CN104059199B - A kind of polycarboxylic acids super-slowly coagulating water reducer and its production and use - Google Patents
A kind of polycarboxylic acids super-slowly coagulating water reducer and its production and use Download PDFInfo
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Abstract
The present invention discloses the preparation method of a kind of polycarboxylic acids super-slowly coagulating water reducer, and described method utilizes macromolecular structure design principle, uses new and high technology means, synthesizes a kind of super-slowly coagulating water reducer having diminishing and slow setting function concurrently.This super-retarder is a kind of organic high molecular compound by several functional monomer copolymerization, containing substantial amounts of hydroxy functional group in its molecular structure, the most similar structure is had to high-efficiency water-reducing agent of poly-carboxylic acid, similar person is compatible, so polycarboxylic acids super-slowly coagulating water reducer prepared by the method for the invention and high-efficiency water-reducing agent of poly-carboxylic acid have extraordinary dissolubility and the compatibility, during compounding use, notable to the retarding effect of fresh concrete.Meanwhile, the invention also discloses the polycarboxylic acids super-slowly coagulating water reducer using described method to prepare, and the purposes that described polycarboxylic acids super-slowly coagulating water reducer is in concrete.
Description
Technical field
The present invention relates to retarder in a kind of concrete and preparation method thereof, especially a kind of for super slow
Super-retarder in solidifying concrete and preparation method thereof.
Background technology
Concrete construction often requires that the setting time delaying concrete, in order to constructing operation and guarantee coagulation
The quality of soil.Concrete construction in hot day, temperature is high, and concrete coagulation is accelerated, and slump-loss is accelerated, very
Lose flowability energy soon, can bring difficulty to construction, affect construction quality, it requires that concrete has longer
Setting time.Mass concrete construction needs to extend the setting time of concrete, delays hydration heat mistake
Journey, reduces the crack produced because of temperature stress, and these are required to fill retarder to improve the performance of concrete.
Retarder is a kind of additive that can extend concrete coagulating time, and retarder is mainly used for delaying water
The hydration and hardening speed of mud, so that fresh concrete keeps plasticity in a long time, is beneficial to the fortune of concrete
Defeated, pour and vibrate；The time that temperature peak of hydration occurs can be postponed, reduce temperature peak of hydration value, prevent substantially
There is thermal cracking in long-pending concrete；The adaptability of high efficiency water reducing agent and cement can be adjusted, reduce concrete and mix
Compound slump-loss.
Component in retarder is different, and they are different to concrete retarding mechanism.The retarder slow setting machine to cement
Reason includes: precipitation hypothesis, complex salt hypothesis, adsorption hypothesis, become karyogenesis hypothesis, core for hinder cement with
The hydration of water, thus reach the purpose of slow setting.
The impact of fresh mixing concrete property is mainly had by retarder: delay concrete just final setting time；Reduce water
Change rate of heat release；Reduce slump-loss.From the point of view of the development of intensity, incorporation retarder, concrete 1d,
3d intensity is low, but has not significant impact later strength.If but volume is excessive, then due to the steaming of moisture
Send out and scatter and disappear, concrete strength can be caused permanent expendable impact.
General goods concrete retarder, owing to having the character introducing air, volume is too much, can cause mixed
The reduction of solidifying soil intensity and harden bad, and the slow setting time is shorter, fundamentally cannot be used need to continue for a long time mixed
The place that solidifying soil condenses, the most common retarder presetting period about 8-10h, it is extremely difficult to guarantor and collapses the time relatively
Long effect.But super-retarder can extend the condensation of concrete for a long time, its slow setting time can be according to mixing
Amount carrys out manual control, and concrete slump-loss within the longer time is less, and general final setting time exists
More than 50h, can effectively reduce the aquation temperature rise of concrete.
Some special engineering, it is desirable to concrete can not condense in more than 10 skies, after once condensing, by force
Degree normally can increase again as normal concrete.In order to distinguish conventional retarder, usual people are delaying
Act on the strongest retarder setting time and be referred to as " super-retarder ".Concrete ultra-retarding agent is to occur the beginning of the nineties
A new concrete admixture kind, it connects stranding face in preventing concrete construction, cold junction and substantially
Long-pending concrete construction occurs that the aspect effects such as thermal cracking are notable.
