CN106380553A - Method for preparing maleic anhydride type superplasticizer by utilizing response surface method to optimize microwave radiation - Google Patents
Method for preparing maleic anhydride type superplasticizer by utilizing response surface method to optimize microwave radiation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- 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
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Abstract
The invention discloses a method for preparing a maleic anhydride type superplasticizer by utilizing a response surface method to optimize microwave radiation. According to the method, allyl polyoxyethylene ether and sodium methallyl sulfonate are used as raw materials and are added with water to be uniformly stirred and mixed; a mixture is heated to a reaction temperature under the microwave radiation condition; then maleic anhydride and ammonium persulfate are added at a constant temperature to perform a reaction for a period of time; variable parameters of the reaction are set by utilizing the response surface method; after the reaction is ended, cooling is carried out; and pH is regulated to obtain the maleic anhydride type superplasticizer. The invention researches a maleic anhydride type superplasticizer synthetic process which is optimized by utilizing the response surface method on the basis of single factor analysis, obtains process conditions relatively suitable for preparing the maleic anhydride type superplasticizer, and aims to provide the scientific test basis for development and popularization of the superplasticizer.
Description
Technical field
The invention belongs to the preparation field of water reducer prepares maleic acid and in particular to a kind of response phase method optimizes microwave
The method of anhydride high efficiency water reducing agent.
Background technology
Maleic anhydride contains anhydride group and carbon-carbon double bond, and this molecular configuration is conducive to producing conjugation, makes double bond (- C
=C-) easily it is copolymerized with olefin monomer, such as methylpropene sodium sulfonate, acrylic acid, allyl polyethenoxy ether, styrene etc.
Monomer, and the maleic anhydride as circulus, because of carbonyl electrophilic inductive effect and disubstituted group in its intramolecule
Space steric effect is so as to be difficult to homopolymerization.So compared with the active olefin being susceptible to homopolymerization, the low work of maleic anhydride
Property can effectively prevent reaction system cruelly poly-, and it is easily controllable to realize reaction condition, simple production process；In addition, maleic anhydride price
Cheap, advantageously reduce product cost, be easy to the popularization and application of high efficiency water reducing agent.
Compared with traditional heating, microwave has fuel factor and the non-thermal effect of uniqueness, not only can achieve to reactant
System is quick, uniformly heating, and can be different according to the dielectric constant of reaction system medium, realizes selectively heating, and by pole
Change acts on, priming reaction group, improves 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, the method can solve Multivariable, and draws optimal processing parameter by regression equation analysis.Exist at present
In the exploitation of high efficiency water reducing agent, such as CN201210274917.1, be using orthogonal experiment method filter out influence index notable because
Element simultaneously provides optimal factor level combination, but exists and cannot find out lacking of the best of breed of factor and response in whole region
More, there is deviation with actual conditions in point, and adopt linear model, the problems such as precision is high.
Content of the invention
Present invention aim to address above-mentioned technical problem, provide a kind of response phase method to optimize microwave and prepare maleic acid
The method of anhydride high efficiency water reducing agent, research, on the basis of single factor analysis, optimizes maleic acid anhydride using response phase method and efficiently subtracts
Aqua synthesis technique, draws relatively to be applied to and prepares maleic anhydride analog high efficiency water reducing agent process conditions it is intended to be high efficiency water reducing agent
Exploitation, popularization provide scientific experimentation foundation.
For realizing above-mentioned purpose, the technical scheme is that：
A kind of response phase method optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent, and it is to be gathered with pi-allyl
Oxygen vinethene and methylpropene sodium sulfonate add water for raw material and are uniformly mixed, and are heated to reaction temperature under the conditions of microwave
Degree, then constant temperature addition maleic anhydride and ammonium persulfate reaction a period of time, sets the variable parameter of reaction using response phase method,
Reaction cools down after terminating, and adjusts pH, obtains final product maleic anhydride analog high efficiency water reducing agent.
