CN104817663B - A kind of application of polycarboxylate water-reducer in montmorillonite side effect is suppressed - Google Patents
A kind of application of polycarboxylate water-reducer in montmorillonite side effect is suppressed Download PDFInfo
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Abstract
The invention belongs to technical field of concrete additives, more particularly to a kind of preparation method and applications of the polycarboxylate water-reducer and its polymerized monomer for suppressing montmorillonite side effect.The preparation method of the polycarboxylate water-reducer polymerized monomer that the application is provided, comprises the following steps：Structural compounds shown in formula (II) carry out epoxy addition substitution reaction, obtain polycarboxylate water-reducer polymerized monomer construction unit compound (I).Compound (I) the only one of which polymerization activity point that the application is provided, the polycarboxylate water-reducer prepared using the monomer has the significant ability for suppressing montmorillonite side effects, the polycarboxylate water-reducer method for preparing monomer reaction temperature that the application is provided is low, energy consumption is small, it is adaptable to carry out industrialized production.
Description
Technical field
Suppressing montmorillonite pair the invention belongs to technical field of concrete additives, more particularly to a kind of polycarboxylate water-reducer
Active application.
Background technology
High performance concrete it is general by Binder Materials, gather materials, high efficiency water reducing agent and water etc. are constituted, wherein, polycarboxylic-acid subtracts
Aqua has that volume is low, water-reducing rate is high, function of slump protection good, shrinkage factor is low, molecular structure designability is strong, high performance potentiality are big
Deng many merits, the Important Projects such as high ferro and bridge are had been widely used for, as additional necessary to prepare high performance concrete
Agent.With the promotion and application of poly carboxylic acid series water reducer, it is to gathering materials in (sandstone) the extremely sensitive shortcoming of clay content gradually
It is exposed.When the clay content in gathering materials is higher, the volume for merely improving poly carboxylic acid series water reducer can not improve it
Diminishing dispersive property, it is impossible to improve fresh concrete workability, seriously constrains poly carboxylic acid series water reducer in ready-mixed concrete row
The promotion and application of industry.
The main cause that the dispersive property of poly carboxylic acid series water reducer is seriously limited by clay in sandstone is clay and cement pair
Polycarboxylate water-reducer molecule forms competitive Adsorption.Clay interlayer structure can largely adsorb polycarboxylate water-reducer molecule, reduce
The polycarboxylic acids molecular amounts in cement particle surface are adsorbed, causes polycarboxylate water-reducer to be deteriorated the dispersive property of cement.Research
Show, and illite class and kaolinite class clay-phase ratio, smectite-group clay to the side effects of poly carboxylic acid series water reducer most
For serious.Prior art research finds that polycarboxylate water-reducer adsorbance on the kaolin is about 10~20mg/g, is approximately cement
5~10 times of granular absorption amount (2~4mg/g)；It is approximately cement and the adsorbance in montmorillonite is up to 110~120mg/g
50 times of grain adsorbance.That is, the montmorillonite in sandstone can greatly weaken dispersive property of the poly carboxylic acid series water reducer to cement, will
The workability of fresh concrete is caused drastically to be deteriorated, so that cannot normal construction.
It is well known that the molecular structure of poly carboxylic acid series water reducer determines its performance.Selection function polymerized monomer, changes
The molecular structure of poly carboxylic acid series water reducer, can strengthen the adaptability of polycarboxylate water-reducer and clay, suppress the side effect of clay
Influence.But, the polycarboxylate water-reducer temperature requirement of suppression montmorillonite side effect prepared by prior art is higher, causes production
High energy consumption, increased production cost, reduce market competition advantage, is unfavorable for mass producing and applies.
Beta-schardinger dextrin is the hollow tube-shape thing being formed by connecting with (Isosorbide-5-Nitrae) glycosidic bond by 7 glucose residues, in molecule cavity
Footpath is about 6.0-6.5 angstroms, and height is about 7.9 angstroms, with significant space steric effect.Beta-schardinger dextrin is as feature
Base group modification poly carboxylic acid series water reducer, but the cyclodextrin polycarboxylate water-reducer monomer reaction active site that prior art is used
Many, each reflecting point can participate in Raolical polymerizable, cause polymerizate for cross-linking type, when the degree of cross linking increases, molecule
Amount increase when, easily obtain can only swelling undissolvable highly cross-linked polymer, cause synthesis polycarboxylic acids molecule without diminishing
Dispersive property.
