CN108383409A - A method of preparing alicyclic water-reducing agent using microwave radiation - Google Patents
A method of preparing alicyclic water-reducing agent using microwave radiation Download PDFInfo
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- CN108383409A CN108383409A CN201810044581.7A CN201810044581A CN108383409A CN 108383409 A CN108383409 A CN 108383409A CN 201810044581 A CN201810044581 A CN 201810044581A CN 108383409 A CN108383409 A CN 108383409A
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- cyclohexanone
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- reducing agent
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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
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G6/00—Condensation polymers of aldehydes or ketones only
- C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones
-
- 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 provides a kind of method preparing alicyclic water-reducing agent using microwave radiation.Using the method for microwave radiation, prepared as raw material using formaldehyde, cyclohexanone and anhydrous sodium sulfite and be condensed alicyclic water-reducing agent --- sulfonation cyclohexanone formaldehyde (CFS) high efficiency water reducing agent, test to obtain optimal synthesis condition by L16 (45) orthogonal experiment, the CFS high efficiency water reducing agents of synthesis in volume 0.5% flowing degree of net paste of cement up to 225mm or more.The microwave radiation condensation time is only 1/6th of heating water bath, it is shown that the features such as it cleans, is efficient, consuming energy low, pollution less.X-ray diffraction (XRD) atlas analysis and scanning electron microscope (SEM) are analyzed in conjunction with FTIR spectrum (FTIR) to further study the essential molecular structure of CFS high efficiency water reducing agents and generate hydrolysis product of cement and the influence of microscopic appearance.Step is simple and convenient to operate, is highly practical.
Description
Technical field
The invention belongs to alicyclic water-reducing agent preparation fields, more particularly to a kind of to prepare alicyclic diminishing using microwave radiation
The method of agent.
Background technology
Aliphatic high-efficiency water reducing agent is to optimize sulfonation, condensation by control using acetone, formaldehyde, sulfonating agent as primary raw material
The parameter of equal synthesis process, anionic polymerisation organic polymer electrolytes surfactant obtained have simple
Production technology, production efficiency is high, production process and concrete are mixed and stirred using process without waste discharge, water-reducing effect is good, concrete
The advantages that gain in strength is good, bleed is few and the no crystalline polamer of use generates in winter.However, in concrete practice of construction mistake
Cheng Zhong, the peony of acetone-formaldehyde sodium sulfite condensation product water-reducing agent itself to the appearance of applied concrete have compared with
Big to influence, it is limited that this apparent defect also results in its application to a certain extent.To change the face of aliphatic water reducing agent
Color, Lei L and Plank J replace the acetone that conventional method uses as raw material, the reactions such as sulfonated, condensation using cyclohexanone
Process obtains the alicyclic water-reducing agent with high molecular weight --- sulfonation cyclohexanone-formaldehyde condensation product high efficiency water reducing agent, experiment
The result shows that sulfonation cyclohexanone-formaldehyde condensation product has very excellent water-reducing effect and peptizaiton.
The frequency of microwave is close between 300MHz and 300GHz with the rotation vibration frequency of numerous chemical groups,
Thus surface layer can be penetrated acted on by the molecular conformation to reactant, activated partial chemically reacts group, instantaneity and
Accurate electronic control can accelerate reaction rate, while reduce side reaction generation, and the spatter property and reaction for improving heating are imitated
Rate.As efficient, the clean heating means distinguished completely with modes such as traditional water bath, electric heating, microwave and substance chemical group
Interaction have unique energy transform mode.
Paper《The synthesis of sulfonation cyclohexanone-formaldehyde aliphatic condensation product and its performance study》Disclose a variety of sulfonation rings
The synthetic method of hexanone-formaldehyde aliphatic condensation product, but due to all using conventional hydrothermal synthesis method, synthesis effect
Rate is relatively low.
Paper《Its performance of the synthesis of high efficiency water reducing agent and research under microwave action》Have studied sulfamic acid under microwave action
The synthesis of series high-efficiency water-reducing agent and aliphatic high-efficiency water reducing agent and its performance study, but it is wider for the application of external wall field
Cyclohexanone-formaldehyde condensation products water-reducing agent do not relate to.