Super-retarder is a kind of novel concrete admixture, is the new class proposed concrete production in recent years
Topic, super-retarder can not only for a long time in setting time of (>=24h) arbitrarily regulation concrete, and right
The performance of concrete, without negative effect, becomes one of focus of additive technical research in recent years.Slow with common
Solidifying agent is compared, and super-retarder can not only make up the limitation on setting time, and it can be avoided that to concrete
The impact of later strength, widens the application of concrete.Ultra-retardation concrete is in mass concrete construction
In, in order to prevent thermal cracking, cold joint, control slump loss from having important application prospect.Extra retarded set mixes
On the one hand solidifying soil require that concrete has longer setting time in early days, and on the other hand, concrete must have again
Enough later strengths.Preparation ultra-retardation concrete it is crucial that control setting time of concrete well, use
Super-retarder is the Main Means making concrete have extra retarded set performance.
Ultra-retardation concrete is mainly used in the mass concrete construction needing continuous placing at present, permissible
Effectively reduce the absolute temperature rise of concrete, it is to avoid temperature stress makes concrete produce crack.For summer high temperature ring
The concrete of construction under border, super-retarder can extend the haulage time of concrete, reduces slump-loss,
It is to ensure that concrete pumping, the effective ways watering and constructing.It addition, a certain amount of super-retarder can be protected
Demonstrate,prove the needs of long-time concrete construction, it is to avoid connect and rub existing cold junction and carry on construction work at night, it is achieved that concrete
The variation of construction technology.
At present, the kind of super-retarder mainly has two big classes:
1, the organic matter non-research work of air entrained type super-retarder with oxygen-containing carboxylate as main component；
2, the inorganic super-retarder with fluosilicate as main component.
To mainly Japan of super-retarder research country earlier.In the eighties in 20th century, latter stage develops the earliest
Out, and be successfully applied to the preparation of ultra-retardation concrete.Compared with developed countries, China is in this regard
Studying relative with technological development later, product relies primarily on import.Within considerable time from now on, super slow
Solidifying agent will be all the high-rise key with Super High underwater pile concrete of preparation, is the most also to improve concrete
The Main Means of high performance, the research carrying out China's autonomous innovation super-retarder becomes the task of top priority.
Super-retarder itself does not have water-reducing property, uses so that compounding with cement water reducing agent, to protect
Card concrete has enough plasticity, setting time and later strength.But at super-retarder and concrete diminishing
During the compounding use of agent, it is frequently encountered by the unmatched problem of the compatibility.
Summary of the invention
One is provided to have diminishing concurrently with slow in place of it is an object of the invention to overcome above-mentioned the deficiencies in the prior art
The polycarboxylic acids super-slowly coagulating water reducer of solidifying function；Meanwhile, present invention also offers described polycarboxylic acids extra retarded set diminishing
The preparation method of agent and the purposes in concrete thereof.
For achieving the above object, the technical scheme that the present invention takes is: a kind of polycarboxylic acids super-slowly coagulating water reducer
Preparation method, said method comprising the steps of:
(1) preparation of hydroxylated methyl glycidyl acrylate
In the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, add glycerol, metering system
Acid glycidyl ester, polymerization inhibitor and catalyst, rise high-temperature to 80～90 DEG C, isothermal reaction 4～6h, to obtain final product
Hydroxylated methyl glycidyl acrylate；
(2) preparation of polycarboxylic acids super-slowly coagulating water reducer
The hydroxylating first that addition water, chain-transferring agent, initiator, step (1) prepare in four-hole boiling flask
The poly-second of base glycidyl acrylate, Hydroxypropyl acrylate, methacrylic acid, maleic anhydride and methoxyl group two
Alcohol methacrylate macromer, is heated to 95 DEG C, reacts 6～8h, is cooled to less than 45 DEG C, adds 30wt%
Alkali liquor, the pH value of regulation system so that pH=7, obtain polycarboxylic acids super-slowly coagulating water reducer.
The preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, utilizes macromolecular structure design principle,
Use new and high technology means, synthesize a kind of super-slowly coagulating water reducer having diminishing and slow setting function concurrently.This extra retarded set
Agent is a kind of organic high molecular compound by several functional monomer copolymerization, contains in its molecular structure
Substantial amounts of hydroxy functional group, it is possible to form stable complex with the calcium ion complexation in cement slurry, covers
On the surface of hydrolysis product of cement, stop hydrated cementitious.On the other hand, the hydroxyl in super-retarder structure is also
Cement particle surface can be directly adsorbed in by hydrogen bond, stop cement granules to contact with the direct of water, stop
The carrying out of aquation.Along with the carrying out of hydration process, this adsorption layer will gradually use up, and aquation will normally continue
Carry out, the most do not affect cement further hydration.The super-slowly coagulating water reducer of gained and polycarboxylate water-reducer adaptability
Preferably, use can also be compounded therewith.
As the preferred implementation of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, described step
Suddenly, in (1), the mole of described glycerol and glycidyl methacrylate is than for 1:0.95～1:0.5, described
The mole of polymerization inhibitor is the 0.02～0.06% of glycidyl methacrylate mole, described catalyst
Mole is the 0.5～3% of glycidyl methacrylate mole.
As the preferred implementation of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, described step
Suddenly in (1) polymerization inhibitor be hydroquinone, at least one in methyl ether phenol, diphenylamines；Described catalyst
For pyridine, tetraalkylammonium salt, FeCl3In at least one.
As the preferred implementation of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, described step
Suddenly hydroxylated methyl glycidyl acrylate, Hydroxypropyl acrylate, methacrylic acid, maleic acid in (2)
The mol ratio of acid anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer is 1:1.5:1:0.5:1, described
The mole of chain-transferring agent and initiator is respectively hydroxylated methyl glycidyl acrylate, acrylic acid hydroxypropyl
Ester, methacrylic acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer integral molar quantity
1～5%, 0.5～5%.
As the preferred implementation of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, described step
Suddenly the chain-transferring agent in (2) is at least in mercaptoethanol, TGA, mercaprol, mercaptopropionic acid
Kind；Described initiator be Ammonium persulfate., potassium peroxydisulfate at least one.
As the preferred implementation of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, described step
Suddenly the water in (2) is deionized water, and the volume of described water is the 0.3～0.5 of four-hole boiling flask volume；Described alkali liquor
For NaOH solution.
As the preferred implementation of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, described step
Suddenly the methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer in (2) uses following methods to be prepared from: at dress
Have in the four-hole boiling flask of agitator, thermometer and reflux condensing tube, add methoxy poly (ethylene glycol), polymerization inhibitor
And initiator, liter high-temperature to 80～85 DEG C, until completely dissolved, disposably adds methacrylic acid, continues
It is warming up to 125～130 DEG C, isothermal reaction 10～12h, obtain the big list of methoxy polyethylene glycol methacrylate-styrene polymer
Body.Described methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer can use approach described above to prepare gained,
Can also directly be purchased from market etc..
As the preferred implementation of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention, described resistance
The mole of poly-agent is the 0.02～0.06% of methoxy poly (ethylene glycol) mole, described methoxy poly (ethylene glycol)
The mole of mole and methacrylic acid is than for 1:1.2～2, and the molecular weight of described methoxy poly (ethylene glycol) is
750～5000, the mole of initiator is methoxy poly (ethylene glycol) and methacrylic acid integral molar quantity
0.5～2.5%；As the more preferably embodiment of the preparation method of polycarboxylic acids super-slowly coagulating water reducer of the present invention,
Described polymerization inhibitor is hydroquinone, at least one in methyl ether phenol, diphenylamines, described initiator was
BP.