As further technical scheme, the above response phase method sets the variable parameter of reaction, 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 mol ratio of ether；B is the mol ratio of maleic anhydride and allyl polyethenoxy ether；C is the reaction time, unit min；D is reaction
Temperature, unit DEG C.
As further technical scheme, the mol ratio of the above methylpropene sodium sulfonate and allyl polyethenoxy ether
For 0.4-0.6, described maleic anhydride is 2.5-3.5 with the mol ratio of allyl polyethenoxy ether, and the described reaction time is 25-
35min, described reaction temperature is 80-90 DEG C.
As further technical scheme, the mol ratio of the above methylpropene sodium sulfonate and allyl polyethenoxy ether
For 0.52, described maleic anhydride is 3.10 with the mol ratio of allyl polyethenoxy ether, and the described reaction time is 33min, described
Reaction temperature is 80 DEG C.
As further technical scheme, the volume of the above ammonium persulfate is allyl polyethenoxy ether and methyl-prop
The 1.5%-2.5% of alkene sodium sulfonate gross mass.
As further technical scheme, the power of the above microwave is 250W-350W.
As further technical scheme, the above adjusts pH, is to be adjusted to the reaction solution pH after cooling down with aqueous slkali
7-8.
As further technical scheme, the above aqueous slkali is NaOH, potassium hydroxide, sodium carbonate, potassium carbonate.
As further technical scheme, the mass fraction of the above NaOH is 20%-40%.
Compared with prior art, beneficial effects of the present invention are：
(1) response phase method of the present invention be suitable for solve nonlinear transportation relevant issues, it enumerate experimental design,
Modeling, the well-formedness of testing model, seek optimum combination condition etc.；By to the regression fit of process and response surface, contour
Draw it is convenient to obtain the response corresponding to each factor level；And find out the response optimal value of prediction based on this
And the experiment condition of response.Compared with orthogonal test, its advantage is：In experimental condition searching process, can be continuously right
Each level of test is analyzed, and the forecast model of gained is continuously, and orthogonal test can only be to the examination isolated one by one
Test and be a little analyzed；Response phase method considers test random error, simultaneously response phase method complicated unknown function is closed tie up to little
In region with simple once or quadratic polynomial model is come matching, calculate easier, be effective hand of solving practical problems
Section.
(2) present invention establishes the secondary multinomial regression equation model of flowing degree of net paste of cement and dependent variable, employing
Design-Expert 8.0 software, with five changed factors, only with four levels, compared with Orthogonal Method, with a small amount of test group
Just can obtain a result, and obtained optimum condition is not the value setting but within the scope of imposing a condition.Pass through
Using response phase method to the mol ratio of methylpropene sodium sulfonate and allyl polyethenoxy ether, maleic anhydride and pi-allyl polyoxy second
The mol ratio of alkene ether, reaction time and reaction temperature are optimized, and the condition obtaining optimizing is：Methylpropene sodium sulfonate and allyl
The mol ratio of base APEO is 0.52, and maleic anhydride is 3.10 with the mol ratio of allyl polyethenoxy ether, the reaction time
For 33min, reaction temperature is 80 DEG C, and the product flowing degree of net paste of cement obtaining is 325.24mm, is that maleic acid anhydride efficiently subtracts
Aqua industrialized production provides a scientific basis.
(3) the inventive method is accurately and reliably.For verifying the validity of model, efficient diminishing is prepared using the inventive method
Agent, and carry out properties of product test.By actual 3 parallel testings, with the ratio of mud for 0.29, it is water in water reducer solid volume
Under the conditions of the 0.5% of shale amount, flowing degree of net paste of cement mean value is 326mm, substantially identical with theoretical expectation values, shows to be based on
Response phase method optimum synthesis technique is accurately and reliably.
(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 is gradually increased and tends towards stability with the volume initial flowing degree of net paste of cement of increase, its
The corresponding initial flowing degree of net paste of cement of middle volume 0.5% reaches 328mm；In addition, extending with the testing time, 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%, this efficient diminishing is described
Agent has good dispersion retentivity, is suitable for concrete long-distance transportation, construction.