Invention content
In order to overcome above-mentioned deficiency, the present invention to provide a kind of method preparing alicyclic water-reducing agent using microwave radiation.With
For the purpose of improving water-reducing agent performance and improving production efficiency, in the conjunction of existing sulfonation cyclohexanone-formaldehyde condensation product high efficiency water reducing agent
At on Process ba- sis, have in conjunction with microwave synthesis reduce reaction activity, promote reaction forward to carry out, reduce by-product and generate,
The features such as high-efficiency environment friendly, optimizes best synthesis technology, and carried out corresponding performance to products therefrom by single factor experiment
Characterization.The experimental results showed that compared with previous heating water bath method, microwave radiation prepares condensation sulfonation cyclohexanone-formaldehyde
(CFS) high efficiency water reducing agent can greatly shorten the reaction time and building-up process is environment friendly and pollution-free, the water-reducing rate of gained water-reducing agent and
The performance indicators such as dispersibility are excellent.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of preparation method of sulfonation cyclohexanone-formaldehyde condensation product, including：
Using cyclohexanone, formaldehyde as raw material, sodium sulfite is sulfonating agent synthesizing cyclohexanone-formaldehyde condensation under microwave action
Object.
The charging sequence of existing SAF types aliphatic water reducing agent generally takes 3 kinds：1) whole cyclohexanone are added at one time,
Formalin is added dropwise again；2) cyclohexanone is first added dropwise, then formalin is added dropwise；3) part formalin is first added dropwise, then hexamethylene is added dropwise
The mixed liquor of ketone and formaldehyde.And different charging sequence can influence water-reducing agent water-reducing rate.For this purpose, the application has studied microwave condition
Under, SAF type aliphatic water reducing agent water-reducing rate of the different charging sequences to cyclohexanone, formaldehyde synthesis.The result shows that：With regard to sulfonation ring
For hexanone-formaldehyde condensation products, the optimal charging sequence under microwave condition is cyclohexanone to be first added dropwise, then formalin is added dropwise.
Preferably, the microwave action condition is：20~35min is condensed under 200W~500W.
Preferably, the sodium sulfite, cyclohexanone, formaldehyde molar ratio be 0.5~0.8：1：1.6~2.2.
Present invention also provides sulfonation cyclohexanone-formaldehyde condensation products prepared by any above-mentioned method.
Preferably, the infrared spectrogram of the sulfonation cyclohexanone-formaldehyde condensation product is as shown in Figure 2.
The application research is found：Different from water-bath, the sulfonation cyclohexanone-formaldehyde condensation product synthesized under microwave condition is still
Some different characteristics are shown, such as：The infrared light of the sulfonation cyclohexanone-formaldehyde condensation product synthesized under microwave condition is set a song to music
Line is in 2931.8cm-1And 2858.5cm-1Locate the methylene peak generated with the increase of sulfonating agent sodium sulfite volume to reduce,
1186.2 cm-1With 1049.3cm-1The increase for locating the sulfonic acid base peak generated also with sulfonating agent sodium sulfite volume reduces.
Present invention also provides a kind of cement water reducing agents, including：Any above-mentioned sulfonation cyclohexanone-formaldehyde condensation product.
It is existing research shows that：After cyclohexanone-formaldehyde condensation products and polycarboxylic acids water reducing agent compositional, cyclohexanone-formaldehyde condensation products
Content in the water-reducing agent of compounding is advisable with being no more than 10wt%, but the application is the study found that the sulphur prepared using microwave method
After content of the change cyclohexanone-formaldehyde condensation product in such compounding water-reducing agent reaches 12wt%, sulfonation cyclohexanone-first is continued growing
The content of aldehyde condensate can just lead to water-reducing rate rapid decrease, this may be the sulfonation cyclohexanone-formaldehyde due to after microwave treatment
The water-reducing rate and dispersibility of condensation product are promoted.Therefore, the content of the preferred sulfonation cyclohexanone-formaldehyde condensation product of the application
For 0~12wt%.
Present invention also provides a kind of compounding cement water reducing agent, by any above-mentioned sulfonation cyclohexanone-formaldehyde condensation product and
Polycarboxylate water-reducer forms, wherein the content of sulfonation cyclohexanone-formaldehyde condensation product is 0~12wt%.
Show in existing research：Influence of the microwave treatment to SAF type aliphatic water reducing agents mainly improve its dispersibility and
Water-reducing rate, but chanced in the application research：For sulfonation cyclohexanone-formaldehyde condensation product, microwave treatment can also be certain
Slump retaining, the frost resistance of concrete are improved in degree.Therefore, present invention also provides microwave treatments to improve sulfonation cyclohexanone-
Application of the formaldehyde condensation products in concrete slump retaining, frost resistance.