The content of the invention
In view of this, it is an object of the invention to provide a kind of polycarboxylate water-reducer for suppressing montmorillonite side effect and its
The preparation method of polymerized monomer, the polymerized monomer that the present invention is used is a kind of functional monomer containing beta-schardinger dextrin, the monomer
Most significant architectural feature is only one of which polymerization activity point, and the polycarboxylate water-reducer prepared using the monomer has line style
Structure, beta-schardinger dextrin group is located at the side chain of polymer；Because the beta-schardinger dextrin with hollow tube-shape solid space structure can be with
The absorption of clay is prevented, there is polycarboxylate water-reducer provided by the present invention significant suppression montmorillonite its dispersive property pair is made
With the ability of influence.Meanwhile, preparation method of the present invention carries out polymerisation and prepares poly- carboxylic using redox initiation system
Sour water reducer, reaction temperature is low, and energy consumption is small, it is adaptable to carry out industrialized production,
Application of the polycarboxylate water-reducer in montmorillonite side effect is suppressed as shown in formula (V) the invention provides one kind,
Wherein, R1 is selected from-CH2CH2OH、-CH2CH2CH2OH or-CH2CH2CH(CH3)OH；
R2 is selected from hydrogen or methyl；
P is the degree of polymerization, 10≤p≤80；
m:n:x:Y is acrylic acid, compound (I), methylpropene sodium sulfonate and isobutene alcohol APEO construction unit
Mol ratio, m:n:x:Y is (1.5~10)：(0.01~0.5)：(0.1~0.8):1；
The structure of the compound (I) is：
R1 is selected from-CH2CH2OH、-CH2CH2CH2OH or-CH2CH2CH(CH3)OH；
R2 is selected from hydrogen or methyl.
Preferably, the preparation method of the compound (I) is comprised the following steps：
A) there is selective single substitution reaction in structural compounds beta-schardinger dextrin shown in formula (IV) and p-methyl benzene sulfonic chloride, obtain
To structural compounds shown in formula (III)；
B) structural compounds shown in formula (III) and hydramine NH2There is substitution reaction in R1, obtain structure chemical combination shown in formula (II)
Thing；
C) structural compounds shown in the formula (II) carry out epoxy ring-opening substitution reaction with ethylene oxidic ester, obtain described
Compound (I)；
Wherein, R1 is selected from-CH2CH2OH、-CH2CH2CH2OH or-CH2CH2CH(CH3)OH；
R2 is selected from hydrogen or methyl.
Preferably, epoxy ring-opening substitution reaction solvent for use described in step c) is dimethylformamide or methyl alcohol.
Preferably, the concentration of structural compounds shown in formula (II) described in step c) is 0.05~0.45mol/L, reaction temperature
Spend is 65~95 DEG C.
Polycarboxylate water-reducer provided by the present invention has the ability for suppressing montmorillonite side effects, with common polycarboxylic acids
Water reducer is compared, and the ability for suppressing montmorillonite side effects improves 2 times.
Compared with prior art, the invention provides a kind of polycarboxylate water-reducer for suppressing montmorillonite side effect and its poly-
Close the preparation method and applications of monomer.Structural compounds obtain polycarboxylic acids diminishing by epoxy ring opening reaction shown in formula (II)
Agent polymerized monomer construction unit compound (I), compound (I) and acrylic acid, methylpropene sodium sulfonate, isobutene alcohol polyoxyethylene
Ether polymerization obtains polycarboxylate water-reducer.The polycarboxylate water-reducer polymerizable monomer compound prepared by preparation method that the present invention is provided
(I) only one of which polymerization activity point, the polycarboxylate water-reducer prepared using the monomer has linear structure, beta-schardinger dextrin base
Cumularsharolith is in the side chain of polymer；The absorption of clay can be prevented due to the beta-schardinger dextrin with hollow tube-shape solid space structure,
Polycarboxylate water-reducer provided by the present invention has the significant ability for suppressing montmorillonite to its dispersive property side effects.This
Reaction temperature is low when inventing the polycarboxylate water-reducer monomer preparation for providing, and energy consumption is small, it is adaptable to carry out industrialized production.