(5) product of the present invention has preferable actual application value.The present invention is probing into maleic anhydride analog high efficiency water reducing agent
On the basis of dispersive property, experiment investigation water reducer application performance.When water reducer solid volume is for the 0.3% of cement quality,
Its corresponding water reducing ratio of cement mortar reaches 35.4%, shows that the high efficiency water reducing agent of preparation under this process conditions can meet high property well
Energy concrete application requirement, has preferable actual application value.
(6) microwave of the present invention effectively increases process efficiency, and energy-conserving and environment-protective, easy to operate, easy to control.
Brief description
Fig. 1 is methylpropene sodium sulfonate of the present invention and the impact to flowing degree of net paste of cement for the allyl polyethenoxy ether mole
Figure；
Fig. 2 is maleic anhydride of the present invention and the impact figure to flowing degree of net paste of cement for the allyl polyethenoxy ether mol ratio；
Fig. 3 is the impact figure to flowing degree of net paste of cement for the ammonium persulfate consumption of the present invention；
Fig. 4 is the impact figure to flowing degree of net paste of cement for the reaction temperature of the present invention；
Fig. 5 is the impact figure to flowing degree of net paste of cement for the present invention reaction time；
Fig. 6 is mol ratio and maleic anhydride and the pi-allyl of methylpropene sodium sulfonate of the present invention and allyl polyethenoxy ether
The response surface figure to flowing degree of net paste of cement for the reciprocation of the mol ratio of APEO；
Fig. 7 be the mol ratio of methylpropene sodium sulfonate of the present invention and allyl polyethenoxy ether and reaction time interact work
With the response surface figure to flowing degree of net paste of cement；
Fig. 8 be the mol ratio of methylpropene sodium sulfonate of the present invention and allyl polyethenoxy ether and reaction temperature interact work
With the response surface figure to flowing degree of net paste of cement；
Fig. 9 is the mol ratio of maleic anhydride of the present invention and allyl polyethenoxy ether and the reciprocation in reaction time to water
The response surface figure of cement paste fluidity；
Figure 10 is maleic anhydride of the present invention and the mol ratio of 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 reaction temperature of the present invention and the reciprocation in the reaction time response surface figure 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
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to
The scope that embodiment represents.
Embodiment 1：
A kind of response phase method optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent, and it is to be gathered with pi-allyl
Oxygen vinethene and methylpropene sodium sulfonate add water for raw material and are uniformly mixed, and are heated to reaction temperature under the conditions of microwave
Degree, then constant temperature addition maleic anhydride and ammonium persulfate reaction a period of time, sets the variable parameter of reaction using response phase method,
Reaction cools down after terminating, and adjusts pH, obtains final product maleic anhydride analog high efficiency water reducing agent.Specifically include following steps：
1st, the preparation of sample
Accurately weigh a certain amount of allyl polyethenoxy ether and methylpropene sodium sulfonate, put into tetra- mouthfuls of the 500mL of cleaning
In reaction flask, put into microwave reactor, and install reflux condensing tube, thermometer, agitator, add water after sealing 50mL, and
Mixture solution is stirred.Start microwave reactor, using microwave power 300W, solution is heated, treat that temperature reaches instead
After answering temperature, under constant temperature, it is simultaneously added dropwise maleic anhydride and initiator ammonium persulfate solution respectively, drips and finish, isothermal reaction is extremely required
Time.Close microwave emitter, after question response solution is cooled to room temperature, the sodium hydroxide solution of dropping mass fraction 30%, adjust
Section mixed solution pH value is 7～8, obtains glassy yellow transparent maleic anhydride analog high efficiency water reducing agent.
2nd, performance test and sign
(1) mensure of solid content：By GB/T 8077-2012《Methods for testing uniformity of concrete admixture》Tested.
(2) mensure of flowing degree of net paste of cement：By GB/T 8077-2012《Methods for testing uniformity of concrete admixture》
Tested, wherein the ratio of mud adopts 0.29, in process optimization, water reducer solid volume is the 0.5% of cement weight.
