CN107129177A - A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method and the application in concrete - Google Patents
A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method and the application in concrete Download PDFInfo
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- CN107129177A CN107129177A CN201710271003.2A CN201710271003A CN107129177A CN 107129177 A CN107129177 A CN 107129177A CN 201710271003 A CN201710271003 A CN 201710271003A CN 107129177 A CN107129177 A CN 107129177A
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- lignosulfonates
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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
- 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
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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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 belongs to the anti-mud technical field of Compositional type polycarboxylate water-reducer, a kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof and the application in concrete are disclosed, particularly containing the application in cement paste.Water reducer of the present invention is by the compound that is constituted including 100 mass parts polycarboxylate water-reducers and the anti-mud sacrifice agent of the quaternized lignosulfonates of 0.01~5 mass parts；The anti-mud sacrifice agent of quaternized lignosulfonates is prepared by the method comprised the following steps：Quaternizing agent, alkali are added into alkaline lignosulfonate solutions, heating response obtains quaternized lignosulfonates.Water reducer of the present invention can significantly improve mud laden water cement paste fluidity, and such as slump or divergence have obvious anti-mud characteristic, and dispersive property is excellent, with low cost, can be applied to concrete field.The anti-mud sacrifice auxiliary agent of quaternized lignosulfonates therein is cooperateed with polycarboxylic acids to play a role, and under identical volume, the product dispersive property added after sacrifice agent is more preferably.
Description
Technical field
The invention belongs to the anti-mud technical field of Compositional type polycarboxylate water-reducer, more particularly to a kind of anti-chamotte mould polycarboxylic acids subtracts
Aqua and preparation method thereof and the application in concrete, particularly containing the application in cement paste.
Background technology
Concrete is today's society application amount maximum, the widest construction material of application.In infrastructure construction,
In order to obtain high performance concrete, it will usually add high-performance water reducing agent to it.In the 1980s, polycarboxylate water-reducer
(PCE) applied as concrete admixture of new generation in concrete.Polycarboxylate water-reducer is single by the unsaturation containing carboxyl
Body and other monomers copolymerization form, make concrete diminishing, protect collapse, be plasticized, shrink and environmental protection in terms of there is premium properties
Serial water reducer, they can significantly reduce the ratio of mud, improve the durability of mobile performance, compressive strength and concrete.
Aggregate is the important component of concrete, and volume fraction of the sandstone in concrete is about 60~70%.With construction industry
Development, high-quality aggregate gradually uses up totally, and the sandstone clay content of production concrete is higher at present.The main component of mud is viscous
There is soil, the layer structure of clay superpower adsorption capacity decline the dispersive property of cement to polycarboxylate water-reducer, further
Damage the workability of fresh concrete and the later strength and structural stability of structures.During its reason is polycarboxylic acids molecule
PEO side chains, which are easily inserted between the manosil AS salt deposit of clay, to be formed ineffective adsorption and causes, and polycarboxylate water-reducer loses it to cement
Dispersive property.
In order to reduce negative effect of the clay to concrete, four kinds of optional schemes are usually taken.Firstth, it is that selection is free of
The high-quality aggregate of mud.Secondth, the species of water reducer is changed, by using the first kind or Equations of The Second Kind and the good diminishing of mud compatibility
Agent.3rd, the consumption of polycarboxylate water-reducer is increased.4th, sacrifice agent is added.Due to the limitation of environment and production cost, typically
For select without mud high-quality aggregate and improve polycarboxylate water-reducer consumption can greatly promote production cost.And if selection first
Or Equations of The Second Kind water reducer, often because water-reducing rate does not reach required performance not enough.Clay particles have Selective adsorption,
Can be a kind of strong in surface of clay absorption affinity by adding, the cheap, sacrifice agent that is easy to get reduces clay to polycarboxylic acids diminishing
The absorption of agent, improves its dispersibility.