Brief description of the drawings
Fig. 1 is the mass spectral analysis figure of the compounds of this invention (III)；
Fig. 2 is the mass spectral analysis figure of the compounds of this invention (II)；
Fig. 3 is the mass spectral analysis figure of polycarboxylate water-reducer polymerizable monomer compound (I) of the present invention；
Fig. 4 is the gel permeation chromatography figure of the gained polycarboxylate water-reducer (V) of the embodiment of the present invention 4；
Fig. 5 is the gel permeation chromatography figure of the gained polycarboxylate water-reducer (V) of the embodiment of the present invention 5；
Fig. 6 is the gel permeation chromatography figure of comparative example of the present invention gained polycarboxylate water-reducer (V).
Specific embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
The invention provides a kind of preparation method of polycarboxylate water-reducer polymerized monomer, comprise the following steps：
Structural compounds shown in formula (II) carry out epoxy ring opening reaction, obtain compound (I)；
R1 is selected from-CH in formula2CH2OH or-CH2CH2CH2OH or-CH2CH2CH(CH3)OH。
First, compound (II) is dissolved in solvent, is transferred in water bath, set reaction temperature, while be added dropwise shrinking
In glyceride to compound (II) solution, a period of time is then stirred under design temperature.After reaction terminates, poor solvent is dropped to
In, separate out precipitation.Crude product is dissolved in good solvent, then is added drop-wise in poor solvent, separate out precipitation, the process repeatedly for three times,
Unreacted ethylene oxidic ester is removed, white solid as target compound is obtained.
The solvent of wherein institute's dissolved compound (II) is preferably dimethylformamide or methyl alcohol；The concentration of compound (II) is excellent
Elect 0.05~0.45mol/L as；More preferably 0.1~0.35mol/L, most preferably preferably 0.15~0.3mol/L；Reaction temperature
Preferably 65~95 DEG C, most preferably more preferably 70~85 DEG C, preferably 75~85 DEG C；R2 in the ethylene oxidic ester is preferably
H or CH3；Compound (II) is 1 with the mol ratio of ethylene oxidic ester：(1.1~2.5), more preferably 1：(1.1~2.0), most preferably
Preferably 1：(1.1~1.8)；Mixing time is preferably 6~12h, more preferably 6~10h, most preferably preferably 8~10h.It is bad
Solvent is preferably n-hexane and acetone, and good solvent is preferably dimethylformamide or methyl alcohol.
Structural compounds shown in formula (II) are prepared according to following steps：
Structural compounds shown in formula (III) and hydramine NH2There is substitution reaction in R1, obtain structural compounds shown in formula (II)；
First, compound (III) is dissolved in organic solvent, adds hydramine, be subsequently placed in water bath, design temperature
Lower stirring some hours.After reaction terminates, reactant mixture is dispersed in a large amount of poor solvent solution, Precipitation is thick
Product.Crude product is dissolved in good solvent, then is added drop-wise in poor solvent, separate out precipitation, the process repeatedly for three times, is removed not anti-
The monoethanolamine answered, is dried to obtain white solid as target compound (II).
Wherein described organic solvent is preferably dimethyl sulfoxide (DMSO) or dimethylformamide；The concentration of compound (III) is preferably
0.1~1.5mol/L, more preferably 0.3~1.2mol/L, most preferably 0.4~0.8mol/L；Hydramine NH2R1 in R1 is preferred
For：-CH2CH2OH ,-CH2CH2CH2OH ,-CH2CH2CH(CH3)OH；Compound (III) and hydramine NH2The mol ratio of R1 is preferably 1：
(10~50), more preferably 1：(10~40), most preferably preferably 1：(15~35)；Reaction temperature is preferably 65~85 DEG C, more excellent
Elect 65~80 DEG C as, most preferably preferably 65~75 DEG C；Mixing time is preferably 2~8h, more preferably 3~6h, most preferably preferably 4
~6h；The poor solvent is preferably n-hexane, dichloromethane and acetone, more preferably n-hexane and acetone；The good solvent
Preferably dimethylformamide or methyl alcohol；Drying temperature is preferably 30~55 DEG C, more preferably 35~50 DEG C, most preferably preferably 35
~45 DEG C.