(3) mensure of water reducing ratio of cement mortar：By GB/T 8077-2012《Methods for testing uniformity of concrete admixture》Carry out
Test.
(4) flowing degree of net paste of cement gradual loss：The ratio of mud is 0.29, after testing initial paste flowing degree, rapidly will be net
Slurry leaves (20 ± 2) DEG C in, relative humidity is in 60%～80% curing box, measures a cement paste stream every 30min
Dynamic degree.
3rd, experiment of single factor
(1) SMAS (i.e. methylpropene sodium sulfonate) and APEG (i.e. allyl polyethenoxy ether) mol ratio are disperseed to water reducer
The impact of performance
In high efficiency water reducing agent molecular structure, methylpropene sodium sulfonate and allyl polyethenoxy ether are respectively configured to provide the moon
Ionic group-SO3 -And long side base-(CH2CH2O)-, wherein-SO3 -Can effectively adsorb in cement particle surface, be conducive in cement
Particle surface forms electric double layer；And polyethoxy-(CH2CH2O)-effective space steric effect can be provided, so electrostatic repulsion and
The cooperative effect of sterically hindered, directly affects Cement Hydration Process.In nMAH:nAPEG=3, initiator ammonium persulfate consumption
Under the conditions of the 2% of total addition level, microwave power 300W, reaction time 30min, 85 DEG C of reaction temperature, methylpropene sodium sulfonate
As shown in Figure 1 with the impact to water reducer dispersive property for the allyl polyethenoxy ether mol ratio.
Fig. 1 shows, flowing degree of net paste of cement is with the increase of methylpropene sodium sulfonate and allyl polyethenoxy ether mol ratio
First increases and then decreases, works as nSMAS:nAPEGWhen=0.5, paste flowing degree reaches maximum 328mm.This is because with SMAS volume
Increase ,-SO in polymer molecule3 -Increase, anionic charge density increases and is conducive to water reducer in the absorption of cement particle surface；
But when SMAS addition is excessive, because SMAS has chain-transferring agent effect, so that polymer molecular weight is reduced, product dispersive property
Decline.
(2) MAH (i.e. maleic anhydride) and APEG (i.e. allyl polyethenoxy ether) mol ratio are to water reducer dispersive property
Impact
According to maleic anhydride molecule configuration, after its hydrolysis, a molecule maleic anhydride will produce two-COO-Functional group, with-
SO3 -Efficiency is the same, the Ca of this group and cement particle surface2+And the Ca in solution2+There is complex reaction, suppress hydrated cementitious,
Improve water reducer dispersive property.In nSMAS:nAPEG=0.5, initiator ammonium persulfate consumption be total addition level 2%, microwave power
Under the conditions of 300W, reaction time 30min, 85 DEG C of reaction temperature, maleic anhydride and allyl polyethenoxy ether mol ratio are to diminishing
The impact of agent dispersive property is as shown in Figure 2.
As shown in Figure 2, work as nMAH:nAPEGWhen 2～3, flowing degree of net paste of cement gradually increases with maleic anhydride volume increase
Greatly, show-COO-The increase of group is conducive to enhancing product performance；And work as nMAH:nAPEGDuring more than 3, due to maleic anhydride volume
Excessive, on main chain, long side chain density reduces, and space steric effect reduces, and electrostatic repulsion is declined with sterically hindered synergy,
Properties of product weaken.
(3) APS (i.e. ammonium persulfate) impact to water reducer dispersive property for the consumption
In nSMAS:nMAH:nAPEG=0.5:3:1st, microwave power 300W, reaction time 30min, 85 DEG C of conditions of reaction temperature
Under, investigate the impact to water reducer dispersive property for the initiator ammonium persulfate consumption, as shown in Figure 3.Fig. 3 shows, works as persulfuric acid
When ammonium volume is always add quality 2%, water reducer dispersive property is optimal.This is because when initiator amount is less, freely
Base polymerization activity center is less, and reaction rate is slower, and within the short time in reaction time 30min, polymerisation is insufficient, water
Cement paste fluidity is relatively low；When ammonium persulfate volume is larger, the degree of polymerization is not high, and polymer molecular weight is low, leads to water reducer
Can reduce.
