CN109749020A - A kind of early strong viscosity reduction type polycarboxylate water-reducer and preparation method thereof containing alkyl - Google Patents
A kind of early strong viscosity reduction type polycarboxylate water-reducer and preparation method thereof containing alkyl Download PDFInfo
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Abstract
The present invention provides a kind of strong viscosity reduction type polycarboxylate water-reducers of morning, the early strong viscosity reduction type polycarboxylate water-reducer that the present invention synthesizes, it mutually acts synergistically between each component, between each functional group, compared with the Early-strength polycarboxylate superplasticizer of prior art synthesis, early strong and viscosity reducing effect is superior and water-reducing rate is unaffected, simultaneously because introducing a large amount of hydrophobic alkyl in PEG side chain, reduces HLB value, surface-active effect is enhanced, there is good decrement performance.Water-reducing agent of the present invention has good promotion hydrated cementitious, improves the effect of early strength of concrete development；Water-reducing agent of the present invention has good water-reducing rate and slump holding capacity.Water-reducing agent of the present invention is early strong and hydrophobic viscosity reduction functional group is located on side chain, the content of adjusting viscosity reduction and Zao Qiang functional group can be passed through, the early strong and viscosity reducing effect of water-reducing agent is adjusted, but does not influence dispersing group to the dispersion effect of cement granules, because of the dispersion and water-reducing effect without influencing water-reducing agent.
Description
Technical field
The present invention relates to technical field of concrete additives more particularly to a kind of early strong viscosity reduction type polycarboxylic acids containing alkyl to subtract
Aqua and preparation method thereof.
Background technique
In recent years, with the increasing of China's infrastructure, high-grade concrete is just with its intensity height, good integrity, self weight
Small feature steps into building materials market, is especially used heavily in science of bridge building.But due to using a large amount of gel rubber material
With lower water-cement ratio, high-grade concrete has that viscosity is larger and flowing velocity is slow, and then the stirring of initiation concrete,
Transport, pumping and construction problem, largely limit the popularization and application of high-strength super high strength concrete.
For engineers and technicians, the high-strength big problem of super high strength concrete viscosity is the technical problem perplexed for a long time.Mesh
Before, the viscosity reducing process of high-strength concrete mainly optimizes grain composition using the superfine powder for improving water-reducing agent volume and optimization.It is right
Concrete viscosity is reduced in improving water-reducing agent volume, fresh concrete will appear bleeding, take off the problems such as bottom, causes centainly to construction
Difficulty causes the excessive slow setting of concrete, extends the demoulding period, increases concrete production cost.The superfine powder optimization of optimization
Grade is matched, to reduce concrete viscosity, though have many research, have certain limitation, the mobility of fresh concrete,
Rely primarily on the strong absorption peptizaiton of high efficiency water reducing agent, optimization grain composition cannot fundamentally solving practical problems.
Poly carboxylic acid series water reducer, as the third generation product of cement water reducing agent, with volume is low, water-reducing rate is high, protects and collapses
The advantages that performance is good, contraction is small, environmentally protective, it has also become one of essential component of high performance concrete.By selecting not
With the monomer of structure and function, the molecular structure of specific polycarboxylate water-reducer is set, optimum organization controls backbone polymerization degree, side
Chain length, functional group's type realize the high performance of poly carboxylic acid series water reducer, is prepared with lower shrinkage, viscosity reduction function
Polycarboxylate water-reducer, to solve, concrete viscosity is big, flowing velocity is slow and shrinks the problems such as big.
Currently, additive used in China's prefabricated components concrete production is based on naphthalene series high-efficiency water-reducing agent, naphthalene water reducer
Concrete flowability it is poor, slump-loss is fast, be easy bleeding, be not easy cloth of constructing.Polycarboxylate high performance water-reducing agent by
In its water-reducing rate is high, reinforcing effect is obvious the advantages that, it has been applied in the production of prefabricated components, but common polycarboxylic-acid
Water-reducing agent has certain deferred action and bleed, extends the setting time of concrete, be unfavorable for the raising of early strength
And the fast demoulding of prefabricated components.Early-strength polycarboxylate superplasticizer early strength with higher and shorter setting time, mesh
There are many reports and patent about Early-strength polycarboxylate superplasticizer for the preceding country, but mature product is seldom, and is used for high standard
When in number concrete, such as Guan Village concrete, it is hard to there is the glutinous material of material, constructional difficulties, the big problem of slump-loss.
