Start microwave reactor, solution is heated using microwave power 300W, to temperature up to instead
After answering temperature, maleic anhydride and initiator ammonium persulfate solution are added dropwise simultaneously respectively under constant temperature, and drop finishes, and isothermal reaction is to required
Time.Microwave emitter is closed, after reaction solution is cooled to room temperature, the sodium hydroxide solution of mass fraction 30% is added dropwise, adjusts
Saving mixed solution pH value is 7~8, obtains the transparent maleic anhydride analog high efficiency water reducing agent of glassy yellow.
2, performance test and characterization
(1) it the measurement of solid content: is tested by GB/T 8077-2012 " Methods for testing uniformity of concrete admixture ".
(2) it the measurement of flowing degree of net paste of cement: presses GB/T 8077-2012 " Methods for testing uniformity of concrete admixture "
It is tested, wherein the ratio of mud uses 0.29, and water-reducing agent solid volume is the 0.5% of cement weight in process optimization.
(3) it the measurement of water reducing ratio of cement mortar: is carried out by GB/T 8077-2012 " Methods for testing uniformity of concrete admixture "
Test.
(4) flowing degree of net paste of cement gradual loss: the ratio of mud 0.29 rapidly will be net after testing initial paste flowing degree
In the curing box that slurry is stored in (20 ± 2) DEG C, relative humidity is 60%~80%, a cement paste stream is measured every 30min
Dynamic degree.
3, experiment of single factor
(1) SMAS (i.e. methylpropene sodium sulfonate) and APEG (i.e. allyl polyethenoxy ether) molar ratio disperse water-reducing agent
The influence of performance
In high efficiency water reducing agent molecular structure, methylpropene sodium sulfonate and allyl polyethenoxy ether are respectively configured to provide yin
Ionic group-SO3 -And long side group-(CH2CH2O)-, wherein-SO3 -It can be effectively adsorbed on cement particle surface, be conducive in cement
Particle surface forms electric double layer；And polyethoxy-(CH2CH2O)-can provide useful space steric effect, so electrostatic repulsion and
Synergistic effect between steric hindrance, directly affects Cement Hydration Process.In nMAH:nAPEG=3, initiator ammonium persulfate dosage
For total addition level 2%, microwave power 300W, reaction time 30min, under the conditions of 85 DEG C of reaction temperature, methylpropene sodium sulfonate
Influence with allyl polyethenoxy ether molar ratio to water-reducing agent dispersion performance is as shown in Figure 1.
Fig. 1 shows flowing degree of net paste of cement with the increase of methylpropene sodium sulfonate and allyl polyethenoxy ether molar ratio
First increases and then decreases works as nSMAS:nAPEGWhen=0.5, paste flowing degree reaches maximum value 328mm.This is because with SMAS volume
Increase ,-SO in polymer molecule3 -Increase, anionic charge density increase is conducive to water-reducing agent in the absorption of cement particle surface；
But when SMAS additive amount is excessive, since SMAS has chain-transferring agent effect, reduce polymer molecular weight, product dispersion performance
Decline.
(2) MAH (i.e. maleic anhydride) and APEG (i.e. allyl polyethenoxy ether) molar ratio are to water-reducing agent dispersion performance
It influences
According to maleic anhydride molecule configuration, two-COO will be generated by hydrolyzing latter molecule maleic anhydride-Functional group, with-
SO3 -Efficiency is the same, the Ca of the group and cement particle surface2+And the Ca in solution2+Complex reaction occurs, inhibits hydrated cementitious,
Improve water-reducing agent dispersion performance.In nSMAS:nAPEG=0.5, initiator ammonium persulfate dosage is the 2% of total addition level, microwave power
300W, reaction time 30min, under the conditions of 85 DEG C of reaction temperature, maleic anhydride and allyl polyethenoxy ether molar ratio are to diminishing
The influence of agent dispersion performance is as shown in Figure 2.
As shown in Figure 2, work as nMAH:nAPEGAt 2~3, flowing degree of net paste of cement gradually increases with the increase of maleic anhydride volume
Greatly, show-COO-The increase of group is conducive to enhance product performance；And work as nMAH:nAPEGWhen greater than 3, due to maleic anhydride volume
Excessive, long side chain density is reduced on main chain, and space steric effect reduces, and the synergistic effect of electrostatic repulsion and steric hindrance declines,
Properties of product weaken.
(3) influence of APS (i.e. ammonium persulfate) dosage to water-reducing agent dispersion performance
In nSMAS:nMAH:nAPEG85 DEG C of=0.5:3:1, microwave power 300W, reaction time 30min, reaction temperature conditions
Under, influence of the initiator ammonium persulfate dosage to water-reducing agent dispersion performance is investigated, as shown in Figure 3.Fig. 3 shows to work as persulfuric acid
When ammonium volume is the 2% of total addition quality, water-reducing agent dispersion performance is best.This is because when initiator amount is smaller, freely
Base polymerization activity center is less, and reaction rate is slower, and polymerization reaction is insufficient within the short time in reaction time 30min, water
Cement paste fluidity is lower；When ammonium persulfate volume is larger, the degree of polymerization is not high, and polymer molecular weight is low, leads to water-reducing agent
It can reduce.
