CN105199032B - A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof - Google Patents
A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof Download PDFInfo
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- CN105199032B CN105199032B CN201510666067.3A CN201510666067A CN105199032B CN 105199032 B CN105199032 B CN 105199032B CN 201510666067 A CN201510666067 A CN 201510666067A CN 105199032 B CN105199032 B CN 105199032B
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Abstract
The invention provides a kind of ultra high early strength poly-carboxylic water reducer, the ultra high early strength poly-carboxylic water reducer is the compound shown in formula (I), the ultra high early strength poly-carboxylic water reducer of the present invention is using surface-active macromonomer as Material synthesis, while the space steric effect of water reducer is further improved, cation is introduced in the molecule, and cation has good anti-mud, so that the water-reducing rate of water reducer is improved, resistance to mud and the adaptability to cement.There is more preferable tolerance to soil, do not occur even intercalation with soil.The cation of the ultra high early strength poly-carboxylic water reducer of the present invention can suppress the expansion of soil, so as to reduce absorption of the soil to additive.The ultra high early strength poly-carboxylic water reducer of the present invention can accelerate water and the change effect of cement, with super hardening effect.The ultra high early strength poly-carboxylic water reducer of the present invention is acted in normal concrete with super hardening, resistance to mud.
Description
Technical field
The present invention relates to a kind of water reducer, and in particular to a kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof.
Background technology
In recent years, the research of concrete admixture has tended to develop towards high-performance, pollution-free direction with production, concrete
Water reducer is that application surface is most wide in concrete admixture, the maximum one kind of usage amount., can in water reducer incorporation fresh concrete
The flocculent structure of cement granules is destroyed, plays a part of disperse cement particles and hydrated cementitious particle, so as to discharge flocculation knot
Free water in structure, increases the mobility of concrete mix.PCEs water reducers belong to anionic surfactant, mix water
In slurry body, adsorb in the cement particle surface with cation, and be dissociated into hydrophilic and oleophilic function organic anion base
Group.
Water reducer molecular skeleton is made up of main chain and more side chain.Contain more active group, and polarity on main chain
Relatively strong, by these active groups, main chain " can be anchored " on cement particle surface, and side chain has hydrophily, Ke Yishen
Exhibition in the liquid phase, so as to form larger three-dimensional adsorption structure in cement particle surface, produces space steric effect, so that water
Mud particle is scattered and stably.Carboxylic acid ion makes the negative electrical charge on cement granules band produce Coulomb repulsion work between cement granules
With, and disperseing cement granules, contact of the increase cement granules with water makes the abundant aquation of cement.In the mistake of disperse cement particles
Cheng Zhong, discharges the Free water that agglomerate is included, improves workability, reduce and mix water.
RCOO-With Ca2+Ionization forms complex compound, reduces the Ca in solution2+Concentration, delays Ca (OH)2Form knot
Crystalline substance, reduces the formation of C-H-S gels, has delayed the aquation of cement.
Polycarboxylate water-reducer (PCEs) with combed molecular structure generally by polyethoxy (PEO) side chain graft to it is cloudy from
Constituted on the main chain of son, PEO side chains produce space steric effect between the cement granules for being suspended in aqueous phase, by adjusting PCEs
Molecular structure, different purposes can be reached, such as slump retaining is good, water-reducing rate is high, and cohesiveness is good, and resistance to mud is good etc., it is in addition low
Cost, it is pollution-free the advantages of, polycarboxylate water-reducer research turn into domestic and international concrete admixture research and develop focus.
The primary raw material of poly carboxylic acid series water reducer has unsaturated acids, such as maleic anhydride, maleic acid and acrylic acid, metering system
The polymerizable carboxylic acid such as acid, the alkenyl material such as polyalkenyl hydrocarbon, ether, alcohol, poly styrene sulfonate or ester and acrylates, ester,
Benzenediol, acrylamide etc., synthetic method generally have the direct copolymerization of polymerisable monomer, polymerization Post functionalization method, in-situ polymerization
With grafting etc..
The direct copolymerization of polymerisable monomer：This synthetic method usually first prepares the big list of pendant reactive with polymerization activity
Body (being usually methoxy polyethylene glycol methacrylate-styrene polymer), then the monomer of certain match ratio is mixed, directly adopt
Finished product is obtained with polymerisation in solution.This polymerization, technique is simple, but on condition that want the polymerizable surface-active macromonomer of synthesizing activity,
And the performance of surface-active macromonomer directly determines and affected the performance of final products polycarboxylate water-reducer.