(4) impact to water reducer dispersive property for the reaction temperature
In nSMAS:nMAH:nAPEG=0.5:3:1st, ammonium persulfate consumption be total addition level 2%, microwave power 300W, reaction
Under the conditions of time 30min, reaction temperature is obvious on pulp flowage impact, as shown in Figure 4.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 reducer performance temperature influence is 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) impact to water reducer dispersive property for the reaction time
In nSMAS:nMAH:nAPEG=0.5:3:1st, ammonium persulfate consumption be total addition level 2%, microwave power 300W, reaction
Under the conditions of 85 DEG C of temperature, as shown in Figure 5, in the range of polymerization time 20min～50min, flowing degree of net paste of cement is with during reaction
Between change less, so under the premise of guaranteeing that starting monomer fully reacts and avoids gelatin phenomenon, being optimal polymerization using 30min
Reaction time.
4th, maleic anhydride analog high efficiency water reducing agent prepares response surface optimization analysis
(1) model is set up and significance test
Each factor due to affecting water reducer dispersive property does not isolate, and tests on the basis of single factor test optimizes, using sound
Surface analysis technology is answered to determine the reciprocation between each factor to water reducer performance impact rule, according to test data analyzer result,
Carry out multiple regression matching, draw quadratic regression equation model, determine 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 result of the test are shown in Table 1, table 2 respectively.
Table 1 factor level table
Table 2 response surface experiments result
Using Design-Expert 8.0 software, it is carried out with multiple matching, obtain 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；The C reaction time；D reaction temperature, variance analysis is shown in Table 3.
Table 3 analysis of variance table
Note：Prob<0.001 is that difference is extremely notable；Prob<0.01 is difference highly significant；Prob<0.05 shows for difference
Write.
From table 3 it can be seen that C (reaction time), AD (nMAH:nAPEGReciprocation with reaction temperature), A2、B2、C2Right
The impact of flowing degree of net paste of cement is significant.Meanwhile, model P=0.0005 (notable), shows that quadratic equation model is notable
's；Lose and intend item P=0.9538 (not notable), illustrate that this regression equation is meaningful, can be used for speculating result of the test.
(2) response surface interactive analysis and optimization
Carry out response phase method analysis using reciprocation between each factor for the Design-Expert 8.0, draw out with water
Cement paste fluidity is the response surface 3D curve map of response, such as Fig. 6-11.Each factor interaction can intuitively be reflected by Fig. 6-11
The impact to flowing degree of net paste of cement for the effect, wherein curve is more precipitous, illustrates that this factor affects on flowing degree of net paste of cement bigger.
From Fig. 6-11 it can be seen that the reaction time affects maximum to water reducer dispersive property, according to its corresponding P=0.0017<0.05,
The impact to flowing degree of net paste of cement for the reaction time reaches the level of signifiance；Meanwhile, within the specific limits flowing degree of net paste of cement with
Reaction temperature and nSMAS:nAPEGIncrease in rising trend, two factor significant interaction.
From Fig. 6-11, there is maximum in response.Obtain microwave by Design-Expert 8.0 software optimization to make
With the lower most preferably theoretical technique preparing high efficiency water reducing agent it is：nSMAS:nAPEG=0.52；nMAH:nAPEG=3.09；Reaction time is
32.67min；Reaction temperature is 80.00 DEG C, and under the conditions of being somebody's turn to do, flowing degree of net paste of cement is 325.24mm.
(3) reliability of response phase method
For verifying the validity of model, high efficiency water reducing agent is prepared using above-mentioned optimize technique, and carries 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, react
Time be 33min, reaction temperature be 80 DEG C.By actual 3 parallel testings, with the ratio of mud for 0.29, mix in water reducer solid
Measure as under the conditions of the 0.5% of cement quality, flowing degree of net paste of cement mean value is 326mm, table substantially identical with theoretical expectation values
Bright based on response phase method optimum synthesis technique accurately and reliably.