Beneficial effects of the present invention
(1) the CFS high efficiency water reducing agents of microwave irradiation synthesis have preferable dispersibility and water-reducing effect, and can be one
Determine the slump retaining of raising concrete, frost resistance in degree.The optimum process condition of microwave irradiation synthesis CFS high efficiency water reducing agents is：
Reactant concentration 42%, sodium sulfite dosage (with cyclohexanone ratio) 0.8, aldehyde ketone is than 2.0, microwave power 400W, is condensed the time
25min。
(2) it compared with traditional water bath heating synthesis, under conditions of same materials match, is synthesized under microwave action
CFS high efficiency water reducing agents have preferably dispersibility and water-reducing effect.Microwave radiation condensation reaction time only needs 25min, and normal
The reaction time of rule heating water bath usually requires 3~4h, and the microwave irradiation synthesis reaction time is about original 1/6th.It fills
Bright microwave radiation defend oneself as a kind of inventive process, because of the particularity of its mechanism of action, can greatly speed up that prepare water-reducing agent anti-
Answer rate, shorten the reaction time, at the same have the characteristics that cleaning, efficiently, energy consumption is low, pollution is few, have be typically prepared technique without
Analogous advantage.
(3) FTIR the results of FT-IR shows the cyclohexanone formaldehyde condensation products synthesized by microwave radiation and conventional water-bath side
The stretching vibration Absorption Characteristics peak of method synthetic product is essentially identical, there is the main base such as hydroxyl, carbonyl, carboxylic salts and sulfonic group
Structured product functional group of group, experiment obtain the CFS high efficiency water reducing agents of anticipation.
(4) XRD test maps show the admixture of CFS high efficiency water reducing agents only to the initial stage aquation to Portland clinker
Produce inhibiting effect so that hydrated cementitious is more abundant, is more advantageous to the plasticizing of concrete mix and the hair of later strength
Exhibition.Also further verification illustrates this point to the SEM image of different larval instar hardened cement.
(5) preparation method of the present invention is simple, combined coefficient is high, highly practical, easy to spread.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is the synthetic route and molecular structure of CFS high efficiency water reducing agents；
Fig. 2 is the FTIR spectrograms of sulfonation cyclohexanone-formaldehyde aliphatic water reducing agent；
Fig. 3 is the XRD spectrum of different larval instar cement-hydrate；
Fig. 4 is the SEM image of different larval instar hardened cement.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has logical with the application person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular shape
Formula is also intended to include plural form, additionally, it should be understood that, when in the present specification use term "comprising" and/or
When " comprising ", existing characteristics, step, operation, device, component and/or combination thereof are indicated.
With reference to specific embodiment, the present invention is described further.
Embodiment 1
1. raw material and test method
1.1 experiment raw material
Cyclohexanone (being abbreviated as C), 37% formalin (being abbreviated as F), 30% sodium hydroxide solution, anhydrous sodium sulfite
(being abbreviated as S) is that analysis is pure；42.5 ordinary portland cement of conch board；Iso standard sand；Make distilled water by oneself.
1.2 key instrument equipment
XH-100 types microwave chemical reactor (Beijing XiangHu Science and Technology Development Co., Ltd.)；NJ-160A type cement pastes stir
Mix machine；JJ-5 type cement mortar mixers；NLD-3 type jumping tables；NDJ-7 type Rotary Viscosimeters；DZF-6020 is dried in vacuo
Case, IRTracer-100 types infrared spectrometer (Japanese Shimadzu Corporation), Hitachi S-4800 type scanning electron microscope (Hitachi, Japan
Company), Bruker 500M types nuclear magnetic resonance chemical analyser (German Brooker company), Bruker D8Advance X-ray diffractions
Instrument (German Brooker company).
The synthesis of 1.3CFS high efficiency water reducing agents
CFS high efficiency water reducing agent microwave irradiation synthesis methods：A certain amount of anhydrous sodium sulfite is weighed, is matched in three-necked flask
The anhydrous sodium sulfite solution of various concentration is made, configured with magnetic stirring apparatus, thermometer, charge pipe and condenser pipe
In microwave chemical reactor, the hydrolysis of anhydrous sodium sulfite is carried out at 45 DEG C, after hydrolysis, at such a temperature
A certain amount of cyclohexanone, sulfonation 40min is added.Then be slowly added dropwise a certain amount of formalin, controlling reaction temperature 50~
Between 65 DEG C, and wait reacting the when of mitigating accelerate that formaldehyde is added dropwise.After formaldehyde all drips off, control microwave chemical reactor is warming up to
90 DEG C, corresponding synthesising reacting time is set, is cooled to 45~50 DEG C after reaction.Synthetic route and molecular structure are as follows
See Fig. 1
CFS high efficiency water reducing agent water-bath synthetic methods:It is added in four-hole boiling flask after anhydrous sodium sulfite and distilled water are weighed,
After heating water bath to reaction 30min at 35 DEG C, cyclohexanone is all added in four-hole boiling flask, after sulfonating reaction 40min, slowly
Formaldehyde is added dropwise, 90 DEG C are warming up to after dripping off, reacts 3 hours.