The active polymeric monomer that current China market is used to produce PCEs water reducers mainly has：
MPEG：Poly glycol monomethyl ether
VPEG:4- hydroxy butyl vinyl ether APEOs
APEG：Allyl alcohol polyethenoxy ether
HPEG：Isobutene alcohol APEO
TPEG：Isoamyl alcohol polyoxyethylene ether
APEG is bar-shaped rigid structure, high to cement adsorbance, and TPEG microstructures are star-shape polymers, with flexibility
Segment microstructure is few to cement adsorbance.
APEG is the primary raw material of synthesizing polycarboxylic acid high-performance water reducing agent, and the PCEs water reducers of synthesis have dispersiveness
Good, volume is low, the advantages of water-reducing rate is high, adaptability is good；Have the disadvantage inferior suitability, Slump Time losing of Large is big.HPEG with
TPEG is the water reducer that raw material is produced, and water-reducing rate is more or less the same, but summer uses, and slump retaining gap is larger, and cement adaptability is slightly
Difference.Using the polycarboxylate water-reducer that TPEG is main material production, water-reducing rate is high, and slump retaining is good, strong to cement adaptability, production
Process equipment is simple, and by polycarboxylate water-reducer, manufacturer favors.But complexity due to China's concrete raw material and various
Property, especially when the soil content of sandstone is big, the slump-loss of concrete is big, the polycarboxylate water-reducer produced by TPEG,
Because even intercalation occurs for PEG side chains and soil, make its resistance to mud poor, can not meet the requirement of concrete construction performance.
The content of the invention
Subtract it is an object of the invention to overcome the weak point of prior art presence there is provided a kind of ultra high early strength poly-carboxylic
Aqua and preparation method thereof, the water reducer has cationic charge in the molecular structure, due to its unique both sexes structure and sky
Between steric effect so that it has unique dispersibility, and water-reducing rate is high, and resistance to soil is good.
To achieve the above object, the technical scheme taken：A kind of ultra high early strength poly-carboxylic water reducer, the poly- carboxylic of super hardening
Sour water reducer is the compound shown in formula (I), and the structural formula of the compound shown in the formula (I) is as follows：
Wherein a is 1~80 integer, and b is 1~80 integer, and c is 1~50 integer；L is 1~50 integer；
A isR be H or
CH3；
B is
C is
M is R2、R3And R4Point
It is not C alone1-3Alkyl；X-For Cl-、Br-Or I-；M be 5~200 integer, n be 0~50 integer, z for 1~150 it is whole
Number.
The invention provides the preparation method of ultra high early strength poly-carboxylic water reducer described above, methods described includes following step
Suddenly：
By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG,
One kind in VPEG and TPEG, ALS, water and molecular weight regulator mixing, is warming up to 85~95 DEG C, is added dropwise and triggers
Agent, time for adding is insulation after 1~10h, completion of dropping, and soaking time is 1~12h, is then cooled to 45~50 DEG C, adds hydrogen
Sodium hydroxide solution adjusts pH to 7.0-8.0, obtains ultra high early strength poly-carboxylic water reducer；
The surface-active macromonomer is the compound shown in formula (II), and the structural formula of the compound shown in the formula (II) is such as
Under：
Wherein R1For H2C==CH --- O --- CH2CH2CH2CH2——、H2C==CHCH2——、OrR2, R3 and R4 are C1-3 alkane alone respectively
Base；X- is Cl-, Br- or I-；
M is 5~200 integer, and n is 0~50 integer, and z is 1~150 integer.
Preferably, the m is 10~180 integer, and the n is 0~40 integer, and the z is 1~100 integer.More
Preferably, the m is 12~100 integer, and the n is 0~30 integer, and the z is 1~80 integer.
Preferably, one kind in the surface-active macromonomer, methacrylic acid, acrylic acid, itaconic acid and maleic anhydride,
A kind of mol ratio of and ALS in APEG, HPEG, VPEG and TPEG is the surface-active macromonomer：Metering system
One kind in acid, acrylic acid, itaconic acid and maleic anhydride：One kind in APEG, HPEG, VPEG and TPEG：ALS
=1.0~3.0：1~6.0：1：0.2~6.0.