5th, maleic anhydride analog high efficiency water reducing agent performance test
For probing into the maleic anhydride analog high efficiency water reducing agent application performance of preparation under this process conditions, check molecular structure function
Change design rationality, test further study the impact (Figure 12) to cement dispersive property for this high efficiency water reducing agent and diminishing effect
Really.
Figure 12 shows, when water reducer volume is 0.15%, initial flowing degree of net paste of cement is 287mm, and with volume
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, extending with the testing time, the flowing degree of net paste of cement under four kinds of different water reducer volumes is declined slightly,
Wherein volume is 0.15%, the 60min flowing degree of net paste of cement gradual loss rate corresponding to 0.30%, 0.50%, 0.70% divides
Not Wei 5.9%, 4.5%, 5.2% and 4.9%, illustrate that this high efficiency water reducing agent has good dispersion retentivity, be suitable for coagulation
Native long-distance transportation, construction.
On the basis of probe into maleic anhydride analog high efficiency water reducing agent dispersive property, experiment investigation water reducer application performance.When
When water reducer solid volume is the 0.3% of cement quality, its corresponding water reducing ratio of cement mortar reaches 35.4%, shows under this process conditions
The high efficiency water reducing agent of preparation can meet high performance concrete application requirement well, has preferable actual application value.
After obtaining optimum process condition, in the present embodiment, the volume of ammonium persulfate can be replaced allyl polyethenoxy
Ether and the 1.8% or 3.0% of methylpropene sodium sulfonate gross mass, the power of microwave 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, only the purpose of the present invention, technical scheme and beneficial effect are further described is concrete
Individual example, the 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 contained within protection scope of the present invention.
Claims (9)
1. a kind of response phase method optimize microwave prepare maleic anhydride analog high efficiency water reducing agent method it is characterised in that：It is
Added water for raw material with allyl polyethenoxy ether and methylpropene sodium sulfonate and be uniformly mixed, heat under the conditions of microwave
To reaction temperature, then constant temperature addition maleic anhydride and ammonium persulfate reaction a period of time, set reaction using response phase method
Variable parameter, reaction cools down after terminating, and adjusts pH, obtains final product maleic anhydride analog high efficiency water reducing agent.
2. response phase method according to claim 1 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：Described response phase method sets the variable parameter of reaction, 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– 10.93A 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
Mol ratio；BMol ratio for maleic anhydride and allyl polyethenoxy ether；CFor reaction time, unit min；DFor reaction
Temperature, unit DEG C.
3. response phase method according to claim 2 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：Described methylpropene sodium sulfonate is 0.4-0.6 with the mol ratio of allyl polyethenoxy ether, described maleic anhydride
Mol ratio with allyl polyethenoxy ether is 2.5-3.5, and the described reaction time is 25-35 min, and described reaction temperature is 80-
90 ℃.
4. response phase method according to claim 3 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：The mol ratio of described methylpropene sodium sulfonate and allyl polyethenoxy ether is 0.52, described maleic anhydride with
The mol ratio of allyl polyethenoxy ether is 3.10, and the described reaction time is 33 min, and described reaction temperature is 80 DEG C.
5. response phase method according to claim 1 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：The volume of described ammonium persulfate is the 1.5%- of allyl polyethenoxy ether and methylpropene sodium sulfonate gross mass
2.5%.
6. response phase method according to claim 1 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：The power of described microwave is 250 W-350 W.
7. response phase method according to claim 1 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：Described tune pH, is, with aqueous slkali, the reaction solution pH after cooling down is adjusted to 7-8.
8. response phase method according to claim 7 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：Described aqueous slkali is NaOH, potassium hydroxide, sodium carbonate, potassium carbonate.
9. response phase method according to claim 8 optimizes the method that microwave prepares maleic anhydride analog high efficiency water reducing agent,
It is characterized in that：The mass fraction of described NaOH is 20%-40%.
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