Lignin is second most abundant and reproducible resource on the earth for be only second to cellulose.Tellurian plant
Annual to synthesize about 150,000,000,000 tons of lignin by photosynthesis, the now is mainly derived from pulping and paper-making waste liquid and biological second
The industrial lignin of alcohol, annual big appointment production 4 × 107~5 × 107t.But the lignin only less than 10% has been obtained effectively
Utilize, more than 90% lignin all can directly be burnt up, and both pollute environment, and waste of resource.Wood in acid polishing effluent
Mahogany sulfonate (LS) is the main application form of industrial lignin, be widely used as cement water reducing agent, pesticide dispersing agent and
Dye dispersant etc..As water reducer, LS has favourable water-retaining property and maintainability to fresh concrete, because it has three
Tie up network structure, bleed performance and retardation capability.It is of the invention first to be obtained by raw material of lignosulfonates by quaterisation
A kind of anti-mud sacrifice agent, then prepares anti-chamotte mould polycarboxylate water-reducer with traditional polycarboxylate water-reducer by simply compounding, and
Applied in containing cement paste, mortar, concrete system, overcome traditional polycarboxylate water-reducer bad dispersibility in system containing mud
Shortcoming.
The content of the invention
In order to overcome shortcoming and deficiency of the above-mentioned polycarboxylate water-reducer traditional in the prior art in system containing cement concrete,
The primary and foremost purpose of the present invention is to provide a kind of anti-chamotte mould polycarboxylate water-reducer.The water reducer of the present invention is polycarboxylate water-reducer
(PCE) with the compound of anti-mud sacrifice agent.Described anti-mud sacrifice agent is quaternized lignosulfonates (QL).
Another object of the present invention is to provide a kind of preparation method of above-mentioned anti-chamotte mould polycarboxylate water-reducer.
Still a further object of the present invention is to provide application of the above-mentioned anti-chamotte mould polycarboxylate water-reducer in concrete, particularly contained
Application in material-mud.When polycarboxylic acids volume is 0.10%, the QL of compounding use can improve the fluidity of montmorillonoid-containing slurry,
This is due to that absorption of the QL in montmorillonite is more much better than than lignosulfonates, and QL can be used as special sacrifice agent, this
The anti-chamotte mould polycarboxylate water-reducer for planting compounding is particularly suitable for use in the cement paste containing mud, mortar and concrete.
The purpose of the present invention is realized by following proposal：
A kind of anti-chamotte mould polycarboxylate water-reducer, by including 100 mass parts polycarboxylate water-reducers and 0.01~5 mass parts quaternary ammonium
Change the compound of the anti-mud sacrifice agent composition of lignosulfonates.
In one of the embodiments, described anti-chamotte mould polycarboxylate water-reducer is by including 100 mass parts polycarboxylic acids diminishings
Agent and the compound of the quaternized lignosulfonates of 0.01~1 mass parts anti-mud sacrifice agent composition.
In one of the embodiments, described anti-chamotte mould polycarboxylate water-reducer is by including 100 mass parts polycarboxylic acids diminishings
Agent and the compound of the quaternized lignosulfonates of 1 mass parts anti-mud sacrifice agent composition.
Described polycarboxylate water-reducer is traditional polycarboxylate water-reducer, can be with different polymeric monomer raw material PEG,
The polycarboxylic acid salt of APEG, MPEG, TPEG synthesis, polycarboxylic acids esters, at least one of polycarboxylic acids Sulfonates water reducer, its
Mass concentration is 0.01~1%.
The anti-mud sacrifice agent of quaternized lignosulfonates is prepared by the method comprised the following steps：Toward alkalescence wood
Quaternizing agent, alkali are added in mahogany sulfonate solution, heating response obtains quaternized lignosulfonates.
In one of the embodiments, the mass concentration of the obtained quaternized lignosulfonates is 1~100%.
In one of the embodiments, lignosulfonates used, quaternizing agent, the mass ratio of alkali are (5~27)：
(15~35)：(1~9), be preferably (7~21)：(21.5~30)：(2~6).
In one of the embodiments, described lignosulfonates are Lignin from Alkaline Wheat Straw sulfonate, bamboo pulp sulfomethylated lignin
At least one in hydrochlorate, wood pulp lignosulfonates, enzymolysis xylogen sulfonate and organic solvent extraction type lignosulfonates
Kind；Preferably Lignin from Alkaline Wheat Straw sodium sulfonate.
In one of the embodiments, described quaternizing agent is 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 2,4- bis-
Chloro- [the 1,3,5]-triazines (BDAT) of (dimethylamino) -6-, expoxy propane base-trimethyl-ammonium salt (OMTMA), the chloro- 2- hydroxypropyls of 3-
At least one of cationic etherifying agent such as TEBA (CTA) and glycidyl trimethyl ammonium chloride (GTA).