In recent years, viscosity reduction type polycarboxylate water-reducer is increasingly becoming the research hotspot in concrete admixture field, but makes a general survey of
The document and patent of viscosity reduction type polycarboxylate water-reducer, the molecular weight (2) that researcher mostly uses (1) to reduce water-reducing agent reduce the side PEG
Chain length (3) introduces hydrophobic functional groups in water-reducing agent molecular structure, such as methyl and ester group, increases the hydrophobicity of product, with
Reach reduction in conjunction with water, discharge Free water to the maximum extent, improves water-cement ratio indirectly, and then reduce concrete mortar viscosity
Purpose.It reduces water-reducing agent molecular weight and PEG side chain lengths, advantage is can to make viscosity reduction type water-reducing agent than ordinary water-reducing agent in freedom
There is higher freedom of motion in water, more can rapidly stretch the strand of water-reducing agent, thus quick adsorption disperse water
Mud particle reduces the viscosity of cement slurry.The disadvantage is that water-reducing agent molecular weight is small, absorption dispersion group-COO-Quantity it is few, diminishing
Agent molecule reduces the absorption dispersion effect of cement granules, and reduces PEG side chain lengths, reduces steric hindrance effect, thus
Greatly reduce the water-reducing rate of polycarboxylate water-reducer.And hydrophobic methyl and ester group are introduced in water-reducing agent molecular structure, such as exist
By introducing methyl acrylic ester, hydroxyethyl methacrylate esters etc. in molecular structure, the polymer of synthesis has certain drop
Viscous effect, but the disadvantage is that hydrophobic functional groups are located on main chain, the content of hydrophobic functional groups receives limitation, if hydrophobicity is poly-
The ratio for closing minor comonomer substituent methyl acrylic acid in the copolymer is excessively high, then adsorbs dispersing group-COO-Content reduce, influence
Absorption and dispersion to cement granules and its hydrated product, water-reducing rate reduce, and if hydrophobic polymerizable minor comonomer is in copolymer
The ratio of middle substituent methyl acrylic acid is too low, then viscosity reducing effect is unobvious, and the purpose for reducing viscosity is not achieved.So research and development
One kind having good viscosity reducing effect, while having high water reducing rate and early powerful polycarboxylate water-reducer, to high grade coagulation
The production and research and development of soil especially the production of the tubular pile concrete of C100 or more superelevation concrete and low slump and are ground
Hair has important social and economic implications.
As described above, research and development have early strength function, while having both the early strong viscosity reduction type polycarboxylic acids diminishing of good viscosity reduction effect
Agent there is the concrete production of early strong demand and construction to have very important society and economy high-intensitive, the small slump
Meaning.
Summary of the invention
For existing above-mentioned technological deficiency, the present invention introduces in the molecular structure according to macromolecular structure design theory
Surface-active macromonomer D with viscosity reduction function and there is early powerful surface-active macromonomer E, makes concrete early stage with higher
Intensity and lower viscosity, so that it is big to solve slow setting and viscosity of the poly carboxylic acid series water reducer in concrete prefabricated element application
The technical issues of.Using ethylation reaction, the PEG viscosity reduction type surface-active macromonomer containing hydrophobic alkyl is synthesized, the activity is big single
The polycarboxylate water-reducer of the copolymerizations such as body and acrylic acid.Since hydrophobic alkyl is located on PEG side chain, imparts the present invention and subtract
Aqua has following 4 major advantages: 1. its content do not influence to adsorb dispersion-COO in copolymer-The content of group, because without
Influence the absorption dispersion effect of water-reducing agent；2. hydrophobic alkyl content can arbitrarily be adjusted, be reached according to the actual needs of viscosity reducing effect
To the purpose for effectively solving the problems, such as that viscosity is big existing for high-grade concrete, flow velocity is slow；3. since PEG side chain contains a large amount of dredge
The Viscosity-reducing alkyl of water, diminishing agent molecule can not form complete water layer film in cement particle surface, but it is defective to form tool
The water layer film of collapsing, this have defective collapsing water layer film assign water-reducing agent following features: (1) can release it is more from
By water, the viscosity of cement slurry is reduced；(2) molecular weight of diminishing agent molecule is not required to be limited by viscosity reduction；(3) PEG side face
Length is not required to be limited by viscosity reduction；4. a large amount of hydrophobic alkyl introduced in PEG side chain, greatly reduces the table of product
Face tension, reduces the convergent force of moisture evaporation, to reduce the shrinkage cracking of concrete, has good Reduce shrinkage effect.