It addition, the present invention also provides for a kind of polycarboxylic acids extra retarded set diminishing using method as defined above to prepare
Agent.Use the polycarboxylic acids super-slowly coagulating water reducer that method described above prepares, have the merit of diminishing and slow setting concurrently
Can, containing substantial amounts of hydroxy functional group in its molecular structure, have the most similar to high-efficiency water-reducing agent of poly-carboxylic acid
Structure, similar person is compatible, so polycarboxylic acids super-slowly coagulating water reducer of the present invention and the efficient diminishing of polycarboxylic acids
Agent has extraordinary dissolubility and the compatibility, during compounding use, notable to the retarding effect of fresh concrete,
And by regulating the mixed ratio of this product and polycarboxylate water-reducer, preparation has the super slow of different setting time
Solidifying concrete.Meanwhile, mix polycarboxylic acids of the present invention and surpass coagulation water reducer, the performance to fresh concrete
Improve clearly, concrete water conservation protect plasticity good, Slump Time losing of Large is little, concreting rear portion from
Analysis, not bleeding, according to different construction requirements, the presetting period that can control concrete is 24～120h.
Finally, present invention also offers the polycarboxylic acids super-slowly coagulating water reducer described above purposes in concrete.
When using polycarboxylic acids super-slowly coagulating water reducer of the present invention to be applied in concrete, the setting time of concrete can
Control with the addition by regulating polycarboxylic acids super-slowly coagulating water reducer of the present invention.Polycarboxylic acids of the present invention surpasses
Retardation water reducing agent is applied in concrete, and dispersibility is strong, and it has the effect of diminishing and slow setting concurrently, newly mixes coagulation
Soil cohesiveness, guarantor mould good water-retaining property, after concreting, and the most significantly isolation, bleeding phenomenon, slow setting
Effect is notable, and late strength of concrete can increase by 10～15%.
In Binder Materials hydration process, retarder forms the film layer of one layer of insoluble character at cement particle surface,
Stop cement granules to contact with the further of water, delay the hydration reaction of cement.The Main Function of retarder is
Adjust at the beginning of fresh concrete, final setting time, delay hydrated cementitious exotherm rate, alleviate or suppress efficiently to subtract
Concrete slump loss caused by water preparation.
The guarantor of concrete collapses the time and final setting time is closely related, and it is longer to protect the time of collapsing, and setting time also has
Increased.How to coordinate the two performance, be the difficult point place of the present invention.Want preparation and protect time length of collapsing
Ultra-retardation concrete mixture is it is necessary to increase the primary slump and the divergence of concrete, but surpasses due to common
Retarder does not have water-reducing property, for reaching the target of extra retarded set it is necessary to improve the volume of super-retarder, increases
Add cost, and if the volume of super-retarder too high, the later strength of concrete can be made to reduce.The present invention is led to
Cross polymer chemistry method, by having diminishing, slow setting, water conservation protects the functional monomer copolymerization of function of collapsing and forms,
Containing substantial amounts of carboxyl functional group in the molecular structure of the polycarboxylic acids super-slowly coagulating water reducer finally given, have good
Good water-reducing property and extra retarded set effect, it has certain effect that causes, it is possible to improve concrete and easily
Property, and described polycarboxylic acids super-slowly coagulating water reducer and polycarboxylate water-reducer have the good compatibility, and can be with it
Compounding use, and by regulating the ratio of the two, can prepare and there is the extra retarded set required different setting time
Concrete.It is excellent polycarboxylic acids that the molecular structure of polycarboxylic acids super-slowly coagulating water reducer of the present invention determines it
Water reducer and retarder, or water conservation plasticity-maintaining agent and slump retention agent, be also that concrete workability is adjusted simultaneously
Joint agent.
Detailed description of the invention
For better illustrating the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment pair
The present invention is described further.
Embodiment 1
A kind of embodiment of polycarboxylic acids super-slowly coagulating water reducer of the present invention, polycarboxylic acids extra retarded set described in the present embodiment subtracts
Water preparation uses following methods to be prepared from:
(1) preparation of hydroxylated methyl glycidyl acrylate
In the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, add glycerol, metering system
Acid glycidyl ester, polymerization inhibitor and catalyst, rise high-temperature to 80～90 DEG C, isothermal reaction 4～6h, to obtain final product
Hydroxylated methyl glycidyl acrylate；
(2) preparation of polycarboxylic acids super-slowly coagulating water reducer
In the four-hole boiling flask that volume is 2000ml add 600ml deionized water, chain-transferring agent, initiator,
Hydroxylated methyl glycidyl acrylate that step (1) prepares, Hydroxypropyl acrylate, metering system
Acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer, be heated to 95 DEG C, reacts 6～8h,
It is cooled to less than 45 DEG C, the NaOH solution of addition 30wt%, the pH value of regulation system so that pH=7,
Obtain polycarboxylic acids super-slowly coagulating water reducer.