1.4 performance tests characterize
(1) viscosity is tested
Using NDJ-7 type Rotary Viscosimeters, the viscosity of diminishing agent solution is tested at 25 DEG C.
(2) water-reducing agent solid content, the test of glue sand water-reducing rate
By GB/T8077-2012《Methods for testing uniformity of concrete admixture》It is tested, mortar fluidity is set as
180mm, the volume of water-reducing agent are the 0.5% of cement quality.
(3) flowing degree of net paste of cement is tested
By GB/T8077-2012《Methods for testing uniformity of concrete admixture》Complete flowing degree of net paste of cement test, water
Gray scale is set as 0.29, and the volume of water-reducing agent is the 0.5% of cement quality.
(4) FTIR spectrum (FTIR) is analyzed
Cyclohexanone --- formaldehyde condensation products are after ethyl alcohol repeated precipitation, dissolving, washing, filtering, 40 DEG C of vacuum drying chambers
It is ground after drying, FTIR analyses is carried out with Fourier Transform Infrared Spectrometer after KBr dry powder sheeting method mixed pressuring plates, scan model
Enclose 400 cm-1~4000cm-1。
(5) X-ray diffraction (XRD) is tested
By the cement paste sample (ratio of mud 0.35) through standard curing to age, surface layer is removed, is crushed, takes its kernel,
It is set to terminate aquation for 24 hours with absolute ethyl alcohol, acetone mixed solution immersion under vacuum.After sampling, the vacuum for being put into temperature 60 C is dry
Dry 12h in dry case, the sample after drying is fully ground to powdered samples, the square hole screen of 0.16mm is crossed, takes a small amount of sample
Product are added on glass slide and are tested, using Cu K α as radiation source, nickel filter plate, and accelerating potential 40kV, electric current 200mA,
Sweep speed 4.00 (°/mm), 0.02 ° of step-length carries out continuous scanning in 2 θ=5 °~65 °.
(6) scanning electron microscope (SEM) is analyzed
It is 1.0% according to water-reducing agent volume, adjusts ratio of mud control blank sample and admixture CFS high efficiency water reducing agent cement is net
It is identical to starch fluidity, carries out the preparation of sample.When sample passes through standard curing to corresponding age, test block is taken out respectively and is broken
5mm particles below are broken into, with core of the sieve interception grain size of aperture 2.36mm and 4.75mm between 2.36~4.75mm
Piecemeal shape relic particle, which is put into ethanol solution, to be impregnated, to be measured to prevent it from continuing aquation.By the hardened paste of each age
It is taken out from alcohol solvent, is put into the drying box of temperature 60 C dry 12h, is handled by metal spraying after drying, observe and analyze
The hardened cement paste microscopic appearance feature of alicyclic high efficiency water reducing agent is mixed and do not mixed to the different larval instar hardened cement paste time.
2 results and discussion
2.1 determine synthetic technological condition
Influence CFS high efficiency water reducing agents has feed way, reactant concentration, Asia to the principal element of cement paste dispersion performance
Sodium sulphate content, aldehyde ketone ratio, microwave power, condensation temp, condensation time etc..Consider these factors, determines charging side
Formula and sodium sulfite hydrolysis temperature and under conditions of the time (45 DEG C, 30min), by reactant concentration, sodium sulfite and cyclohexanone
The ratio between, aldehyde ketone ratio, microwave power, condensation temp, condensation time be set as five factors, chosen in each factor it is four horizontal, into
The horizontal orthogonal experiment of five factor of row four, L16 (45) factor level are shown in Table 1.