Polymeric monomer E contains a large amount of cationic charge in the molecular structure, promotes hydrated reaction of cement, accelerates hardening coagulation
The early strength development of soil, has super hardening effect, shortens mold releasability and turn around time, concrete prefabricated element may be implemented
It is non-evaporating support and exempt from pressure steam Dan Shuan exempt from technique.It is located in PEG side chain with early powerful cation group, and can be according to morning
Strong needs arbitrarily adjust the content of cation group, to reach the demand to early strength development.
To achieve the above object, the technical solution taken: a kind of morning strong viscosity reduction type polycarboxylate water-reducer, the morning drop by force
Viscous type polycarboxylate water-reducer is formula (I) compound represented, and the structural formula of formula (I) compound represented is as follows:
The integer that a is 10~80, the integer that b is 1~60, the integer that c is 1~80, the integer that d is 1~60, e 1-80
Integer；Preferably, e is the integer of 10-60；
A isR1For H or CH3；
B isR2For H or CH3, R3For CH2、CH2CH2
Or OCH2CH2CH2CH2, m1For 0~50 integer, m2For 5~50 integer；
C isR4For H or CH3, R5For CH2、CH2CH2Or
OCH2CH2CH2CH2, n is the integer of 1-80；
D isR6 is H or CH3, R7For
CH2、CH2CH2Or OCH2CH2CH2CH2, the integer of m=2~6, the integer that x is 1~60；It is highly preferred that x is the integer of 10-60；
E:
n1For the integer of 5-60, n2For the integer of 0-50, n3For the integer of 5-60, R11、R12And R13It is respectively alone C1-3Alkane
Base, Z Cl, Br or I.
The present invention provides a kind of preparation method of strong viscosity reduction type polycarboxylate water-reducer of morning, the preparation method includes following
Step:
By reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E, oxidant are soluble in water obtains solution 1, will
Reaction monomers A and chain-transferring agent is soluble in water obtains solution 2, dissolves reduce agent in water and obtains solution 3, under normal temperature conditions,
Solution 2 and solution 3 are added drop-wise in solution 1 and reacted, solution 2 and solution 3 start simultaneously at dropwise addition, and solution 2 drips in 2~3h
Add complete, 10~30min is added dropwise than solution more than 2 in solution 3, is added dropwise in 2.5~3.5h, and the reaction was continued 4~8h will react
The pH of solution afterwards is adjusted to 7~8, up to early strong viscosity reduction type polycarboxylate water-reducer；
The reaction monomers A is at least one of acrylic acid, methacrylic acid；
The reaction monomers B is at least one of APEG/PPG, HPEG/PPG, VPEG/PPG, TPEG/PPG；
The reaction monomers C is at least one of APEG, HPEG, VPEG and TPEG；
The reaction monomers D is viscosity reduction shrinkage type surface-active macromonomer, shown in structural formula such as formula (II),
Wherein, R6=H or CH3, R7=CH2、CH2CH2Or OCH2CH2CH2CH2；The integer of m=2~6, x are 1~60
Integer.Preferably, x is the integer of 10-60.
Shown in the structural formula such as formula (III) of the reaction monomers E,
n1For the integer of 5-60, n2For the integer of 0-50, n3For the integer of 5-60, R11、R12And R13It is respectively alone C1-3Alkane
Base, Z Cl, Br or I.
Preferably, the reaction monomers D is prepared by following methods:
Initiator enol is mixed with catalyst, under protective gas atmosphere, alkylene oxide is at the uniform velocity added dropwise at 80~120 DEG C
Hydrocarbon is added dropwise in 2~4h, the reaction was continued at 90~110 DEG C 6~12h, obtains reaction monomers D；
Shown in the structural formula of the epoxyalkane such as formula (IV),
The integer that m is 2~6.
Reaction equation is as follows:
Preferably, the enol is at least one in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ether and prenol
Kind, the catalyst is sodium hydride or sodium, and the protective gas is nitrogen.
Preferably, the methallyl alcohol, epoxyalkane molar ratio be 1:1~60.It is highly preferred that the methallyl
Alcohol, epoxyalkane molar ratio be 1:10~60.
Preferably, the molar ratio of the reaction monomers A, reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E
For 5~10:0.4~1.0:0.6~1.2:0.8~2.0:0.8~2.0.
Preferably, the additional amount of the chain-transferring agent is the 0.05~5% of overall reaction monomer molar number, the oxidant
Additional amount is the 0.05~5% of overall reaction monomer molar number, and the additional amount of the reducing agent is the 20%~100% of oxidant.
Overall reaction monomer molar number refers to the molal quantity of reaction monomers A, reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E
The sum of.