(4) influence of the reaction temperature to water-reducing agent dispersion performance
In nSMAS:nMAH:nAPEG=0.5:3:1,2% that ammonium persulfate dosage is total addition level, microwave power 300W, reaction
Under the conditions of time 30min, reaction temperature influences obviously, as shown in Figure 4 pulp flowage.Fig. 4 shows when temperature is by 65 DEG C
When increasing to 85 DEG C, flowing degree of net paste of cement increases to 328mm from 183mm, and water-reducing agent performance is affected by temperature larger；Followed by of continuing rising
When high polymerization temperature is to 90 DEG C, flowing degree of net paste of cement is declined slightly, therefore optimal reaction temperature is 85 DEG C.
(5) influence of the reaction time to water-reducing agent dispersion performance
In nSMAS:nMAH:nAPEG=0.5:3:1,2% that ammonium persulfate dosage is total addition level, microwave power 300W, reaction
Under the conditions of 85 DEG C of temperature, as shown in Figure 5, within the scope of polymerization time 20min~50min, when flowing degree of net paste of cement is with reaction
Between change less, so under the premise of ensuring that starting monomer sufficiently reacts and avoids gelatin phenomenon, using 30min is most preferably to polymerize
Reaction time.
4, maleic anhydride analog high efficiency water reducing agent prepares response surface optimization analysis
(1) model foundation and significance test
Each factor due to influencing water-reducing agent dispersion performance does not isolate, and test utilizes sound on the basis of single factor test optimization
Reciprocation between answering surface analysis technology to determine each factor to water-reducing agent performance affecting laws, according to test data analyzer as a result,
Multiple regression fitting is carried out, quadratic regression equation model is obtained, determines optimum process condition.Research and utilization Design-Expert
8.0.6 software, with nSMAS:nAPEG(A)、nMAH:nAPEG(B), reaction time (C), reaction temperature (D) are independent variable, take cement net
Slurry fluidity is response, and each factor level and test result are shown in Table 1, table 2 respectively.
1 factor level table of table
2 response surface experiments result of table
It is repeatedly fitted using 8.0 software of Design-Expert, obtains response flowing degree of net paste of cement
Encoding equtions is as follows: flowing degree of net paste of cement (mm)=320.00+0.83A+2.33B+4.92C-0.42D-1.50AB-
3.25AC-4.75AD-4.50CD–10.93A2–5.93B2-8.31C2+1.44D2, in formula: A-nSMAS:nAPEG；B—nMAH:
nAPEG；C-reaction time；D-reaction temperature, variance analysis are shown in Table 3.
3 analysis of variance table of table
Note: Prob < 0.001 is that difference is extremely significant；Prob < 0.01 is difference highly significant；Prob < 0.05 is aobvious for difference
It writes.
From table 3 it can be seen that C (reaction time), AD (nMAH:nAPEGWith the reciprocation of reaction temperature), A2、B2、C2It is right
The influence of flowing degree of net paste of cement is significant.Meanwhile model P=0.0005 (significant), show that quadratic equation model is significant
's；Quasi- item P=0.9538 (not significant) is lost, illustrates that the regression equation is significant, can be used for speculating test result.
(2) response surface interactive analysis and optimization
Response phase method analysis is carried out between the reciprocation each factor using Design-Expert 8.0, is drawn out with water
Cement paste fluidity is the response surface 3D curve graph of response, such as Fig. 6-11.Each factor interaction can intuitively be reflected by Fig. 6-11
The influence to flowing degree of net paste of cement is acted on, wherein curve is more precipitous, and it is bigger to illustrate that the factor influences flowing degree of net paste of cement.
From Fig. 6-11 it can be seen that the reaction time water-reducing agent dispersion performance is influenced it is maximum, according to its corresponding P=0.0017 < 0.05,
Influence of the reaction time to flowing degree of net paste of cement reaches the level of signifiance；Meanwhile in a certain range flowing degree of net paste of cement with
Reaction temperature and nSMAS:nAPEGIncrease it is in rising trend, two factor significant interactions.
By Fig. 6-11 it is found that response there are maximum values.Microwave is obtained by 8.0 software optimization of Design-Expert to make
With the lower best theoretical technique for preparing high efficiency water reducing agent are as follows: nSMAS:nAPEG=0.52；nMAH:nAPEG=3.09；Reaction time is
32.67min；Reaction temperature is 80.00 DEG C, and flowing degree of net paste of cement is 325.24mm under this condition.
(3) reliability of response phase method
For the validity for verifying model, high efficiency water reducing agent is prepared using above-mentioned optimization technique, and carry out properties of product test.