In one of the embodiments, described alkali be in the highly basic such as sodium hydroxide, potassium hydroxide and calcium hydroxide extremely
Few one kind.
In one of the embodiments, the heating response, which refers to, is heated to 80~90 DEG C, reacts 1~5h.
In one of the embodiments, first the alkaline lignosulfonate solutions are preheated, adds quaternizing agent.
The preheating, which refers to, is heated to 75~85 DEG C.
In one of the embodiments, the alkaline lignosulfonate solutions are first preheated to 75~80 DEG C, add season
After ammonium reagent, 80~85 DEG C are heated to, alkali, heating response is added.
In one of the embodiments, the addition quaternizing agent is preferably added dropwise under agitation, more preferably in stirring speed
Spend under 150~400r/min, to be added dropwise with 5~8mL/min speed.
In one of the embodiments, the pH of the alkaline lignosulfonate solutions is preferably 11~13, more preferably
12.Its pH for adjusting lignosulfonate solutions by using alkali lye is obtained.The alkali lye can for sodium hydroxide, potassium hydroxide and
At least one of strong base solutions such as calcium hydroxide, preferably sodium hydroxide solution.
In one of the embodiments, the concentration of the alkaline lignosulfonate solutions is 10~30wt%.
In one of the embodiments, described quaternizing agent can be made into the solution that concentration is 50~70wt% and be used further to
Reaction.
In one of the embodiments, described alkali can be made into the solution that concentration is 10~30wt% and be used further to reaction.
Further, the anti-mud sacrifice agent of the quaternized lignosulfonates is prepared into by the method comprised the following steps
Arrive：Lignosulfonate solutions pH is adjusted to 11~13, and is preheated to dropwise addition quaternizing agent under 75~80 DEG C, stirring, plus
Heat adds alkali to 80~85 DEG C, and 80~90 DEG C of 1~5h of reaction obtain quaternized lignosulfonates.
The anti-chamotte mould polycarboxylate water-reducer of the present invention, by polycarboxylate water-reducer and the anti-mud sacrifice of quaternized lignosulfonates
After agent compounding, it is 4~10 that can adjust pH by acid or alkali.The compounding can be carried out at 10~50 DEG C.
In one of the embodiments, described alkali be in the highly basic such as sodium hydroxide, potassium hydroxide and calcium hydroxide extremely
Few one kind, preferably sodium hydroxide.
In one of the embodiments, the concentration of described alkali is 10~30wt%.
In one of the embodiments, the mass ratio of the amount of alkali used and polycarboxylate water-reducer is 1:1~1:10.
In one of the embodiments, described acid is at least one of strong acid such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid,
Preferably sulfuric acid.
In one of the embodiments, the mass ratio of sour amount used and polycarboxylate water-reducer is 1:1~1:10.
In one of the embodiments, the solution concentration obtained after the regulation pH is 0.01~1wt%.
The preparation method of the anti-chamotte mould polycarboxylate water-reducer of the present invention, by by polycarboxylate water-reducer and quaternized lignin
The anti-mud sacrifice agent stirring compounding of sulfonate is obtained.
The anti-chamotte mould polycarboxylate water-reducer of the present invention can significantly improve mud laden water cement paste fluidity, such as slump or extension
Degree, there is obvious anti-mud characteristic, and dispersive property is excellent, with low cost, concrete field is can be applied to, particularly containing cement paste
Field, can be applied in the system containing cement concrete that clay content is 1~10%.It is applied to the cement paste of montmorillonoid-containing
In, mix what compounding was obtained with the anti-mud sacrifice agent of the quaternized lignosulfonates of 1 mass parts with 100 mass parts polycarboxylate water-reducers
When compounding anti-chamotte mould polycarboxylate water-reducer, paste flowing degree is increased.