Preferably, the oxidant be hydrogen peroxide, the reducing agent be one of ascorbic acid, sodium hydrogensulfite or
Two kinds, the chain-transferring agent is one or both of thioacetic acid, mercaptopropionic acid.
The present invention provides early strong viscosity reduction type polycarboxylate water-reducers described above to prepare the purposes in concrete.
The present invention has synthesized early strong viscosity reduction type polycarboxylate water-reducer, and the water-reducing agent is while keeping high water reducing rate, tool
There is significant early strong and viscosity reducing effect.
It is living that the initiators such as present invention prenol have synthesized the PEG containing alkyl hydrophobic functional group with alkyl epoxide
Property polymeric monomer D, the polymeric monomer and reactive monomer A, B, C, E carry out combined polymerization, the polycarboxylate water-reducer of synthesis, hydrophobic alkyl official
Energy cumularsharolith, in the case where not influencing water-reducing rate, can arbitrarily be adjusted hydrophobic on side chain according to the actual demand of viscosity reducing effect
It is hydrophobic to avoid the prior art to meet the needs of to viscosity reducing effect for content of the alkyl functional group in entire molecular structure
Property functional group content influence water-reducing rate technological deficiency；Simultaneously as introducing a large amount of hydrophobicity in water-reducing agent PEG side chain
Alkyl reduces HLB value, enhances surface-active effect, has good decrement performance, diminishing agent molecule is in cement granules table
Face can not form complete water layer film, but form the water layer film for having defective collapsing, this has the water layer of defective collapsing
Film assigns water-reducing agent following features: (1) can release more Free waters, reduce the viscosity of cement slurry；(2) water-reducing agent point
The molecular weight of son is not required to be limited by viscosity reduction；(3) the PEG side chain of diminishing agent molecule is not required to be limited by viscosity reduction, is avoided
Viscosity reduction type polycarboxylate water-reducer is to realize viscosity reducing effect and reduce polymer molecular weight and PEG side chain in the prior art, thus shadow
Ring the technological deficiency of product water-reducing rate.
On the other hand, the present invention is in the molecular structure of water-reducing agent, the PPG chain with hydrophobic effect introduced in the side chain
Section, and a large amount of hydrophobic alkyl functional group introduced by polymeric monomer D, the water-reducing agent for assigning synthesis have good reduction table
The ability of face tension reduces the convergent force of moisture evaporation, to reduce the shrinkage cracking of concrete.
The a large amount of quaternary ammonium salt cationic charges introduced in the molecular structure by surface-active macromonomer E promote hydrated reaction of cement,
The early strength development for accelerating maturing, has super hardening effect, shortens mold releasability and turn around time, may be implemented to mix
The non-evaporating of solidifying soil prefabricated components is supported and exempts from that steaming Dan Shuan is pressed to exempt from technique.It is located in PEG side chain with early powerful cation group,
And the content of cation group can be arbitrarily adjusted according to early strong needs, to reach the demand to early strength development.
The utility model has the advantages that
The early strong viscosity reduction type polycarboxylate water-reducer that the present invention synthesizes mutually acts synergistically between each component, between each functional group, with
The reduction of prior art synthesis is glued type polycarboxylate water-reducer and is compared, and has the advantages that
1, early strong and hydrophobic group functional group is located on side chain, can be adjusted by adjusting early strong and viscosity reduction functional group content
The early strong and viscosity reducing effect of aqua is reduced, but does not influence dispersing group to the dispersion effect of cement granules, because without influencing diminishing
The dispersion and water-reducing effect of agent.
2, the molecular weight of water-reducing agent is not limited by water-reducing agent viscosity reduction and early strong effect.
3, the PEG side chain length in water-reducing agent molecular structure is not limited by water-reducing agent viscosity reduction and early strong effect；
4, there is good promotion hydrated cementitious, quickly improve the effect of early strength of concrete development；
5, viscosity reducing effect is superior and water-reducing rate is unaffected.
6, there is better adaptability to cement.
7, there is good water-reducing rate and slump holding capacity.
8, there is good viscosity reducing effect.
9, there is good Reduce shrinkage effect, add the concrete of product of the present invention, shrinking percentage is low, does not crack.
10, it is applied in prefabricated components concrete, promotes early strength of concrete development, shortens mold turn around time, it is real
It is now non-evaporating to support and exempt from that steaming Dan Shuan is pressed to exempt from technique.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.The preparation method of reaction monomers E of the present invention is shown in the surface-active macromonomer N in patent 201510666758.3.