Structural compounds shown in formula (III) are prepared according to following steps：
There is selective single substitution reaction in structural compounds beta-schardinger dextrin shown in formula (IV), obtain with p-methyl benzene sulfonic chloride
Structural compounds shown in formula (III)；
First, beta-schardinger dextrin (IV) is added to the water, and forms suspension, and alkali lye is slowly dropped into beta-schardinger dextrin under agitation
Suspension in, the second cyanogen solution of p-methyl benzene sulfonic chloride is then slowly added dropwise again, at room temperature continue stir.Obtained after filtering anti-
Liquid is answered, the pH value of filtrate is adjusted with acid solution, then stand overnight filtrate at low temperature.Precipitation is collected, is then recrystallized with water
Three times, dried at 60 DEG C, gained white solid is target product (III).
The concentration of wherein described beta-schardinger dextrin suspension is preferably 0.05~0.5mol/L, more preferably 0.05~
0.3mol/L, most preferably 0.1~0.2mol/L；Alkali lye is preferably sodium hydroxide solution, more preferably potassium hydroxide solution, hydrogen
Sodium hydroxide solution；Beta-schardinger dextrin is preferably 1 with the mol ratio of alkali lye：(1.5~15), more preferably 1：(1.5~8), it is optimal excellent
Elect 1 as：(2~5)；The beta-schardinger dextrin is preferably 1 with the mol ratio of p-methyl benzene sulfonic chloride：(1~8), more preferably 1：(1
~5), most preferably preferably 1：(1~2.5)；The dropping temperature of p-methyl benzene sulfonic chloride solution is preferably 0~10 DEG C, more preferably 0
~6 DEG C, most preferably preferably 0~5 DEG C；The time for adding of p-methyl benzene sulfonic chloride solution is preferably 30~150min, more preferably
45~120min, most preferably preferably 55~100min；Mixing time is preferably 1~5h, more preferably 1~3.5h at room temperature, most
It is good to be preferably 1~2.5h；Acid solution is preferably dilute hydrochloric acid solution；The preferred position 4~6.5 of pH value, more preferably 5~6.5, it is optimal preferred
It is 5.5~6.5；The low temperature is preferably 0~10 DEG C, most preferably more preferably 0~6 DEG C, preferably 0~4 DEG C.
The compound (I) and acrylic acid, methylpropene sodium sulfonate, isobutene alcohol APEO in molar ratio (0.01
~0.5)：(1.5~10)：(0.1~0.8):1 polymerization, obtains polycarboxylate water-reducer (V).
The R1 is selected from-CH2CH2OH or-CH2CH2CH2OH or-CH2CH2CH (CH3) OH；
The R2 is selected from hydrogen or methyl；
The p is the degree of polymerization, 10≤p≤80.
Polycarboxylate water-reducer polymerized monomer and isobutene alcohol APEO is soluble in water, form solution (A), its quality
Concentration is preferably 50~80%, more preferably 55~75%, most preferably preferably 60~70%；The isobutene alcohol APEO
Degree of polymerization p be preferably 10≤p≤80, more preferably 20≤p≤60, most preferably preferably 25≤p≤55.
Acrylic acid and methylpropene sodium sulfonate is soluble in water, form solution (B), its mass concentration is preferably 50~
80%, more preferably 55~75%, most preferably preferably 60~75%.