1 microwave irradiation synthesis CFS water-reducing agent orthogonal design factors of table and level
Table1.Orthogonal design factors and levels of synthesis of CFS
superplasticizer under
microwave irradiation
Under conditions of the volume that the ratio of mud is 0.29, CFS water-reducing agents is the 0.5% of cement quality, five factors will be changed
The prepared CFS high efficiency water reducing agents obtained of condition are mixed respectively to cement paste, are referred to using the flowing time measured as evaluation
Mark, by investigate five factors to be added to condensation sulfonation cyclohexanone-formaldehyde water-reducing agent cement paste dispersion performance influence,
To determine the optimal processing parameter of microwave irradiation synthesis CFS high efficiency water reducing agents.Specific experiment Orthogonal experiment results are shown in Table with analysis
2。
Table 2L16(45) Orthogonal experiment results with analysis
Table 2Analysis of the results of the orthogonal experiment L16(45)
The result shows that in five factors to be mixed with CFS high efficiency water reducing agents flowing degree of net paste of cement influence from big to small
It is followed successively by:Sodium sulfite dosage ＞ aldehyde ketone ratio ＞ microwave powers ＞ is condensed time ＞ reactant concentration.In conjunction with the experiment number of table 2
According to, use by very poor interpretation of result obtain microwave radiation prepare the best compound experiment optimal conditions of CFS high efficiency water reducing agents for
A2B4C3D3E2, i.e. reactant concentration 42%, n (S):N (C)=0.8, n (F):N (C)=2.0, microwave power 400W, condensation
Time 25min.4 repeated authentication experiments (experimental result is shown in Table 3) have been carried out under optimum experimental condition, and CFS is added and efficiently subtracts
The flowing degree of net paste of cement of aqua illustrates that the reproducibility of optimal conditions experiment is good, CFS in 225mm or more, average out to 228mm
Being influenced on the dispersion performance of cement paste for high efficiency water reducing agent is more notable.
Table 3 optimizes the repetition experimental result of reaction condition
Table3Experimental results of the repeated optimized reaction
conditions
The FTIR test analysis of 2.2CFS high efficiency water reducing agents
By using the CFS high efficiency water reducing agents of conventional heating water bath method synthesis, (A, sulfonating agent volume are respectively 0.8) and micro-
Amplitude shooting method optimum experimental condition synthesis CFS high efficiency water reducing agents B and C (sulfonating agent volume is respectively 0.8,0.9) respectively into
Row FTIR spectrum (FTIR) measures, and the results of FT-IR is as shown in Figure 2.The conventional water it can be seen from Fig. 2 curves A, B
The CFS high efficiency water reducing agents infrared spectrum curve of bath method and microwave irradiation synthesis is all in 3734.5cm-1And 3469.9cm-1Place goes out
The stretching vibration Absorption Characteristics peak of hydroxyl, 2931.8cm are showed-1And 2858.5cm-1Occur being located on linear condensation product long-chain
The stretching vibration absworption peak of methylene, 1705.1cm-1There is the stretching vibration absworption peak of hexamethylene ketone carbonyl, 1606.7cm-1Go out
Existing carboxylic salts absorption peak, 1448.5cm occur with C.H keys asymmetrical deformation vibration absorption peak, 1186.2cm on cyclohexanone carbocyclic ring-1
And 1049.3cm-1There is the stretching vibration absworption peak of sulfonic acid group on cyclohexanone side chain.This illustrates the ring synthesized by microwave radiation
Hexanone formaldehyde condensation products and the product of conventional water bath Method are essentially identical, have hydroxyl, carbonyl, carboxylic salts and sulfonic group etc. main
Unit structure, experiment is wanted to obtain the CFS high efficiency water reducing agents of anticipation.Wherein sulfonic acid group imparts cyclohexanone formaldehyde condensation point
It dissipates performance and water-reducing property, hydroxyl and sulfonic acid group has a significant impact to its water solubility.Sulfonation is synthesized by heat source of microwave radiation
Cyclohexanone-formaldehyde condensation product high efficiency water reducing agent, synthesising reacting time are about original 1/6th, building-up process wiper ring
It protects, embodies the great advantage that microwave irradiation synthesis aliphatic high-efficiency water reducing agent has.
Simultaneously as can be seen that the sulfonating agent volume of microwave radiation means synthesis is respectively 0.8,0.9 from Fig. 2 curves B, C
Cyclohexanone-formaldehyde aliphatic water reducing agent two infrared spectrum curves in 2931.8cm-1And 2858.5cm-1What place generated
Methylene peak reduces with the increase of sulfonating agent sodium sulfite volume, while in 1186.2cm-1With 1049.3cm-1What place generated
Sulfonic acid base peak reduces also with the increase of sulfonating agent sodium sulfite volume.Reason may be that the raising of sodium sulfite dosage is reduced
The opposite degree of functionality of reaction product, so as to cause the reduction of the length of the molecular weight and strand of condensation product, this
Reducing finally and successfully can be grafted to the quantity of the sulfonic acid group on reaction product macromolecular chain, be embodied in sulfonic group
At the decline of peak intensity.