Embodiment 1
The preparation method of morning strong viscosity reduction type polycarboxylate water-reducer of the present invention, the preparation method comprises the following steps:
(1) synthesis of viscosity reduction type surface-active macromonomer D:
In four mouthfuls of glass flasks for having blender, thermometer, reflux condensing tube, Dropping feeder, 1mol methyl is added
1mol epoxyalkane is at the uniform velocity added dropwise at 80 DEG C, is added dropwise in 2h for allyl alcohol, 2g sodium hydride, under nitrogen protection, stirring,
The reaction was continued at 90 DEG C 6h, obtains viscosity reduction shrinkage type surface-active macromonomer D.
(2) synthesis of early strong viscosity reduction type polycarboxylate water-reducer
By reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E, oxidant are soluble in water obtains solution 1, will
Reaction monomers A and chain-transferring agent is soluble in water obtains solution 2, dissolves reduce agent in water and obtains solution 3, under normal temperature conditions,
Solution 2 and solution 3 are added drop-wise in solution 1 and reacted, solution 2 and solution 3 start simultaneously at dropwise addition, and solution 2 is added dropwise in 3h
It finishes, 30min is added dropwise than solution more than 2 in solution 3, is added dropwise in 3.5h, the reaction was continued 6h, by the pH tune of the solution after reaction
To 7, up to early strong viscosity reduction type polycarboxylate water-reducer.
The reaction monomers A is methacrylic acid, and the reaction monomers B is HPEG/PPG, and the reaction monomers C is
HPEG, the reaction monomers D are the viscosity reduction type surface-active macromonomer D that step (1) obtains.It is the reaction monomers A, reaction monomers B, anti-
Answer monomer C, reaction monomers D, reaction monomers E molar ratio be 6:0.8:0.8:1:1.2.
The oxidant is hydrogen peroxide, and the reducing agent is sodium hydrogensulfite, and the chain-transferring agent is thioacetic acid.Chain
The additional amount of transfer agent is the 2% of overall reaction monomer molar number, and the additional amount of oxidant is the 2% of overall reaction monomer molar number,
The additional amount of reducing agent is the 80% of oxidant.
Embodiment 2
The preparation method of morning strong viscosity reduction type polycarboxylate water-reducer of the present invention, the preparation method comprises the following steps:
(1) synthesis of viscosity reduction type surface-active macromonomer D:
In four mouthfuls of glass flasks for having blender, thermometer, reflux condensing tube, Dropping feeder, 1mol methyl is added
10mol epoxyalkane is at the uniform velocity added dropwise at 90 DEG C, is added dropwise in 3h for allyl alcohol, 2g sodium hydride, under nitrogen protection, stirring,
The reaction was continued at 100 DEG C 8h, obtains viscosity reduction type surface-active macromonomer D.
(2) synthesis of early strong viscosity reduction type polycarboxylate water-reducer
By reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E, oxidant are soluble in water obtains solution 1, will
Reaction monomers A and chain-transferring agent is soluble in water obtains solution 2, dissolves reduce agent in water and obtains solution 3, under normal temperature conditions,
Solution 2 and solution 3 are added drop-wise in solution 1 and reacted, solution 2 and solution 3 start simultaneously at dropwise addition, and solution 2 is added dropwise in 3h
It finishes, 30min is added dropwise than solution more than 2 in solution 3, is added dropwise in 3.5h, the reaction was continued 6h, by the pH tune of the solution after reaction
To 7, up to early strong viscosity reduction type polycarboxylate water-reducer.
The reaction monomers A is methacrylic acid, and the reaction monomers B is HPEG/PPG, and the reaction monomers C is
HPEG, the reaction monomers D are the viscosity reduction type surface-active macromonomer D that step (1) obtains.It is the reaction monomers A, reaction monomers B, anti-
Answer monomer C, reaction monomers D, reaction monomers E molar ratio be 6:0.8:0.8:1:1.2.
The oxidant is hydrogen peroxide, and the reducing agent is sodium hydrogensulfite, and the chain-transferring agent is thioacetic acid.Chain
The additional amount of transfer agent is the 2% of overall reaction monomer molar number, and the additional amount of oxidant is the 2% of overall reaction monomer molar number,
The additional amount of reducing agent is the 80% of oxidant.
Embodiment 3
The preparation method of morning strong viscosity reduction type polycarboxylate water-reducer of the present invention, the preparation method comprises the following steps:
(1) synthesis of viscosity reduction type surface-active macromonomer D:
In four mouthfuls of glass flasks for having blender, thermometer, reflux condensing tube, Dropping feeder, 1mol methyl is added
Allyl alcohol, 2g sodium hydride, under nitrogen protection, 30mol epoxyalkane is at the uniform velocity added dropwise at 110 DEG C, drips in 3h for stirring
Finish, the reaction was continued at 100 DEG C 10h obtains viscosity reduction shrinkage type surface-active macromonomer D.