Preferably, the molecular weight regulator is at least one of sulfhydryl compound and isopropanol, and the molecular weight is adjusted
The consumption of agent is saved for the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG,
The 0.005~5% of the total mole number of a kind of and acrylamide and ALS in HPEG, VPEG and TPEG.More preferably
Ground, the molecular weight regulator is at least one of 3- mercaptopropionic acids, TGA, mercaptoethanol, sodium formaldehyde sulfoxylate and isopropanol,
The consumption of the molecular weight regulator is the surface-active macromonomer, in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride
The 1~3.5% of a kind of a kind of total mole number with APEG, HPEG, VPEG and TPEG.Most preferably, the molecular weight is adjusted
The consumption for saving agent is the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride and APEG,
1.2~2.5% of a kind of total mole number in HPEG, VPEG and TPEG.
Preferably, the time for adding of the initiator is 2~3h；The soaking time is 2~4h.
Preferably, the mass concentration of the sodium hydroxide solution is 30%；The initiator is potassium peroxydisulfate, persulfuric acid
One kind in the aqueous solution of ammonium, hydrogen peroxide and benzoyl peroxide, the consumption of the initiator is the surface-active macromonomer, methyl
One kind and acrylamide in one kind in acrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, VPEG and TPEG
With the 0.05%~5% of the total mole number of ALS.
Preferably, the cation quaternary ammonium salt PEO surface-active macromonomers are prepared from by following methods：
(1) by one kind in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol, oxirane and ring
One kind in the mixture of oxidative ethane and expoxy propane, is mixed with epoxyhalopropane, adds catalyst, is 80~150 in temperature
Reacted 2~10 hours under the conditions of DEG C, obtain reactive intermediate；Its reaction equation is as follows：
(2) quarternary ammonium salt compound is mixed with polymerization inhibitor, the reactive intermediate for being slowly added to step (1) synthesis is in temperature
1~10h is reacted under the conditions of 10~80 DEG C, the surface-active macromonomer is obtained；Its reaction equation is as follows：
The quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is C alone respectively1-3Alkyl.
Preferably, in the step (1) in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol one
Kind, one kind in the mixture of oxirane and oxirane and expoxy propane, the mol ratio with epoxyhalopropane is allyl alcohol,
One kind in isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol：Oxirane and oxirane and expoxy propane it is mixed
One kind in compound：Epoxyhalopropane=1:5~250:1~150.
Preferably, the mol ratio of quarternary ammonium salt compound and reactive intermediate is 0.2 in the step (2):1~2:1.
Preferably, catalyst is sodium hydride or sodium in the step (1)；Polymerization inhibitor is hydroquinones in the step (2)
Or to methyl ether phenol, the consumption of the polymerization inhibitor is the 0.02%~0.08% of the reactive intermediate molal quantity.
The beneficial effects of the present invention are：The invention provides a kind of ultra high early strength poly-carboxylic water reducer, relative to existing skill
Art, its advantage is：
The ultra high early strength poly-carboxylic water reducer of the present invention is entering using cation quaternary ammonium salt PEO surface-active macromonomers as Material synthesis
While one step improves the space steric effect of water reducer, cation is introduced in the molecule, and cation has good anti-mud,
So as to improve the water-reducing rate of water reducer, resistance to mud and the adaptability to cement.There is more preferable tolerance to soil, with soil not
Generation connects intercalation.
The cation of the ultra high early strength poly-carboxylic water reducer of the present invention can suppress the expansion of soil, so as to reduce soil to additional
The absorption of agent.When the ultra high early strength poly-carboxylic water reducer of the present invention is added in cement slurry, the anionic charge absorption of main chain
In positively charged cement particle surface, and the positive charge of side chain end group is then adsorbed in negatively charged cement particle surface, point
Bulk cement particle.Because polyhydroxy and water are into hydrogen bond, the viscosity of cement slurry is added, the flowing of concrete mix is improved
Property and cohesiveness.