In above-mentioned steps (1), the mole of described glycerol and glycidyl methacrylate than for 1:0.95,
The mole of described polymerization inhibitor is the 0.02% of glycidyl methacrylate mole, rubbing of described catalyst
Your amount is the 3% of glycidyl methacrylate mole, and described polymerization inhibitor is hydroquinone, described catalysis
Agent is tetraalkylammonium salt.
In above-mentioned steps (2), hydroxylated methyl glycidyl acrylate, Hydroxypropyl acrylate, methyl-prop
The mol ratio of olefin(e) acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer is 1:1.5:1:
0.5:1, the mole of described chain-transferring agent and initiator be respectively hydroxylated methyl glycidyl acrylate,
Hydroxypropyl acrylate, methacrylic acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer
The 5% of integral molar quantity, 0.5%；Described chain-transferring agent is mercaptoethanol, and described initiator is potassium peroxydisulfate.
Methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer in step described above (2) uses following methods
It is prepared from: in the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, adds methoxyl group and gather
Ethylene glycol, polymerization inhibitor and initiator, liter high-temperature, to 80～85 DEG C, until completely dissolved, disposably adds first
Base acrylic acid, is continuously heating to 125～130 DEG C, and isothermal reaction 10～12h obtains methoxy poly (ethylene glycol) first
Base acrylate polymeric monomer；The mole of described polymerization inhibitor is the 0.02% of methoxy poly (ethylene glycol) mole, institute
Stating the mole of methoxy poly (ethylene glycol) and the mole of methacrylic acid ratio for 1:1.2, described methoxyl group gathers
The molecular weight of ethylene glycol is 750～5000, and the mole of initiator is methoxy poly (ethylene glycol) and methacrylic acid
The 0.5% of integral molar quantity；Described polymerization inhibitor is to methyl ether phenol, and described initiator is benzoyl peroxide.
Embodiment 2
A kind of embodiment of polycarboxylic acids super-slowly coagulating water reducer of the present invention, polycarboxylic acids extra retarded set described in the present embodiment subtracts
Water preparation uses following methods to be prepared from:
(1) preparation of hydroxylated methyl glycidyl acrylate
In the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, add glycerol, metering system
Acid glycidyl ester, polymerization inhibitor and catalyst, rise high-temperature to 80～90 DEG C, isothermal reaction 4～6h, to obtain final product
Hydroxylated methyl glycidyl acrylate；
(2) preparation of polycarboxylic acids super-slowly coagulating water reducer
In the four-hole boiling flask that volume is 2000ml add 800ml deionized water, chain-transferring agent, initiator,
Hydroxylated methyl glycidyl acrylate that step (1) prepares, Hydroxypropyl acrylate, metering system
Acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer, be heated to 95 DEG C, reacts 6～8h,
It is cooled to less than 45 DEG C, the NaOH solution of addition 30wt%, the pH value of regulation system so that pH=7,
Obtain polycarboxylic acids super-slowly coagulating water reducer.
In above-mentioned steps (1), the mole of described glycerol and glycidyl methacrylate is than for 1:0.5
The mole of described polymerization inhibitor is the 0.04% of glycidyl methacrylate mole, rubbing of described catalyst
1% that your amount is glycidyl methacrylate mole, described polymerization inhibitor is diphenylamines and to methyl ether phenol
Mixture, described catalyst is tetraalkylammonium salt and FeCl3Mixture.
In above-mentioned steps (2), hydroxylated methyl glycidyl acrylate, Hydroxypropyl acrylate, methyl-prop
The mol ratio of olefin(e) acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer is 1:1.5:1:
0.5:1, the mole of described chain-transferring agent and initiator be respectively hydroxylated methyl glycidyl acrylate,
Hydroxypropyl acrylate, methacrylic acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer
The 4% of integral molar quantity, 1%；Described chain-transferring agent is the mixture of TGA and mercaprol, described initiation
Agent is Ammonium persulfate..
Methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer in step described above (2) uses following methods
It is prepared from: in the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, adds methoxyl group and gather
Ethylene glycol, polymerization inhibitor and initiator, liter high-temperature, to 80～85 DEG C, until completely dissolved, disposably adds first
Base acrylic acid, is continuously heating to 125～130 DEG C, and isothermal reaction 10～12h obtains methoxy poly (ethylene glycol) first
Base acrylate polymeric monomer；The mole of described polymerization inhibitor is the 0.04% of methoxy poly (ethylene glycol) mole, institute
Stating the mole of methoxy poly (ethylene glycol) and the mole of methacrylic acid ratio for 1:1.6, described methoxyl group gathers
The molecular weight of ethylene glycol is 750～5000, and the mole of initiator is methoxy poly (ethylene glycol) and methacrylic acid
The 1% of integral molar quantity；Described polymerization inhibitor is the mixture to methyl ether phenol and diphenylamines, and described initiator was
BP.
Embodiment 3
A kind of embodiment of polycarboxylic acids super-slowly coagulating water reducer of the present invention, polycarboxylic acids extra retarded set described in the present embodiment subtracts
Water preparation uses following methods to be prepared from:
(1) preparation of hydroxylated methyl glycidyl acrylate
In the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, add glycerol, metering system
Acid glycidyl ester, polymerization inhibitor and catalyst, rise high-temperature to 80～90 DEG C, isothermal reaction 4～6h, to obtain final product
Hydroxylated methyl glycidyl acrylate；
(2) preparation of polycarboxylic acids super-slowly coagulating water reducer
In the four-hole boiling flask that volume is 2000ml add 900ml deionized water, chain-transferring agent, initiator,
Hydroxylated methyl glycidyl acrylate that step (1) prepares, Hydroxypropyl acrylate, metering system
Acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer, be heated to 95 DEG C, reacts 6～8h,
It is cooled to less than 45 DEG C, the NaOH solution of addition 30wt%, the pH value of regulation system so that pH=7,
Obtain polycarboxylic acids super-slowly coagulating water reducer.
In above-mentioned steps (1), the mole of described glycerol and glycidyl methacrylate is than for 1:0.8
The mole of described polymerization inhibitor is the 0.05% of glycidyl methacrylate mole, rubbing of described catalyst
You amount for glycidyl methacrylate mole 2%, described polymerization inhibitor be hydroquinone, diphenylamines and
Mixture to methyl ether phenol, described catalyst is pyridine, tetraalkylammonium salt and FeCl3Mixture.
In above-mentioned steps (2), hydroxylated methyl glycidyl acrylate, Hydroxypropyl acrylate, methyl-prop
The mol ratio of olefin(e) acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer is 1:1.5:1:
0.5:1, the mole of described chain-transferring agent and initiator be respectively hydroxylated methyl glycidyl acrylate,
Hydroxypropyl acrylate, methacrylic acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer
The 2% of integral molar quantity, 3%；Described chain-transferring agent is the mixture of TGA, mercaprol and mercaptopropionic acid,
Described initiator is the mixture of Ammonium persulfate. and potassium peroxydisulfate.
Methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer in step described above (2) uses following methods
It is prepared from: in the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, adds methoxyl group and gather
Ethylene glycol, polymerization inhibitor and initiator, liter high-temperature, to 80～85 DEG C, until completely dissolved, disposably adds first
Base acrylic acid, is continuously heating to 125～130 DEG C, and isothermal reaction 10～12h obtains methoxy poly (ethylene glycol) first
Base acrylate polymeric monomer；The mole of described polymerization inhibitor is the 0.06% of methoxy poly (ethylene glycol) mole, institute
State the mole of methoxy poly (ethylene glycol) and the mole of methacrylic acid than for 1:2, the poly-second of described methoxyl group
The molecular weight of glycol is 750～5000, the mole of initiator be methoxy poly (ethylene glycol) and methacrylic acid total
The 2.5% of mole；Described polymerization inhibitor is hydroquinone, mixture to methyl ether phenol and diphenylamines, described
Initiator is benzoyl peroxide.