Reduction components in chain-transferring agent and initiator are soluble in water, solution (C) is formed, its mass concentration is preferably
0.005~0.04%, more preferably 0.01~0.03%, most preferably preferably 0.015~0.03%；The chain-transferring agent is preferably
TGA and mercaptopropionic acid；The initiator is redox initiation system, preferably L-AA/hydrogen peroxide and mistake
Ammonium sulfate/sodium hydrogen sulfite system, its reducing component is preferably L-AA and bisulfite.
Solution (A) is warming up to setting reaction temperature, the oxidation component in initiation system is added in (A), oxidation group
Divide and be preferably hydrogen peroxide and ammonium persulfate, then solution (B) and (C) are added drop-wise in (A) in different time, treat whole drops
Add after finishing, be further continued for reaction a period of time, reacting liquid temperature is then down to room temperature, pH value is adjusted with alkali lye, that is, contained
There is the polycarboxylate water-reducer of compound synthesized by the present invention (I).
Each reaction monomers (acrylic acid, polycarboxylate water-reducer polymerizable monomer compound (I), methylpropene sodium sulfonate and
Isobutene alcohol APEO) mol ratio m:n:x:Y is preferably (1.5~10)：(0.01~0.5)：(0.1~0.8):1, more
Preferably (1.5~8)：(0.02~0.4)：(0.1~0.5):1, most preferably it is preferably (2~5)：(0.03~0.3)：(0.15~
0.3):1；The ratio that the initiator accounts for compound (I) is preferably 0.05~0.25%, more preferably 0.05~0.2%, most preferably
Preferably 0.1~0.2%；The ratio that the chain-transferring agent accounts for compound (I) is preferably 0.01~0.1%, more preferably 0.01
~0.08%, most preferably preferably 0.01~0.05%；45~75 DEG C of the reaction temperature, it is more preferably 50~70 DEG C, optimal excellent
Elect 55~65 DEG C as；The time for adding of solution (B) is preferably 2~4h, more preferably 2.5~4h, most preferably preferably 3~4h；It is molten
The time for adding of liquid (C) is preferably 2.5~4.5h, more preferably 3~4.5h, most preferably preferably 3.5~4.5h；After completion of dropping
The continuation reaction time is preferably 0.5~2.5h, more preferably 0.5~2h, most preferably preferably 0.5~1.5h；Alkali lye is preferably hydrogen
Sodium hydroxide solution, its mass concentration is preferably 10~45%, more preferably 20~40%, most preferably preferably 25~35%；PH value
Preferably 4~7, more preferably 5~7, most preferably preferably 5.5~6.5.
The invention provides a kind of functional monomer containing beta-schardinger dextrin, with beta-schardinger dextrin, p-methyl benzene sulfonic chloride, alcohol
Amine and ethylene oxidic ester are raw material, by selective sulfonylation, hydramine substitution reaction and epoxy ring opening reaction, have synthesized one
Plant function monomer compound (I)；Using the monomer and acrylic acid, methylpropene sodium sulfonate and isobutene alcohol APEO etc.,
Using redox initiation system, Raolical polymerizable is carried out, obtain the polycarboxylate water-reducer that side chain contains beta-schardinger dextrin.
The polymerizable monomer compound (I) that the present invention is used is a kind of functional monomer containing beta-schardinger dextrin, and the monomer is most
Significant architectural feature is only one of which polymerization activity point, and the polycarboxylate water-reducer prepared using the monomer has line style knot
Structure, beta-schardinger dextrin group is located at the side chain of polymer；Because the beta-schardinger dextrin with hollow tube-shape solid space structure can hinder
The only absorption of clay, polycarboxylate water-reducer provided by the present invention has significant suppression montmorillonite to its dispersive property side effect
The ability of influence.Meanwhile, preparation method of the present invention carries out polymerisation and prepares polycarboxylic acids using redox initiation system
Water reducer, reaction temperature is low, and energy consumption is small, it is adaptable to carry out industrialized production.
For the sake of becoming apparent from, it is described in detail below by following examples.