(2) synthesis of early strong viscosity reduction type polycarboxylate water-reducer
By reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E, oxidant are soluble in water obtains solution 1, will
Reaction monomers A and chain-transferring agent is soluble in water obtains solution 2, dissolves reduce agent in water and obtains solution 3, under normal temperature conditions,
Solution 2 and solution 3 are added drop-wise in solution 1 and reacted, solution 2 and solution 3 start simultaneously at dropwise addition, and solution 2 is added dropwise in 3h
It finishes, 30min is added dropwise than solution more than 2 in solution 3, is added dropwise in 3.5h, the reaction was continued 6h, by the pH tune of the solution after reaction
To 7, up to early strong viscosity reduction type polycarboxylate water-reducer.
The reaction monomers A is methacrylic acid, and the reaction monomers B is HPEG/PPG, and the reaction monomers C is
HPEG, the reaction monomers D are the viscosity reduction type surface-active macromonomer D that step (1) obtains.It is the reaction monomers A, reaction monomers B, anti-
Answer monomer C, reaction monomers D, reaction monomers E molar ratio be 6:0.8:0.8:1:1.2.
The oxidant is hydrogen peroxide, and the reducing agent is sodium hydrogensulfite, and the chain-transferring agent is thioacetic acid.Chain
The additional amount of transfer agent is the 2% of overall reaction monomer molar number, and the additional amount of oxidant is the 2% of overall reaction monomer molar number,
The additional amount of reducing agent is the 80% of oxidant.
Embodiment 4
The preparation method of morning strong viscosity reduction type polycarboxylate water-reducer of the present invention, the preparation method comprises the following steps:
(1) synthesis of viscosity reduction type surface-active macromonomer D:
In four mouthfuls of glass flasks for having blender, thermometer, reflux condensing tube, Dropping feeder, 1mol methyl is added
Allyl alcohol, 2g sodium hydride, under nitrogen protection, 60mol epoxyalkane is at the uniform velocity added dropwise at 120 DEG C, drips in 4h for stirring
Finish, the reaction was continued at 110 DEG C 12h obtains viscosity reduction type surface-active macromonomer D.
(2) synthesis of early strong viscosity reduction type polycarboxylate water-reducer
By reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E, oxidant are soluble in water obtains solution 1, will
Reaction monomers A and chain-transferring agent is soluble in water obtains solution 2, dissolves reduce agent in water and obtains solution 3, under normal temperature conditions,
Solution 2 and solution 3 are added drop-wise in solution 1 and reacted, solution 2 and solution 3 start simultaneously at dropwise addition, and solution 2 is added dropwise in 3h
It finishes, 30min is added dropwise than solution more than 2 in solution 3, is added dropwise in 3.5h, the reaction was continued 6h, by the pH tune of the solution after reaction
To 7, up to early strong viscosity reduction type polycarboxylate water-reducer.
The reaction monomers A is methacrylic acid, and the reaction monomers B is HPEG/PPG, and the reaction monomers C is
HPEG, the reaction monomers D are the viscosity reduction type surface-active macromonomer D that step (1) obtains.It is the reaction monomers A, reaction monomers B, anti-
Answer monomer C, reaction monomers D, reaction monomers E molar ratio be 6:0.8:0.8:1:1.2.
The oxidant is hydrogen peroxide, and the reducing agent is sodium hydrogensulfite, and the chain-transferring agent is thioacetic acid.Chain
The additional amount of transfer agent is the 2% of overall reaction monomer molar number, and the additional amount of oxidant is the 2% of overall reaction monomer molar number,
The additional amount of reducing agent is the 80% of oxidant.
Embodiment 5
The preparation method of morning strong viscosity reduction type polycarboxylate water-reducer of the present invention, the preparation method comprises the following steps:
(1) synthesis of viscosity reduction type surface-active macromonomer D:
In four mouthfuls of glass flasks for having blender, thermometer, reflux condensing tube, Dropping feeder, 1mol allyl is added
Alcohol, 2g sodium hydride, under nitrogen protection, 30mol epoxyalkane is at the uniform velocity added dropwise at 110 DEG C, is added dropwise in 3h, 100 for stirring
The reaction was continued at DEG C 10h, obtains viscosity reduction type surface-active macromonomer D.