The anti-mud of quaternized lignosulfonates of the present invention sacrifices auxiliary agent can be by reducing yield stress and rheological property
Index is so as to improving the rheological property that montmorillonoid-containing is starched only, and its absorption in montmorillonite is more much better than than lignosulfonates,
It is adsorbed in montmorillonite by very strong electrostatic adsorption, rather than in stratum's absorption mud laden water cement paste.And can be with
Polycarboxylic acids collaboration plays a role, and its scattered viscosity reducing capability is better than commercially available conventional sacrificial agent.It is prepared because of the cheap price of lignin
Anti- mud sacrifice agent cost it is low compared with polycarboxylic acids by 5%.With compounding polycarboxylic acid in use, alternative 10~15% polycarboxylic acids product.Plus
Enter the product after sacrifice agent of the present invention compared with traditional polycarboxylic acids product, under identical volume, the product point added after sacrifice agent
Scattered performance is more preferably.The characteristics such as original dispersibility can be lifted, production cost can be reduced again.
The present invention has the following advantages and beneficial effect relative to prior art：
The present invention uses cheap industrial lignin for raw material, with three innovative points.First, using lignin sulfonic acid
Salt is not only due to that its is cheap, and green is sustainable, it is often more important that because the modified anti-mud sacrifice agent of lignin-base is still
Original feature of lignin is so remained, slow setting, water conservation, guarantor can be played in mud laden water cement paste, mortar and concrete by applying
The effect collapsed.2nd, using 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides as ammonium reagent, reaction condition is gentle, reaction efficiency
Height, it is quaternized after lignosulfonates carry positive electricity, can be drawn together with cement granules by very strong electrostatic interaction,
But simultaneously because the three-dimensional effect of lignin so that montmorillonite is difficult to inhale again after quaternized lignosulfonates sacrifice agent is adsorbed
Agglomeration carboxylic acid molecules.3rd, lignosulfonates quaternized products are applied first and anti-mud sacrifice is used as in mud laden water slurry body
Agent, has widened the developing thought of anti-mud sacrifice agent, and added season can be determined according to the content of soil in compounding
Ammonium lignosulfonates, realize the Modulatory character of auxiliary agent addition, reach the regulation and control of the mobility of overall polycarboxylic acids.The present invention's
The quaternized anti-mud sacrifice agent of lignosulfonates can significantly improve the initial flux degree of mud laden water cement paste.By anti-mud sacrifice agent
Part is substituted after polycarboxylic acids, the initial performance under the identical volume polycarboxylic acids of analogy, mixes the items of the anti-mud sacrifice agent of lignin-base
More preferably, it has broad application prospects and market potential performance.
Brief description of the drawings
Fig. 1 is the infrared signature spectrogram of lignin and quaternized lignosulfonates.
Fig. 2 is the Zeta potential test curve figure of lignosulfonates and quaternized lignosulfonates.
Fig. 3 is blank sample and to mix montmorillonoid-containing cement after the quaternized anti-mud sacrifice agent of lignosulfonates of the invention net
The rheological curve figure of slurry.
Fig. 4 is the paste flowing degree test chart of montmorillonoid-containing cement paste after blank PCE and incorporation QL, LS.
Fig. 5 is on influenceing the XRD determined after blank montmorillonite, PCE, QL incorporation on cheating engaging layer spacing size.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The reagent used in the following example can be obtained from commercial channel.
Embodiment 1
(1) 70g Lignin from Alkaline Wheat Straw sodium sulfonates are dissolved in beaker, add 280mL deionized waters, adjusted with sodium hydroxide
PH is 12, is sufficiently stirred for dissolving standby.Lignin from Alkaline Wheat Straw sodium sulfonate solution is poured into a four-hole boiling flask, using mechanical agitation
And heating water bath, to 80 DEG C, speed of agitator is 200r/min.
(2) 28.01g 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CHPTAC) add solvent in 15.09g water, then adopt
3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution is added dropwise to above-mentioned four-hole boiling flask with peristaltic pump, persistently stirs.Add
14.9g 20%NaOH solution, continues to be heated to 85 DEG C.
(3) after 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides solution is added and finished, it can be obtained after 85 DEG C of insulation reaction 4h
Product.
Application test (cement paste stream of the anti-mud sacrifice agent of quaternized lignosulfonates of the present invention in containing cement paste
Dynamic degree is with reference to Chinese Industrial Standards (CIS) GB 8077~2000《Concrete admixture homogeneity test method》Determine).