2.3 add the cement-hydrate XRD material phase analysis of CFS high efficiency water reducing agents
Various crystals in hardened cement paste using x-ray diffractometer to that will mix and not mix the high-effect water-reducing agents of CFS
Matter carries out qualitative and quantitative analysis.By the cement paste sample (ratio of mud 0.35) through standard curing to 3d and 7d ages, remove
Surface layer is crushed, and takes its kernel, impregnated with absolute ethyl alcohol, acetone mixed solution under vacuum makes its termination aquation for 24 hours.After sampling,
It is put into the vacuum drying chamber of temperature 60 C dry 12h, the sample after drying is fully ground to powdered samples, mistake
The square hole screen of 0.16mm takes a small amount of sample to be added on glass slide and is tested.The cement paste after CFS high efficiency water reducing agents is added
The results are shown in Figure 3 with the XRD diffraction spectrograms of blank cement paste 3d and 7d age.
When clinker is in contact with water, hydration reaction can occur rapidly.When aquation initial stage, tricalcium silicate, silicic acid two
The ordinary portland cement clinkers ingredient such as calcium, tricalcium aluminate, tetra calcium aluminoferrite and calcium sulfate surface can be contacted with water rapidly concurrently
The hydration of raw process complexity gradually appears several hydrated products and the phenomenon that clinker coexists.In this process,
React generate drated calcium aluminate and cement in mixed with gypsum will continue to reaction be converted to entringite, i.e. acicular crystal aquation
Calcium sulphoaluminate；Over time, hydrated product is continuously increased, and hydrated calcium aluminate sulfate can also be reacted with tricalcium silicate, is generated
Aquation list calcium sulphoaluminate.
In figure 3 it can be seen that the diffraction maximum of the objects phase such as calcium hydroxide, entringite, C-S-H gels.With the increase of age,
Calcium hydroxide diffraction peak intensity variation in XRD spectrum is obvious.Therefore calcium hydroxide diffraction peak intensity variation
It can be as the important investigation foundation of hydrated cementitious process size.As can be seen, the primary product at aquation initial stage is hydrogen in Fig. 3
Calcium oxide crystal and entringite, with the growth of age, C-S-H gels gradually increase.Comparing the curve of two 3d ages can see
Go out, slower in the cement initial stage hydration rate that CFS water-reducing agents are added, the diffraction peak intensity of calcium hydroxide is more than blank group.Only
The degree of hydration of the clinker of CFS water-reducing agents is added to the later stage (after 7d) and is not added with the water of the clinker of water-reducing agent
The X ray diffracting spectrum of change is identical, i.e., hydration process reaches identical degree.Illustrate CFS water-reducing agents only to portland cement
The initial stage aquation of clinker produces inhibiting effect, has substantially no effect on the development of the anaphase of hydration process.Reason may be
CFS water-reducing agents are typical aliphatic anionic high molecular surfactants, and it is sulfonic group to dominate group.Due in water
The surface of change initial stage cement particle is conducive to the absorption of anion surfactant with positive charge, and then causes to delay water
The effect of mud hydration reaction so that the dispersibility of cement particle improves.On the other hand, contain in CFS water-reducing agent molecular structures
Hydroxyl and other active groups, the free calcium ion generated with hydrated cementitious in the alkaline medium of cement mortar generates not
Stable complex compound hinders the precipitation of mineral most first phase, reduces the generation of hydrated product CH crystal and inhibits initial stage water
Change.But with the continuous slow development of hydration process, its meeting automatic classifying does not influence continuing for aquation, diminishing agent molecule
It fades away to the inhibiting effect of hydrated cementitious, thus the effect inhibited only is generated to cement initial stage aquation.Thus CFS high
The excellent dispersibility that has of effect water-reducing agent so that hydrated cementitious is more abundant, be more advantageous to concrete mix plasticizing and
The development of later strength.
2.4 add the cement-hydrate sem analysis of CFS high efficiency water reducing agents
The important side that scanning electron microscope (SEM) changes hydrated product microscopic appearance in portland cement hardening process
Method.The hardened paste of each age is taken out from acetone solvent, it is right by green body sample knock sheet fritter sample after drying
Its cross-section morphology carries out SEM observations.Handled by metal spraying after drying, analysis the different larval instar hardened cement paste time mix with not
The hardened cement paste microscopic appearance feature of aliphatic high-efficiency water reducing agent is mixed, Fig. 4 is blank sample and admixture CFS high efficiency water reducing agents
Cement-hydrate microscopic appearance photo.