(2) synthesis of early strong viscosity reduction type polycarboxylate water-reducer
By reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E, oxidant are soluble in water obtains solution 1, will
Reaction monomers A and chain-transferring agent is soluble in water obtains solution 2, dissolves reduce agent in water and obtains solution 3, under normal temperature conditions,
Solution 2 and solution 3 are added drop-wise in solution 1 and reacted, solution 2 and solution 3 start simultaneously at dropwise addition, and solution 2 is added dropwise in 3h
It finishes, 30min is added dropwise than solution more than 2 in solution 3, is added dropwise in 3.5h, the reaction was continued 6h, by the pH tune of the solution after reaction
To 7, up to early strong viscosity reduction type polycarboxylate water-reducer.
The reaction monomers A is methacrylic acid, and the reaction monomers B is HPEG/PPG, and the reaction monomers C is
HPEG, the reaction monomers D are the viscosity reduction type surface-active macromonomer D that step (1) obtains.It is the reaction monomers A, reaction monomers B, anti-
Answer monomer C, reaction monomers D, reaction monomers E molar ratio be 6:0.8:0.8:1:1.2.
The oxidant is hydrogen peroxide, and the reducing agent is sodium hydrogensulfite, and the chain-transferring agent is thioacetic acid.Chain
The additional amount of transfer agent is the 2% of overall reaction monomer molar number, and the additional amount of oxidant is the 2% of overall reaction monomer molar number,
The additional amount of reducing agent is the 80% of oxidant.
Embodiment 6
1~5 parameter of the embodiment of the present invention such as table 1, using the poly- carboxylic of early strong viscosity reduction type synthesized in the embodiment of the present invention 1~5
Sour water-reducing agent prepares concrete, as a comparison case with commercially available Early-strength polycarboxylate superplasticizer.Then by such as the following table 2 proportion preparation
Concrete out measures the performance of concrete.
1 embodiment of the present invention of table, 1~5 parameter
2 concrete mix of table (C40)
Additive of the invention is the early strong viscosity reduction type polycarboxylate water-reducer of embodiment 1-5 and common water reducing type polycarboxylic acids diminishing
The mixture (solid content 20%) of agent (weight ratio 80:20).
The additive of comparative example is commercially available Early-strength polycarboxylate superplasticizer and common water reducing type polycarboxylate water-reducer (weight ratio
Mixture 80:20).
1~5 early strong viscosity reduction type polycarboxylate water-reducer and commercially available Early-strength polycarboxylate superplasticizer through the embodiment of the present invention
The concrete effect of preparation compares such as table 3:
3 concrete effect of table
From table 3 it can be seen that the concrete of the early strong viscosity reduction type polycarboxylate water-reducer of the present invention is added, with diminishing agent molecule
In structure in viscosity reduction type polymeric monomer D the PEG degree of polymerization increase, compared with adding commercially available Early-strength polycarboxylate superplasticizer concrete,
Water-reducing agent has preferably dispersibility and more high water reducing rate, has lower viscosity, better mobility, and maturing has
Smaller decrement.This test result theoretical model can be explained as follows according to the present invention:
Cement slurry viscosity depends on the water film thickness of cement particle surface, and water film thickness depends on initially adding
Water and the moisture being wrapped in floccule body.It is relied primarily in the case where low water binder ratio to improve high-grade concrete intensity
The absorption peptizaiton of additive and reduction release more Free waters in conjunction with water, in this theoretical basis, present invention reason
It is as follows by model:
Hydrophobic alkyl is located on PEG side chain, reduces the hydrophily of PEG side chain, its hydrophobicity is improved, due to a large amount of
The presence of hydrophobicity group, diminishing agent molecule can not form complete water layer film in cement particle surface, but formed to have and be lacked
The water layer film of sunken collapsing, can release more Free waters, to substantially reduce the viscosity of cement slurry, reduce simultaneously
The surface tension of water-reducing agent, reduces the convergent force of moisture evaporation, to reduce the shrinkage cracking of concrete, has good decrement
Effect, concrete crushing strength improve.Wherein the effect of embodiment 4 is best.