The ultra high early strength poly-carboxylic water reducer of the present invention can accelerate water and the change effect of cement, with super hardening effect.This hair
Bright ultra high early strength poly-carboxylic water reducer is in normal concrete, with the effect of resistance to mud, in pipe pile body concrete, with super
Early strength function, can be achieved pile tube singly exempt from and it is double exempt from technique, without adding any active mineral admixture.
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.
Embodiment 1
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
5mol prenols, 5g sodium hydrides, 25mol oxirane, and 5mol epoxy chlorine are injected in the autoclave of closing
Propane, stirring, 80 DEG C of reaction 10h produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
1mol triethylamines and 0.001mol hydroquinones are added in flask, 10 DEG C is warming up to, is slowly added dropwise containing 5mol
After the triethylamine solution of the reactive intermediate of step (1) synthesis, completion of dropping, under the conditions of 10 DEG C, continue insulation reaction 10h,
Produce surface-active macromonomer.
Embodiment 2
A kind of embodiment of the preparation method of cation quaternary ammonium salt PEO surface-active macromonomers of the present invention：
1), the synthesis of reactive intermediate
5mol isobutene alcohols, 20g sodium hydrides, 500mol oxirane, 250mol epoxies are injected in the autoclave of closing
Propane, and 750mol epoxy bromopropanes, stirring, 150 DEG C of reaction 2h produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
3mol trimethylamines and 0.004mol hydroquinones are added in flask, 30 DEG C is warming up to, is slowly added dropwise containing 5mol
After the trimethylamine solution of the reactive intermediate of step (1) synthesis, completion of dropping, under the conditions of 30 DEG C, continue insulation reaction 10h,
Produce surface-active macromonomer.
Embodiment 3
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
5mol allyl alcohols, 10g sodium hydrides, 1000mol oxirane, and 400mol epoxies are injected in the autoclave of closing
Iodopropane, stirring, 100 DEG C of reaction 6h produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
5mol tripropyl amine (TPA)s and 0.0015mol hydroquinones are added in flask, 50 DEG C is warming up to, is slowly added dropwise containing 5mol
After the tripropyl amine (TPA) solution of the reactive intermediate of step (1) synthesis, completion of dropping, under the conditions of 50 DEG C, continue insulation reaction 8h, i.e.,
Obtain surface-active macromonomer.
Embodiment 4
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
The injection 5mol 4- hydroxy butyl vinyl ethers in the autoclave of closing, 10g sodium hydrides, 50mol oxirane,
5mol expoxy propane and 500mol Epiiodohydrins, stir 120 DEG C of reaction 5h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 7mol N, N- dimethyl amines and 0.0025mol are added in flask to methyl ether phenol, are warming up to 70 DEG C, slowly
It is added dropwise after the N of the reactive intermediate synthesized containing 5mol steps (1), N- dimethyl amine solution, completion of dropping, in 70 DEG C of conditions
Under, continue insulation reaction 4h, produce surface-active macromonomer.
Embodiment 5
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
The injection 5mol allyl alcohols in the autoclave of closing, 10g sodium, 900mol oxirane, 150mol expoxy propane, and
250mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 10mol N, N- diethyl methyl amines and 0.002mol are added in flask to methyl ether phenol, are warming up to 80 DEG C, slowly
It is added dropwise after the N of the reactive intermediate synthesized containing 5mol steps (1), N- diethyl methyl amine solution, completion of dropping, in 80 DEG C of conditions
Under, continue insulation reaction 1h, produce surface-active macromonomer.