Test specimen is to contain cement, montmorillonite, polycarboxylate water-reducer, the quaternized anti-mud sacrifice agent of lignosulfonates,
3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CHPTAC) or lignosulfonates, water.The mass ratio of each composition is 297:3:0.3:
x:87.Four groups of experiments are designed, x is respectively equal to 0 or 0.3.The initial flux degree that three parts of montmorillonites are mixed in 0.3 part of polycarboxylic acids is made
For blank control group test, be separately added into 0.3 part polycarboxylate water-reducer, the anti-mud sacrifice agent of quaternized lignosulfonates,
(what wherein, x=0 was represented is that blank control group is real for 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CHPTAC) or lignosulfonates
Test, x=0.3 is experimental group).
Paste flowing degree testing inspection is carried out to embodiment, it is as a result as follows：
Fig. 1 is the infrared signature spectrogram of lignin and quaternized lignosulfonates.Compared with lignin, one very
Obvious characteristic absorption peak appears in 1625cm-1Place, is the shock absorption peak of N-C keys.1138cm-1Locate the absorption peak intensity occurred
Degree weakens the reduction of content of phenolic hydroxyl groups in explanation lignin.This all illustrates that quaternary ammonium group has been successfully introduced into lignin, i.e., wooden
Quality success is quaternized.Table 1 is the elementary analysis situation of lignin and quaternized lignosulfonates, hence it is evident that the content of N element
Greatly increase.Also being successfully introduced into for quaternary ammonium group can be explained.
Table 1QL and LS element constitute table
Fig. 2 is the Zeta potential test curve figure of lignosulfonates and quaternized lignosulfonates.Test concentrations are equal
For 0.05g/L.It is 1~12 to adjust PH respectively with HCl solution and NaOH solution.With PH increase, lignosulfonates
Zeta scopes are -39.5mV to -21.7mV, and the Zeta scopes of quaternized lignosulfonates are -17.0mV to 4.9mV.This is
Because quaternary ammonium group positively charged so that the carried charge of quaternized lignosulfonates is integrally shuffled, i.e. positively charged amount increase, this also says
Quaternary ammonium group has been successfully introduced into bright lignin.
Fig. 3 is to carry out rheology to not mixing quaternized lignosulfonates and mixing the sample after quaternized lignosulfonates
The 0min rheological curves of performance test, rheological behaviour test is tested at 25 DEG C, and blank control sample is 10% PCE, test
Sample is 10%PCE and 0.01%QL compositional liquors, and ratio of mud selection is 0.29, is tested according to GB/T8077-2012.As a result table
The incorporation of bright sacrifice agent can significantly reduce the shear stress of mud laden water slurry body.
Fig. 4 is to not mixing quaternized lignosulfonates or other auxiliary agents and mixing the sample after quaternized lignosulfonates
Product carry out the fluidity loss figure curve that the test of rheology gradual loss is obtained, and blank control sample is 10% PCE, and test specimens are
10%PCE and 0.01%QL compositional liquors and 10%PCE and 0.01%LS compositional liquors, ratio of mud selection is 0.29, according to GB/
T8077-2012 is tested.As a result show that the addition of sacrifice agent is conducive to the holding of the mobile performance containing slurry body.
In the blank control group experiment for only mixing 0.3 part of polycarboxylic acids, the stream at initial stage containing cement paste of three parts of montmorillonites of incorporation
Dynamic degree is 190mm, with the anti-mud sacrifice agent of quaternized lignosulfonates, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides
(CHPTAC) or lignosulfonates add 0.03 part of fluidity containing slurry body increase respectively to 215mm, 188mm,
192mm.After 0.03 part of quaternized lignosulfonates sacrifice agent is mixed, fluidity increase 25mm.