Embodiment 1
Beta-schardinger dextrin 24g is added in 180ml water, forms suspension.NaOH 2.6g are dissolved in 20ml water, are subsequently adding
To in the suspension of beta-schardinger dextrin, beta-schardinger dextrin solution is formed.P-methyl benzene sulfonic chloride 4.03g is dissolved in 20ml second cyanogen,
In the mixed solution for being slowly dropped to beta-schardinger dextrin at 4 DEG C, time for adding is 70min, continues to stir 2h at room temperature.Filtering is anti-
Liquid is answered, precipitation is removed, the pH value (pH ≈ 6) of filtrate is adjusted with watery hydrochloric acid, then by filtrate in 4 DEG C of left overnights.Collect heavy
Form sediment, then recrystallized three times with water, dried at 60 DEG C, obtain white solid, yield is about 31%.
Mass spectral analysis is carried out to gained sample, accompanying drawing 1 is seen, in figure shown 1312.01 signal peak from [(III)+
Na]+, it was confirmed that gained white solid is the product that p-methyl benzene sulfonic chloride carries out selective single substitution reaction with beta-schardinger dextrin
(Ⅲ)。
Embodiment 2
Compound (III) 20g is dissolved in 30ml dimethylformamides, monoethanolamine 30ml is added, then reaction bulb is put
In water bath, in reacting 6h at 75 DEG C.After reaction terminates, reactant mixture is dispersed in 2L acetone solns, precipitated
Separate out crude product.Crude product is dissolved in 300ml dimethylformamides, then is separated out with acetone, the process repeatedly for three times, is removed not
The monoethanolamine of reaction, dries at 40 DEG C, obtains white solid, and yield is 88%.
Mass spectral analysis is carried out to gained sample, accompanying drawing 2 is seen, a signal peak 1178.4 is only existed in figure, from target
Product (II) [(II)+H]+, show the white solid for obtaining for compound (III) occurs the product of substitution reaction with monoethanolamine
(Ⅱ)。
Embodiment 3
Compound (II) 30g is dissolved in 80ml dimethylformamides, is transferred in water bath, set reaction temperature as 80
DEG C, while being added dropwise in GMA to compound (II) solution, then stir 10h.After reaction terminates, it is added dropwise
To in 5L acetone, precipitation is separated out.After filtering, gained crude product is dissolved in 20ml dimethylformamides, then is added drop-wise to 3L acetone
In, precipitation is separated out, the process repeatedly for three times, removes unreacted GMA, obtains white solid, yield
It is 84%.
Mass spectral analysis is carried out to gained sample, accompanying drawing 3 is seen, a signal peak 1320.7 is only existed in figure, from poly- carboxylic
Sour water reducer polymerized monomer, shows that the white solid for obtaining is poly- carboxylic with the product of epoxide group ring-opening reaction for compound (II)
Sour water reducer polymerizable monomer compound (I).
Embodiment 4
Gained polycarboxylate water-reducer polymerized monomer (I) (18g) of embodiment 3 and isobutene alcohol APEO (p=52)
(145g) is dissolved in 85g water, forms solution (A)；
Acrylic acid (11g) and methylpropene sodium sulfonate (2g) are dissolved in 6g water, solution (B) is formed；
Mercaptopropionic acid (0.5g) and L-AA (0.25g) are dissolved in water (45g), solution (C) is formed；
Solution (A) is warming up to 60 DEG C, hydrogen peroxide (1.5g) is added in (A), it is then that solution (B) and (C) is same
When be added drop-wise in (A), the time for adding of solution (B) is 3h, and the time for adding of solution (C) is 3.5h, after after whole completion of dropping,
It is further continued for reacting 1h, reacting liquid temperature is then down to room temperature, pH value is adjusted with the sodium hydroxide solution that mass concentration is 30%,
PH ≈ 6, obtain final product the polycarboxylate water-reducer (V) that side chain contains cyclodextrin structure.
Gel osmoticing chromatogram analysis have been carried out to gained polycarboxylate water-reducer (V), accompanying drawing 4 has been seen.Gel permeation chromatography result
Show, the peak molecular weight of this polycarboxylate water-reducer (V) is 9043, and weight average molecular weight is 18390, and polydispersity index is
2.34。
Polycarboxylate water-reducer polymerizable monomer compound (I) only one of which polymerization prepared by the preparation method that the present invention is provided
Reactivity point, the polycarboxylate water-reducer prepared using the monomer has linear structure, and beta-schardinger dextrin group is located at polymer
Side chain；The absorption of clay can be prevented due to the beta-schardinger dextrin with hollow tube-shape solid space structure, it is provided by the present invention
Polycarboxylate water-reducer has the significant ability for suppressing montmorillonite to its dispersive property side effects.