Embodiment 6
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer described in 1.0mol embodiments 1,1mol methacrylic acids, 1.0mol APEG, 0.2mol ALS and
400ml deionized waters, the molecular weight regulator is 3- mercaptopropionic acids, and the consumption of the molecular weight regulator is big for the activity
Monomer, methacrylic acid, the 0.005% of ALS and APEG total mole numbers, are warming up to 85 DEG C, and the water of initiator is added dropwise
Solution, the initiator is potassium peroxydisulfate, and the consumption of the initiator is the surface-active macromonomer, methacrylic acid, pi-allyl
The 0.05% of sodium sulfonate and APEG total mole numbers, after time for adding is 1h, completion of dropping, insulation reaction 1h is cooled at 50 DEG C,
The NaOH solution that mass concentration is 30% is added, pH=7.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 7
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer described in 2mol embodiments 2,2mol acrylic acid, 1mol HPEG, 1mol ALS and 600ml deionizations
Water, the molecular weight regulator is TGA, the consumption of the molecular weight regulator is the surface-active macromonomer, acrylic acid,
The 5% of ALS and HPEG total mole numbers, is warming up to 95 DEG C, and the aqueous solution of initiator is added dropwise, and the initiator was
Ammonium sulfate, the consumption of the initiator is the surface-active macromonomer, acrylic acid, ALS and HPEG total mole numbers
5%, after time for adding is 10h, completion of dropping, insulation reaction 12h is cooled at 45 DEG C, and it is 30% to add mass concentration
NaOH solution, adjusts pH=8.0, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 8
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 6mol acrylic acid, 1mol TPEG, 6mol ALS and 500ml deionizations described in 3mol embodiments 3
Water, the molecular weight regulator is mercaptoethanol, the consumption of the molecular weight regulator is the surface-active macromonomer, acrylic acid,
The 1% of ALS and TPEG total mole numbers, is warming up to 90 DEG C, and the aqueous solution of initiator is added dropwise, and the initiator was
BP, the consumption of the initiator is the surface-active macromonomer, acrylic acid, ALS and TPEG total mole numbers
0.1%, after time for adding is 5h, completion of dropping, insulation reaction 6h is cooled at 50 DEG C, and it is 30% to add mass concentration
NaOH solution, adjusts pH=7.5, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 9
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 3mol methacrylic acids, 1.0mol VPEG, 3mol ALS and 400ml described in 3mol embodiments 4
Deionized water, the molecular weight regulator is isopropanol, and the consumption of the molecular weight regulator is the surface-active macromonomer, methyl
The 3.5% of acrylic acid, ALS and VPEG total mole numbers, is warming up to 85 DEG C, and the aqueous solution of initiator is added dropwise, described to draw
Hair agent is hydrogen peroxide, and the consumption of the initiator is that the surface-active macromonomer, methacrylic acid, ALS and VPEG are total
The 3% of molal quantity, after time for adding is 2h, completion of dropping, insulation reaction 2h is cooled at 50 DEG C, is added mass concentration and is
30% NaOH solution, adjusts pH=7.0, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 10
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 1mol acrylic acid, 1mol HPEG, 3mol ALS and 600ml deionizations described in 3mol embodiments 5
Water, the molecular weight regulator is TGA, the consumption of the molecular weight regulator is the surface-active macromonomer, acrylic acid,
The 1.2% of ALS and HPEG total mole numbers, is warming up to 95 DEG C, and the aqueous solution of initiator is added dropwise, and the initiator is
Ammonium persulfate, the consumption of the initiator is the surface-active macromonomer, acrylic acid, ALS and HPEG total mole numbers
2%, after time for adding is 3h, completion of dropping, insulation reaction 4h is cooled at 45 DEG C, adds the NaOH that mass concentration is 30%
Solution, adjusts pH=8.0, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 11
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 4mol acrylic acid, 1mol TPEG, 4mol ALS and 500ml deionizations described in 1mol embodiments 1
Water, the molecular weight regulator is mercaptoethanol, the consumption of the molecular weight regulator is the surface-active macromonomer, acrylic acid,
The 2.5% of ALS and TPEG total mole numbers, is warming up to 90 DEG C, and the aqueous solution of initiator is added dropwise, and the initiator is
Benzoyl peroxide, the consumption of the initiator is the surface-active macromonomer, acrylic acid, ALS and TPEG total moles
Several 1%, after time for adding is 7h, completion of dropping, insulation reaction 8h is cooled at 50 DEG C, and it is 30% to add mass concentration
NaOH solution, adjusts pH=7.5, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 12
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer described in 1.6mol embodiments 2,1.2mol methacrylic acids, 1.0mol APEG, 1.6mol ALS and
400ml deionized waters, the molecular weight regulator is 3- mercaptopropionic acids, the consumption of the molecular weight regulator is the activity
Polymeric monomer, methacrylic acid, the 2% of ALS and APEG total mole numbers, are warming up to 85 DEG C, and the water-soluble of initiator is added dropwise
Liquid, the initiator is potassium peroxydisulfate, and the consumption of the initiator is the surface-active macromonomer, methacrylic acid, pi-allyl sulphur
The 1.5% of sour sodium and APEG total mole number, after time for adding is 9h, completion of dropping, insulation reaction 10h is cooled at 50 DEG C, plus
Enter the NaOH solution that mass concentration is 30%, adjust pH=7.0, produce ultra high early strength poly-carboxylic water reducer.