By the SEM image of different larval instar hardened cement as can be seen, by 3d, two kinds of calcium in sample aluminite are largely given birth to
At (figure a, b), the calcium hydroxide production quantity of blank group higher than adding CFS high efficiency water reducing agents, and the crystal grain of calcium hydroxide compared with
It is coarse, illustrates that CFS high efficiency water reducing agents have the aquation at cement initial stage certain inhibiting effect.The degree of hydration of sample at this time
Also not high, for structure than more loose, entringite has enough spaces for growth, forms typical more coarse needle, rodlike crystalline substance
Body is overlapped to form tridimensional network.As degree of hydration gradually increases, hydrated product is more and more, from the electron microscope of 28d
As can be seen, the Behavior of Hardened Cement Paste consistent internal structure for adding CFS high efficiency water reducing agents is fine and close (figure d), macropore is reduced, while being had a large amount of
C-S-H gels generate, and then interior tissue is loose and has more hole for blank group (figure c).This is also further illustrated
CFS high efficiency water reducing agents only produce inhibiting effect to the initial stage aquation of Portland clinker, and excellent dispersibility makes
It is more abundant to obtain hydrated cementitious, is more advantageous to the development of later strength, this is strong to the plasticizing of fresh concrete mixtures and later stage
The growth of degree is highly beneficial.
The CFS high efficiency water reducing agent performance comparisons of 2.5 microwave radiation means and water bath Method synthesis
Under conditions of same materials match, the efficient diminishings of CFS that will be synthesized under microwave radiation means optimum experimental condition
The CFS high efficiency water reducing agents that agent is synthesized with water bath Method carry out dispersibility and water-reducing effect and slump retaining, frost resistance index pair
Than.As a result the dispersibility to cement paste of the CFS high efficiency water reducing agents (M-CFS) of microwave radiation means synthesis has been fully demonstrated
And the slump retaining of concrete, frost resistance can be influenced more notable.
1) dispersibility and water-reducing effect
4 microwave radiation of table and heating water bath synthesize CFS water-reducing agent performance test Comparative results
Table4Experimental results of the CFSsuperplasticizer under microwave
irradiation and water-heating
2) frost resistance (freezing and thawing test of concrete)
Test water mud is 42.5 grades of Portland cements of P.O, the production of Fusui conch Cement Co., Ltd, water
Mud physical and mechanical property indexs, as shown in table 5.Concrete batching is two area's river sand of grading, fineness modulus 2.6, concrete with sand
Limestone gravel, continuous grading, nominal maximum aggregate size 37.5mm are produced using Guangxi Fangcheng Port with stone.
5 cement physical and mechanical property indexs of table
C-0 groups (not adding normal concrete), C-1 groups (adding heating water bath CFS water-reducing agents 1%), C-2 groups (are added
Microwave heating CFS water-reducing agents 1%) 3 groups of carry out concrete freezing and thawing tests.
6 concrete mix of table
By above-mentioned 3 groups of concrete with identical match ratio mix uniform and with test specimen it is die-filling, standard curing is carried out after demoulding,
Start freezing-thawing test after reaching 28 day age.Experiment test specimen is taken out from standard curing room, and is soaked into the water within 4 days in advance
Bubble is until freezing-thawing test.
7 concrete quality loss late (%) of table
Because C-0 groups are the normal concrete without adding any water-reducing agent, bubble is not carried in concrete,
So A-0 groups concrete has reached 4.97% in 100 mass losses later of Frozen-thawed cycled, and pass through 100 Frozen-thawed cycleds
There is apparent destruction.Therefore, the freezing and thawing performance of concrete can be significantly improved by adding CFS water-reducing agents, be from the perspective of from side
CFS water-reducing agents, which are illustrated, certain air-entraining function, this is also corresponding with SEM picture water-reducing agent effects before.Add with water-bath is added
The concrete of hot CFS water-reducing agents 1% is compared, and the concrete C-2 groups for adding microwave heating CFS water-reducing agents 1% pass through Frozen-thawed cycled
Mass loss becomes smaller, and reason may be that the concrete hole structure of admixture microwave heating CFS water-reducing agents more optimizes, therefore mixes
The compactness for coagulating soil is correspondingly improved, and the freezing tolerance of concrete is further improved.
3) slump retaining (concrete through when degree of collapsing variation experiment)
Table 8 be do not add the concrete of water-reducing agent with add CFS water-reducing agents and M-CFS water-reducing agents through when slump-loss pair
Than testing as a result, concrete match ratio such as table 6.