Embodiment 5
By gained polycarboxylate water-reducer polymerizable monomer compound (I) (18g) of embodiment 3 and isobutene alcohol APEO (p
=52) (145g) be dissolved in 85g water, formed solution (A)；
Acrylic acid (11g) and methylpropene sodium sulfonate (2g) are dissolved in 6g water, solution (B) is formed；
Sodium hydrogensulfite (0.5g) is dissolved in water (45g), solution (C) is formed；
Solution (A) is warming up to 60 DEG C, ammonium persulfate (0.23g) is added in (A), it is then that solution (B) and (C) is same
When be added drop-wise in (A), the time for adding of solution (B) is 3h, and the time for adding of solution (C) is 3.5h, after after whole completion of dropping,
It is further continued for reacting 1h, reacting liquid temperature is then down to room temperature, pH value is adjusted with the sodium hydroxide solution that mass concentration is 30%,
PH ≈ 6, obtain final product the polycarboxylate water-reducer (V) that side chain contains cyclodextrin structure.
Gel osmoticing chromatogram analysis have been carried out to gained polycarboxylate water-reducer (V), accompanying drawing 5 has been seen.Gel permeation chromatography result
Show, the peak molecular weight of this polycarboxylate water-reducer (V) is 9442, and weight average molecular weight is 18600, and polydispersity index is
3.02。
Polycarboxylate water-reducer polymerized monomer (I) the only one of which polymerisation prepared by preparation method that the present invention is provided is lived
Property point, the polycarboxylate water-reducer prepared using the monomer has a linear structure, and beta-schardinger dextrin group is located at the side chain of polymer；By
The absorption of clay can be prevented in the beta-schardinger dextrin with hollow tube-shape solid space structure, polycarboxylic acids provided by the present invention subtracts
Aqua has the significant ability for suppressing montmorillonite to its dispersive property side effects.The polycarboxylate water-reducer that the present invention is provided
Reaction temperature is low when prepared by monomer, and energy consumption is small, it is adaptable to carry out industrialized production.
Comparative example
Isobutene alcohol APEO (p=52) (145g) is dissolved in 85g water, solution (A) is formed；
Acrylic acid (11g) and methylpropene sodium sulfonate (2g) are dissolved in 6g water, solution (B) is formed；
Mercaptopropionic acid (0.5g) and L-AA (0.25g) are dissolved in water (45g), solution (C) is formed；
Solution (A) is warming up to 60 DEG C, hydrogen peroxide (1.5g) is added in (A), it is then that solution (B) and (C) is same
When be added drop-wise in (A), the time for adding of solution (B) is 3h, and the time for adding of solution (C) is 3.5h, after after whole completion of dropping,
It is further continued for reacting 1h, reacting liquid temperature is then down to room temperature, pH value is adjusted with the sodium hydroxide solution that mass concentration is 30%,
PH ≈ 6, obtain final product the polycarboxylate water-reducer (V) that side chain contains cyclodextrin structure.
Gel osmoticing chromatogram analysis have been carried out to gained polycarboxylate water-reducer (V), accompanying drawing 6 has been seen.Gel permeation chromatography result
Show, the peak molecular weight of this polycarboxylate water-reducer is 8659, and weight average molecular weight is 14050, and polydispersity index is 3.10.
By the polycarboxylate water-reducer (V) obtained by polycarboxylate water-reducer (V) synthesized in embodiment 4 and 5 and comparative example
Press《Methods for testing uniformity of concrete admixture》(GB 8077-2000) tests flowing degree of net paste of cement with montmorillonite content
Change, W/C=0.29, water reducer volume is the 0.2wt% of cement, and cement is Zhujiang River Guangdong show cement P.O 42.5, and montmorillonite contains
, according to cement weight meter, concrete outcome is referring to table 1 for amount.