In view of the operability of technological parameter, each technological parameter is modified to n respectivelySMAS:nAPEG=0.52, nMAH:nAPEG=3.10, it reacts
Time is 33min, reaction temperature is 80 DEG C.It is mixed with the ratio of mud for 0.29 in water-reducing agent solid by practical 3 parallel testings
Under the conditions of amount is the 0.5% of cement quality, flowing degree of net paste of cement average value is 326mm, is coincide substantially with theoretical expectation values, table
It is bright accurate and reliable based on response phase method optimum synthesis technique.
5, maleic anhydride analog high efficiency water reducing agent performance test
To probe into the maleic anhydride analog high efficiency water reducing agent application performance prepared under the process conditions, molecular structure function is examined
Change design rationality, test further studies influence (Figure 12) and diminishing effect of the high efficiency water reducing agent to cement dispersion performance
Fruit.
Figure 12 shows that initial flowing degree of net paste of cement is 287mm, and with volume when water-reducing agent volume is 0.15%
Increase initial flowing degree of net paste of cement to be gradually increased and tend towards stability, wherein the corresponding initial pulp flowage of volume 0.5%
Degree reaches 328mm；In addition, the flowing degree of net paste of cement under four kinds of different water-reducing agent volumes is declined slightly as the testing time extends,
Wherein volume is 60min flowing degree of net paste of cement gradual loss rate corresponding to 0.15%, 0.30%, 0.50%, 0.70% point
Not Wei 5.9%, 4.5%, 5.2% and 4.9%, illustrate the high efficiency water reducing agent have good dispersion retentivity, be suitable for coagulation
Native long-distance transportation, construction.
Probe into maleic anhydride analog high efficiency water reducing agent dispersion performance on the basis of, experiment investigation water-reducing agent application performance.When
When water-reducing agent solid volume is the 0.3% of cement quality, corresponding water reducing ratio of cement mortar shows under the process conditions up to 35.4%
The high efficiency water reducing agent of preparation can meet high performance concrete application requirement well, have preferable practical application value.
After obtaining optimum process condition, in the present embodiment, the volume of ammonium persulfate can be replaced allyl polyethenoxy
The 1.8% or 3.0% of ether and methylpropene sodium sulfonate gross mass, the power of microwave radiation can be replaced 250W or 350W, alkali soluble
Liquid can be replaced potassium hydroxide, sodium carbonate or potassium carbonate, and the mass fraction of aqueous slkali can be replaced 20% or 40%.
Above-described embodiment is only further described the purpose of the present invention, technical scheme and beneficial effects specific
A example, present invention is not limited to this.All any modification, equivalent substitution and improvement done within the scope of disclosed by the invention
Deng being all included in the scope of protection of the present invention.
Claims (6)
1. a kind of method that response phase method optimization microwave radiation prepares maleic anhydride analog high efficiency water reducing agent, it is characterised in that: it is
It adds water and stirs using allyl polyethenoxy ether and methylpropene sodium sulfonate as raw material uniformly mixed, is heated under the conditions of microwave radiation
To reaction temperature, then maleic anhydride and ammonium persulfate reaction a period of time is added in constant temperature, utilizes response phase method setting reaction
Variable parameter cools down after reaction, adjusts pH to get maleic anhydride analog high efficiency water reducing agent；
The variable parameter of the response phase method setting reaction, passes through following secondary multinomial regression equation:
Y=320.00 + 0.83A + 2.33B + 4.92C - 0.42D - 1.50AB - 3.25AC - 4.75AD -
4.50CD – 10.93A 2 – 5.93B 2 - 8.31C 2 + 1.44D 2；
In formula: responseYFor flowing degree of net paste of cement, unit mm；AFor methylpropene sodium sulfonate and allyl polyethenoxy ether
Molar ratio；BFor the molar ratio of maleic anhydride and allyl polyethenoxy ether；CFor reaction time, unit min；DFor reaction temperature,
Unit DEG C；
The molar ratio of the methylpropene sodium sulfonate and allyl polyethenoxy ether is 0.4-0.6, the maleic anhydride and allyl
The molar ratio of base polyoxyethylene ether is 2.5-3.5, and the reaction time is 25-35 min, and the reaction temperature is 80-90 DEG C；
The power of the microwave radiation is 250 W-350 W.
2. the method that response phase method optimization microwave radiation according to claim 1 prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized by: the molar ratio of the methylpropene sodium sulfonate and allyl polyethenoxy ether be 0.52, the maleic anhydride with
The molar ratio of allyl polyethenoxy ether is 3.10, and the reaction time is 33 min, and the reaction temperature is 80 DEG C.
3. the method that response phase method optimization microwave radiation according to claim 1 prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized by: the volume of the ammonium persulfate is the 1.5%- of allyl polyethenoxy ether and methylpropene sodium sulfonate gross mass
2.5%。
4. the method that response phase method optimization microwave radiation according to claim 1 prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized by: the tune pH, is that reaction solution pH after cooling is adjusted to 7-8 with aqueous slkali.
5. the method that response phase method optimization microwave radiation according to claim 4 prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized by: the aqueous slkali is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
6. the method that response phase method optimization microwave radiation according to claim 5 prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized by: the mass fraction of the sodium hydroxide is 20%-40%.
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