Embodiment 13
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer described in 1.0mol embodiments 3,2mol acrylic acid, 1mol HPEG, 2.0mol ALS and 600ml go
Ionized water, the molecular weight regulator is TGA, and the consumption of the molecular weight regulator is the surface-active macromonomer, propylene
The 0.1% of sour, ALS and HPEG total mole numbers, is warming up to 95 DEG C, and the aqueous solution of initiator, the initiator is added dropwise
For ammonium persulfate, the consumption of the initiator is the surface-active macromonomer, acrylic acid, ALS and HPEG total mole numbers
0.5%, after time for adding is 3h, completion of dropping, insulation reaction 4h is cooled at 45 DEG C, and it is 30% to add mass concentration
NaOH solution, adjusts pH=8.0, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 14
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention：
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer described in 1mol embodiments 4,1mol acrylic acid, 1mol TPEG, 1mol ALS and 500ml deionizations
Water, the molecular weight regulator is mercaptoethanol, the consumption of the molecular weight regulator is the surface-active macromonomer, acrylic acid,
The 0.01% of ALS and TPEG total mole numbers, is warming up to 90 DEG C, and the aqueous solution of initiator is added dropwise, and the initiator is
Benzoyl peroxide, the consumption of the initiator is the surface-active macromonomer, acrylic acid, ALS and TPEG total moles
Several 4%, after time for adding is 1h, completion of dropping, insulation reaction 12h is cooled at 50 DEG C, and it is 30% to add mass concentration
NaOH solution, adjusts pH=7.5, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 15：Practical application technique effect of the ultra high early strength poly-carboxylic water reducer of the present invention in concrete
Concrete is prepared using the ultra high early strength poly-carboxylic water reducer synthesized in the embodiment of the present invention 6~14, gathered with common
As a comparison, common polycarboxylate water-reducer is the polycarboxylate water-reducer without cation quaternary ammonium salt to carboxylic acid water reducer.Survey first
Determine the ultra high early strength poly-carboxylic water reducer that is synthesized in the embodiment of the present invention 6~14 and the water-reducing rate of common polycarboxylate water-reducer,
Then concrete is prepared by following proportioning, determines setting time, 2h slump-loss and the maturing intensity of concrete
The performances such as development.
The match ratio of normal concrete is as follows：
Cement：Flyash：Miberal powder：River sand：Rubble：Water：Common polycarboxylate water-reducer=200：90：60：800：1080：
165：8.5；
The match ratio of concrete is as follows made from the ultra high early strength poly-carboxylic water reducer of the embodiment of the present invention 6~14：
Cement：Flyash：Miberal powder：River sand：Rubble：Water：Polycarboxylate water-reducer=200 of the present invention：9：60：800：1080：
165：7.0.
The coagulation prepared by the ultra high early strength poly-carboxylic water reducer of the embodiment of the present invention 6~14 and common polycarboxylate water-reducer
Native effect is compared as follows：
As can be seen here, ultra high early strength poly-carboxylic water reducer of the invention is used in concrete, with common polycarboxylate water-reducer
Compare, have more preferable dispersiveness to cement slurry, water-reducing rate is improved, simultaneously because the cation of side chain is adsorbed with suppression to clay
Make and use, resistance to mud is good；There is super hardening effect simultaneously, cement hydrationization can be promoted to react, the intensity to maturing is sent out
Exhibition plays a driving role.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention
And scope.
Claims (10)
1. a kind of ultra high early strength poly-carboxylic water reducer, it is characterised in that the ultra high early strength poly-carboxylic water reducer is the change shown in formula (I)
Compound, the structural formula of the compound shown in the formula (I) is as follows：
Wherein a isInteger, b isInteger, c isInteger；L isInteger；
A isR is H or CH3；
B is
C is
M is R2、R3And R4Point
It is not C alone1-3Alkyl；X-It is Cl-、Br-Or I-；M isInteger, n is Integer, z isInteger.