The flowing degree of net paste of cement of the polycarboxylate water-reducer of table 1 with montmorillonite content change
As shown in Table 1, after side chain provided by the present invention contains the polycarboxylate water-reducer and cement mixing of cyclodextrin structure
Flowing degree of net paste of cement be slightly larger than ordinary water-reducing agent, show that the Cyclodextrin groups in side chain can improve polycarboxylate water-reducer
Water-reducing rate；When the content of montmorillonite is 1%, the flowing degree of net paste of cement of the polycarboxylate water-reducer that the present invention is provided only is reduced
9%, and common polycarboxylate water-reducer reduces 30%；When montmorillonite content is 1.5%, the cement of common polycarboxylate water-reducer is net
Without mobility, this explanation montmorillonite already leads to common polycarboxylate water-reducer and completely loses diminishing dispersibility slurry；And this hair
Still above 180mm, this shows the polycarboxylic acids of present invention offer to the flowing degree of net paste of cement of bright provided polycarboxylate water-reducer
Water reducer has the significant ability for suppressing montmorillonite to its dispersive property side effects.With common polycarboxylate water-reducer phase
Than the ability that the polycarboxylate water-reducer that the present invention is provided suppresses montmorillonite side effect improves 2 times.
Compared with common polycarboxylate water-reducer, the polycarboxylate water-reducer polymerization prepared by the preparation method that the present invention is provided is single
Body contains beta-schardinger dextrin group, and only one of which polymerization activity point, and the polycarboxylate water-reducer prepared using the monomer is had
There is linear structure, beta-schardinger dextrin group is located at the side chain of polymer；Due to the β with hollow tube-shape solid space structure-ring paste
Essence can prevent the absorption of clay, so that polycarboxylate water-reducer provided by the present invention has significant suppression montmorillonite pair
The ability of its dispersive property side effects.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (4)
1. application of the polycarboxylate water-reducer in montmorillonite side effect is suppressed as shown in formula (V),
Wherein, R1 is selected from-CH2CH2OH、-CH2CH2CH2OH or-CH2CH2CH(CH3)OH；
R2 is selected from hydrogen or methyl；
P is the degree of polymerization, 10≤p≤80；
m:n:x:Y rubs for acrylic acid, compound (I), methylpropene sodium sulfonate and isobutene alcohol APEO construction unit
You compare, m:n:x:Y is (1.5~10)：(0.01~0.5)：(0.1~0.8):1；
The structure of the compound (I) is：
R1 is selected from-CH2CH2OH、-CH2CH2CH2OH or-CH2CH2CH(CH3)OH；
R2 is selected from hydrogen or methyl.
2. application according to claim 1, it is characterised in that the preparation method of the compound (I) is comprised the following steps：
A) there is selective single substitution reaction in structural compounds beta-schardinger dextrin shown in formula (IV) and p-methyl benzene sulfonic chloride, obtain formula
(III) structural compounds shown in；
B) structural compounds shown in formula (III) and hydramine NH2There is substitution reaction in R1, obtain structural compounds shown in formula (II)；
C) structural compounds shown in the formula (II) carry out epoxy ring-opening substitution reaction with ethylene oxidic ester, obtain the chemical combination
Thing (I)；
Wherein, R1 is selected from-CH2CH2OH、-CH2CH2CH2OH or-CH2CH2CH(CH3)OH；
R2 is selected from hydrogen or methyl.
3. application according to claim 2, it is characterised in that molten used by epoxy ring-opening substitution reaction described in step c)
Agent is dimethylformamide or methyl alcohol.
4. application according to claim 2, it is characterised in that structural compounds is dense shown in formula (II) described in step c)
It is 0.05~0.45mol/L to spend, and reaction temperature is 65~95 DEG C.
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| CN106519142A (en) * | 2016-11-21 | 2017-03-22 | 山东交通学院 | Mud resistant type polycarboxylate superplasticizer with controllable molecular structure and preparation method of mud resistant type polycarboxylate superplasticizer |
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