Table 8 add water-reducing agent to concrete through when collapse the influence of slump-loss
The slump is a main basis for estimation of site operation concrete pumpable performance.As can be seen from Table 8, water-bath
Heating and microwave heating prepare CFS water-reducing agents incorporation after, can to a certain degree improve concrete through when the slump,
Compared with the concrete for adding heating water bath CFS water-reducing agents 1%, the concrete C-2 groups of microwave heating CFS water-reducing agents 1% are added
Through when the slump have higher retention, illustrate that microwave heating CFS water-reducing agents have better function of slump protection to a certain extent,
The pumping of concrete can preferably be improved.
3 conclusions
(1) the CFS high efficiency water reducing agents of microwave irradiation synthesis have preferable dispersibility and water-reducing effect, and can be one
Determine the slump retaining of raising concrete, frost resistance in degree.The optimum process condition of microwave irradiation synthesis CFS high efficiency water reducing agents is：
Reactant concentration 42%, sodium sulfite dosage (with cyclohexanone ratio) 0.8, aldehyde ketone is than 2.0, microwave power 400W, is condensed the time
25min。
(2) it compared with traditional water bath heating synthesis, under conditions of same materials match, is synthesized under microwave action
CFS high efficiency water reducing agents have preferably dispersibility and water-reducing effect.Microwave radiation condensation reaction time only needs 25min, and normal
The reaction time of rule heating water bath usually requires 3~4h, and the microwave irradiation synthesis reaction time is about original 1/6th.It fills
Bright microwave radiation defend oneself as a kind of inventive process, because of the particularity of its mechanism of action, can greatly speed up that prepare water-reducing agent anti-
Answer rate, shorten the reaction time, at the same have the characteristics that cleaning, efficiently, energy consumption is low, pollution is few, have be typically prepared technique without
Analogous advantage.
(3) FTIR the results of FT-IR shows the cyclohexanone formaldehyde condensation products synthesized by microwave radiation and conventional water-bath side
The stretching vibration Absorption Characteristics peak of method synthetic product is essentially identical, there is the main base such as hydroxyl, carbonyl, carboxylic salts and sulfonic group
Structured product functional group of group, experiment obtain the CFS high efficiency water reducing agents of anticipation.
(4) XRD test maps show the admixture of CFS high efficiency water reducing agents only to the initial stage aquation to Portland clinker
Produce inhibiting effect so that hydrated cementitious is more abundant, is more advantageous to the plasticizing of concrete mix and the hair of later strength
Exhibition.Also further verification illustrates this point to the SEM image of different larval instar hardened cement.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, according to
It can so modify to the technical solution recorded in previous embodiment, or equivalent replacement is carried out to which part.It is all this
Within the spirit and principle of invention, any modification, equivalent replacement, improvement and so on should be included in the protection model of the present invention
Within enclosing.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art
The various modifications or changes that can be made need not be made the creative labor still within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfonation cyclohexanone-formaldehyde condensation product, which is characterized in that including：
Using cyclohexanone, formaldehyde as raw material, sodium sulfite is sulfonating agent synthesizing cyclohexanone-formaldehyde condensation products under microwave action.
2. the method as described in claim 1, which is characterized in that the charging sequence is：Cyclohexanone is first added dropwise, then formaldehyde is added dropwise
Solution.
3. the method as described in claim 1, which is characterized in that the microwave action condition is：It is condensed 20 under 200W~500w
~35min.
4. the method as described in claim 1, which is characterized in that the sodium sulfite, cyclohexanone, formaldehyde molar ratio be 0.5
~0.8：1：1.6~2.2.
5. sulfonation cyclohexanone-formaldehyde condensation product prepared by claim 1-4 any one of them methods.
6. sulfonation cyclohexanone-formaldehyde condensation product as claimed in claim 5, which is characterized in that infrared spectrogram is as shown in Figure 2.
7. sulfonation cyclohexanone-formaldehyde condensation product as claimed in claim 5, which is characterized in that infrared spectrum curve exists
2931.8cm-1And 2858.5cm-1Locate the methylene peak generated with the increase of sulfonating agent sodium sulfite volume to reduce,
1186.2cm-1With 1049.3cm-1The increase for locating the sulfonic acid base peak generated also with sulfonating agent sodium sulfite volume reduces.
8. a kind of cement water reducing agent, which is characterized in that including：Claim 5-7 any one of them sulfonation cyclohexanone-formaldehydes contract
Close object.
9. a kind of compounding cement water reducing agent, which is characterized in that by claim 5-7 any one of them sulfonation cyclohexanone-formaldehydes
Condensation product and polycarboxylate water-reducer composition, wherein the content of sulfonation cyclohexanone-formaldehyde condensation product is 0~12wt%.
10. application of the microwave treatment in improving sulfonation cyclohexanone-formaldehyde condensation product slump retaining, frost resistance.
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