The superior early strong effect of concrete is derived from a large amount of cationic season contained by the PEG side chain that polymeric monomer E is introduced
The early strength function of ammonium salt groups is located in the side chain of diminishing agent molecule due to quaternary ammonium salt group, and its content can be adjusted arbitrarily, is assigned
The superpower early powerful of water-reducing agent is given.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (9)
1. a kind of morning strong viscosity reduction type polycarboxylate water-reducer, which is characterized in that the morning strong viscosity reduction type polycarboxylate water-reducer is formula (I)
The structural formula of compound represented, formula (I) compound represented is as follows:
The integer that a is 10~80, the integer that b is 1~60, the integer that c is 1~80, the integer that d is 1~60, e are the whole of 1-80
Number；Preferably, e is the integer of 10-60；
A isR1For H or CH3；
B isR2For H or CH3, R3For CH2、CH2CH2Or
OCH2CH2CH2CH2, m1For 0~50 integer, m2For 5~50 integer；
C isR4For H or CH3, R5For CH2、CH2CH2Or OCH2CH2CH2CH2,
N is the integer of 1-80；
D isR6For H or CH3, R7For CH2、
CH2CH2Or OCH2CH2CH2CH2, the integer of m=2~6, the integer that x is 1~60；
E:
n1For the integer of 5-60, n2For the integer of 0-50, n3For the integer of 5-60, R11、R12And R13It is respectively alone C1-3Alkyl, Z
For Cl, Br or I.
2. a kind of preparation method of morning strong viscosity reduction type polycarboxylate water-reducer, which is characterized in that the preparation method includes following step
It is rapid:
By reaction monomers B, reaction monomers C, reaction monomers D, reaction monomers E, oxidant is soluble in water obtains solution 1, will react
Monomer A and chain-transferring agent is soluble in water obtains solution 2, dissolves reduce agent in water and obtains solution 3, under normal temperature conditions, will be molten
Liquid 2 and solution 3, which are added drop-wise in solution 1, to be reacted, and solution 2 and solution 3 start simultaneously at dropwise addition, and solution 2 drips in 2~3h
Finish, 10~30min is added dropwise than solution more than 2 in solution 3, is added dropwise in 2.5~3.5h, the reaction was continued 4~8h, after reaction
The pH of solution is adjusted to 7~8, up to early strong viscosity reduction type polycarboxylate water-reducer；
The reaction monomers A is at least one of acrylic acid, methacrylic acid；
The reaction monomers B is at least one of APEG/PPG, HPEG/PPG, VPEG/PPG, TPEG/PPG；
The reaction monomers C is at least one of APEG, HPEG, VPEG and TPEG；
The reaction monomers D is viscosity reduction shrinkage type surface-active macromonomer, shown in structural formula such as formula (II),
Wherein, R6=H or CH3, R7=CH2、CH2CH2Or OCH2CH2CH2CH2；The integer of m=2~6, the integer that x is 1~60；
Shown in the structural formula such as formula (III) of the reaction monomers E,
n1For the integer of 5-60, n2For the integer of 0-50, n3For the integer of 5-60, R11、R12And R13It is respectively alone C1-3Alkyl, Z
For Cl, Br or I.
3. preparation method according to claim 2, which is characterized in that the reaction monomers D is prepared by following methods:
Initiator enol is mixed with catalyst, under protective gas atmosphere, epoxyalkane is at the uniform velocity added dropwise at 80~120 DEG C,
It is added dropwise in 2~4h, the reaction was continued at 90~110 DEG C 6~12h obtains reaction monomers D；
Shown in the structural formula of the epoxyalkane such as formula (IV),
The integer that m is 2~6.
4. preparation method according to claim 3, which is characterized in that the enol is allyl alcohol, isobutene alcohol, 4- hydroxyl fourth
At least one of base vinyl ethers and prenol, the catalyst are sodium hydride or sodium, and the protective gas is nitrogen.
5. preparation method according to claim 3, which is characterized in that the methallyl alcohol, epoxyalkane and epoxy fourth
The molar ratio of acid esters is 1:1~60.
6. preparation method according to claim 2, which is characterized in that the reaction monomers A, reaction monomers B, reaction monomers
C, reaction monomers D, reaction monomers E molar ratio be 5~10:0.4~1.0:0.6~1.2:0.8~2.0:0.8~2.0.
7. preparation method according to claim 2, which is characterized in that the additional amount of the chain-transferring agent is overall reaction monomer
The 0.05~5% of molal quantity, the additional amount of the oxidant are the 0.05~5% of overall reaction monomer molar number, the reducing agent
Additional amount be oxidant 20%~100%.
8. preparation method according to claim 2, which is characterized in that the oxidant is hydrogen peroxide, the reducing agent
For one or both of ascorbic acid, sodium hydrogensulfite, the chain-transferring agent be one of thioacetic acid, mercaptopropionic acid or
Two kinds.
9. early strong viscosity reduction type polycarboxylate water-reducer as described in claim 1 is preparing the purposes in concrete.
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