Compare the blank sample and the anti-mud sacrifice agent of quaternized lignosulfonates, the chloro- 2- hydroxypropyls of 3- under identical PCE volumes
The loss contrast of the paste flowing degree containing slurry body after base trimethyl ammonium chloride (CHPTAC) or lignosulfonates.Blank sample
0.3 part of polycarboxylic acids of middle incorporation, test specimen be 0.3 part of polycarboxylic acids and 0.03 part of quaternized anti-mud sacrifice agent of lignosulfonates,
3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CHPTAC) or lignosulfonates.Test the loss discovery of its paste flowing degree, blank
Sample initial flux degree is 229mm, 30mm, 60mm, and rear fluidity is 167min, 135min.Quaternized lignosulfonates resist
The net slurry stream containing slurry body after mud sacrifice agent, 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides (CHPTAC) or lignosulfonates
Dynamic degree is respectively in 0min, 30min, 60min paste flowing degree：215mm、175mm、145mm；188mm、131mm、95mm；
192mm、146mm、115mm.Damaged this it appears that adding slurry fluidity after the anti-mud sacrifice agent of quaternized lignosulfonates
Mistake has reduced, all smaller than CHPTAC, LS fluidity loss.
Fig. 5 is, to blank montmorillonite sample, to mix the montmorillonite sample after the montmorillonite sample after sacrifice agent, incorporation polycarboxylic acids
Product, and polycarboxylic acids and sacrifice agent mix the XRD of the montmorillonite sample of incorporation, before testing, montmorillonite and PCE solution, QL
Solution is mixed, and mixed proportion is respectively 10:1 and 5:5.As a result the absorption of sacrifice agent energy intercalation is shown between cheating engaging layer, and it is sacrificial
Domestic animal agent add after, polycarboxylic acids will not again intercalation between cheating engaging layer.
Table 2 is that the rheological curve obtained to not mixing the sample progress rheology testing after sacrifice agent and incorporation sacrifice agent enters
The fitting data that row fitting is obtained.As a result the yield stress of mud laden water slurry body can be significantly reduced by showing the incorporation of polycarboxylic acids, modeling
Property viscosity and rheological behavior index.
The rheology of table 2 is fitted
Embodiment 2
(1) 70g bamboo pulp sodium lignin sulfonates are dissolved in beaker, add 280mL deionized waters, adjusted with sodium hydroxide
PH is 12, is sufficiently stirred for dissolving standby.Bamboo pulp lignin sulfonic acid sodium solution is poured into a four-hole boiling flask, using mechanical agitation
And heating water bath, to 80 DEG C, speed of agitator is 200r/min.
(2) by 28.01g 2, chloro- [1,3, the 5]-triazines (BDAT) of 4- bis- (dimethylamino) -6- are added in 15.09g water, so
It is added dropwise, is persistently stirred to above-mentioned four-hole boiling flask using peristaltic pump afterwards, is added 14.9g20%NaOH solution, continue to be heated to
85℃。
(3) after treating that chloro- [1,3, the 5]-triazine solution additions of 2,4- bis- (dimethylamino) -6- in step (2) are finished, 85 DEG C
Product is obtained after insulation reaction 4h.
Embodiment 3
(1) 70g wood pulp sodium lignin sulfonates are dissolved in beaker, add 280mL deionized waters, adjusted with sodium hydroxide
PH is 12, is sufficiently stirred for dissolving standby.Wood pulp lignin sulfonic acid sodium solution is poured into a four-hole boiling flask, using mechanical agitation
And heating water bath, to 80 DEG C, speed of agitator is 200r/min.
(2) 28.01g expoxy propane base-trimethyl-ammonium salt (OMTMA) is added in 15.09g water, then using peristaltic pump
Expoxy propane base-trimethyl-ammonium salt solution is added dropwise to above-mentioned four-hole boiling flask, persistently stirs, 14.9g 20%NaOH are added
Solution, continues to be heated to 85 DEG C.
(3) the expoxy propane base in step (2)-trimethyl-ammonium salt (OMTMA) solution is added after finishing, 85 DEG C of insulations
Product is obtained after reaction 4h.
Embodiment 4
(1) 70g enzymolysis xylogen sodium sulfonates are dissolved in beaker, add 280mL deionized waters, adjusted with sodium hydroxide
PH is 12, is sufficiently stirred for dissolving standby.Enzymolysis xylogen sodium sulfonate solution is poured into a four-hole boiling flask, using mechanical agitation
And heating water bath, to 80 DEG C, speed of agitator is 200r/min.
(2) the chloro- 2- hydroxypropyls TEBAs (CTA) of 28.01g 3- are added in 15.09 water, then using wriggling
The chloro- 2- hydroxypropyls TEBA solution of 3- is added dropwise to above-mentioned four-hole boiling flask in pump, persistently stirs, and adds 14.9g 20%
NaOH solution, continues to be heated to 85 DEG C.