2. a kind of preparation method of ultra high early strength poly-carboxylic water reducer as claimed in claim 1, it is characterised in that methods described bag
Include following steps：
By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, VPEG and
One kind in TPEG, ALS, water and molecular weight regulator mixing, is warming up to 85~95 DEG C, initiator is added dropwise, be added dropwise
Time is insulation after 1~10h, completion of dropping, and soaking time is 1~12h, is then cooled to 45~50 DEG C, adds sodium hydroxide
Solution adjusts pH to 7.0-8.0, obtains ultra high early strength poly-carboxylic water reducer；
The surface-active macromonomer is the compound shown in formula (II), and the structural formula of the compound shown in the formula (II) is as follows：
Wherein R1For H2C=CH-O-CH2CH2CH2CH2-、H2C=CHCH2-、
R2、R3And R4It is C alone respectively1-3Alkyl；X-For Cl-、Br-Or I-；
M isInteger, n isInteger, z isInteger.
3. preparation method according to claim 2, it is characterised in that the surface-active macromonomer, methacrylic acid, propylene
A kind of mole of and ALS in one kind in acid, itaconic acid and maleic anhydride, APEG, HPEG, VPEG and TPEG
Than for the surface-active macromonomer：One kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride：APEG、HPEG、VPEG
With one kind in TPEG：ALS=1.0~3.0：1~6.0：1：0.2~6.0.
4. preparation method according to claim 2, it is characterised in that the molecular weight regulator is sulfhydryl compound and different
At least one of propyl alcohol, the consumption of the molecular weight regulator is the surface-active macromonomer, methacrylic acid, acrylic acid, clothing
One kind in health acid and maleic anhydride, a kind of and acrylamide and ALS in APEG, HPEG, VPEG and TPEG
The 0.005~5% of total mole number.
5. preparation method according to claim 2, it is characterised in that the time for adding of the initiator is 2~3h；It is described
Soaking time is 2~4h.
6. preparation method according to claim 2, it is characterised in that the mass concentration of the sodium hydroxide solution is
30%；The initiator is one kind in potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide, the initiator
Consumption is the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG,
The 0.05%~5% of the total mole number of a kind of and acrylamide and ALS in VPEG and TPEG.
7. preparation method according to claim 2, it is characterised in that the surface-active macromonomer prepared by following methods and
Into：
(1) by one kind in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol, oxirane and epoxy second
One kind in the mixture of alkane and expoxy propane, is mixed with epoxyhalopropane, adds catalyst, is 80~150 DEG C of bars in temperature
Reacted 2~10 hours under part, obtain reactive intermediate；
(2) quarternary ammonium salt compound is mixed with polymerization inhibitor, be slowly added to step (1) synthesis reactive intermediate temperature be 10~
1~10h is reacted under the conditions of 80 DEG C, the surface-active macromonomer is obtained；
The quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is C alone respectively1-3Alkyl.
8. preparation method according to claim 7, it is characterised in that allyl alcohol, isobutene alcohol, 4- in the step (1)
One in the mixture of one kind in hydroxy butyl vinyl ether and prenol, oxirane and oxirane and expoxy propane
Kind, the mol ratio with epoxyhalopropane is one kind in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol：
One kind in the mixture of oxirane and oxirane and expoxy propane：
9. preparation method according to claim 7, it is characterised in that quarternary ammonium salt compound and activity in the step (2)
The mol ratio of intermediate is 0.2:1~2:1.
10. preparation method according to claim 7, it is characterised in that in the step (1) catalyst be sodium hydride or
Sodium；Polymerization inhibitor is for hydroquinones or to methyl ether phenol in the step (2), and the consumption of the polymerization inhibitor is the reactive intermediate
The 0.02%~0.08% of molal quantity.
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| CN106365534B (en) * | 2016-08-27 | 2018-03-06 | 广东红墙新材料股份有限公司 | Purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared |
| CN106587708B (en) * | 2016-12-20 | 2018-10-16 | 浙江建研科之杰新材料有限公司 | A kind of pervious concrete polycarboxylate water-reducer and preparation method thereof |
| CN106632891A (en) * | 2016-12-27 | 2017-05-10 | 陕西友邦新材料科技有限公司 | Polycarboxylate superplasticizer mother solution based on steam-cured concrete and preparation method of polycarboxylate superplasticizer mother solution |
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