(3) after chloro- 2- hydroxypropyls TEBA (CTA) solution of the 3- in step (2) is added and finished, 85 DEG C of insulations
Product is obtained after reaction 4h.
Embodiment 5
(1) 70g organic solvent extraction type sodium lignin sulfonates are dissolved in beaker, add 280mL deionized waters, use hydrogen
Sodium oxide molybdena regulation pH is 12, is sufficiently stirred for dissolving standby.Organic solvent extraction type lignin sulfonic acid sodium solution is poured into one four
In mouth flask, using mechanical agitation, simultaneously heating water bath is to 80 DEG C, and speed of agitator is 200r/min.
(2) by 28.01g glycidyl trimethyl ammonium chlorides (GTA) add 15.09g water in, then using peristaltic pump to
Glycidyl trimethyl ammonium chloride solution is added dropwise in above-mentioned four-hole boiling flask, persistently stirs, and adds 14.9g 20%NaOH molten
Liquid, continues to be heated to 85 DEG C.
(3) after the glycidyl trimethyl ammonium chloride solution in step (2) is added and finished, after 85 DEG C of insulation reaction 4h
Obtain product.
Tested using paste flowing degree same as Example 1, rheological curve test, rheology gradual loss, XRD analysis with
And rheology fitting, it is as a result essentially identical.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of anti-chamotte mould polycarboxylate water-reducer, it is characterised in that by including 100 mass parts polycarboxylate water-reducers and 0.01~5 matter
Measure the compound of the anti-mud sacrifice agent composition of the quaternized lignosulfonates of part；
The anti-mud sacrifice agent of quaternized lignosulfonates is prepared by the method comprised the following steps：Toward alkalescence lignin
Quaternizing agent, alkali are added in sulfonate solution, heating response obtains quaternized lignosulfonates.
2. anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that：Lignosulfonates used, quaternary ammonium
Change reagent, the mass ratio of alkali is (5~27)：(15~35)：(1~9).
3. anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that：Described lignosulfonates are wheat
Vegetation mahogany sulfonate, bamboo pulp lignosulfonates, wood pulp lignosulfonates, enzymolysis xylogen sulfonate and organic solvent are carried
Take at least one of type lignosulfonates；
Described quaternizing agent be 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 2,4- bis- (dimethylamino) -6- it is chloro- [1,3,
5]-triazine, expoxy propane base-trimethyl-ammonium salt, the chloro- 2- hydroxypropyls TEBAs of 3- and dehydration glyceryl trimethyl chlorine
Change at least one of ammonium；
Described alkali is at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
4. anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that：The heating response, which refers to, is heated to 80
~90 DEG C, react 1~5h.
5. anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that：First by the alkaline lignin sulfonic acid
Salting liquid is preheated, and adds quaternizing agent；The preheating, which refers to, is heated to 75~85 DEG C.
6. anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that the quaternized lignosulfonates
Anti- mud sacrifice agent is prepared by the method comprised the following steps：Lignosulfonate solutions pH is adjusted to 11~13, and in advance
Heat is to 75~80 DEG C, and stirring is lower to be added dropwise quaternizing agent, is heated to 80~85 DEG C, adds alkali, and 80~90 DEG C of 1~5h of reaction are obtained
To quaternized lignosulfonates.
7. anti-chamotte mould polycarboxylate water-reducer according to claim 1, it is characterised in that by subtracting including 100 mass parts polycarboxylic acids
The compound of aqua and the anti-mud sacrifice agent composition of the quaternized lignosulfonates of 0.01~5 mass parts.
8. the preparation method of the anti-chamotte mould polycarboxylate water-reducer described in a kind of any one of claim 1~7, it is characterised in that pass through
The anti-mud sacrifice agent stirring compounding of the polycarboxylate water-reducer and quaternized lignosulfonates is obtained.
9. preparation method according to claim 8, it is characterised in that：By the polycarboxylate water-reducer and quaternized lignin
After the anti-mud sacrifice agent compounding of sulfonate, it is 4~10 to adjust pH by acid or alkali.
10. application of the anti-chamotte mould polycarboxylate water-reducer in concrete field described in any one of claim 1~7.
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