Embodiment 4
A kind of embodiment of polycarboxylic acids super-slowly coagulating water reducer of the present invention, polycarboxylic acids extra retarded set described in the present embodiment subtracts
Water preparation uses following methods to be prepared from:
(1) preparation of hydroxylated methyl glycidyl acrylate
In the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, add glycerol, metering system
Acid glycidyl ester, polymerization inhibitor and catalyst, rise high-temperature to 80～90 DEG C, isothermal reaction 4～6h, to obtain final product
Hydroxylated methyl glycidyl acrylate；
(2) preparation of polycarboxylic acids super-slowly coagulating water reducer
In the four-hole boiling flask that volume is 2000ml add 1000ml deionized water, chain-transferring agent, initiator,
Hydroxylated methyl glycidyl acrylate that step (1) prepares, Hydroxypropyl acrylate, metering system
Acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer, be heated to 95 DEG C, reacts 6～8h,
It is cooled to less than 45 DEG C, the NaOH solution of addition 30wt%, the pH value of regulation system so that pH=7,
Obtain polycarboxylic acids super-slowly coagulating water reducer.
In above-mentioned steps (1), the mole of described glycerol and glycidyl methacrylate than for 1:0.6,
The mole of described polymerization inhibitor is the 0.06% of glycidyl methacrylate mole, rubbing of described catalyst
Your amount is the 0.5% of glycidyl methacrylate mole, and described polymerization inhibitor is diphenylamines, described catalysis
Agent is pyridine.
In above-mentioned steps (2), hydroxylated methyl glycidyl acrylate, Hydroxypropyl acrylate, methyl-prop
The mol ratio of olefin(e) acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer is 1:1.5:1:
0.5:1, the mole of described chain-transferring agent and initiator be respectively hydroxylated methyl glycidyl acrylate,
Hydroxypropyl acrylate, methacrylic acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer
The 1% of integral molar quantity, 5%；Described chain-transferring agent is mercaptoethanol, TGA, mercaprol and sulfydryl third
The mixture of acid, described initiator is Ammonium persulfate..
Methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer in step described above (2) is directly purchased from market.
Embodiment 5
Polycarboxylic acids super-slowly coagulating water reducer effect test of the present invention
Test arranges matched group and test group, and matched group uses added with high-efficiency water-reducing agent of poly-carboxylic acid in prior art
Concrete, the match ratio (mass ratio) of described concrete is cement: flyash: fluvial sand: (5-25mm)
Rubble: water: high-efficiency water-reducing agent of poly-carboxylic acid=300:60:770:1070:7.2:170, test group is divided into examination
Testing group 1～4, test group 1～4 is respectively as follows:
Test group 1 uses polycarboxylic acids super-slowly coagulating water reducer of the present invention to replace matched group 15% (part by weight)
The concrete that high-efficiency water-reducing agent of poly-carboxylic acid prepares；
Test group 2 uses polycarboxylic acids super-slowly coagulating water reducer of the present invention to replace matched group 30% (part by weight)
The concrete that high-efficiency water-reducing agent of poly-carboxylic acid prepares；
Test group 3 uses polycarboxylic acids super-slowly coagulating water reducer of the present invention to replace matched group 60% (part by weight)
The concrete that high-efficiency water-reducing agent of poly-carboxylic acid prepares；
Test group 4 uses polycarboxylic acids super-slowly coagulating water reducer of the present invention to replace matched group 100% (part by weight)
The concrete that high-efficiency water-reducing agent of poly-carboxylic acid prepares.
Detect matched group, the setting time of test group 1～4 concrete respectively, protect collapse time and slump-loss,
Result is as follows:
The concrete of matched group, presetting period: 6-8h, final setting time: 8-10h, protect collapse 0.5-2h, 0.5h
Slump-loss is 30%, and 2h slump-loss is 50%；
Test group 1, can reach more than 24h the setting time of fresh concrete, protects and collapses 3～5h, and 3h collapses
Degree loss is 5%, and 5h slump-loss is 15%；
Test group 2, can reach more than 36h the setting time of fresh concrete, protects and collapses 5～7h, and 5h collapses
Degree loss is 10%, and 7h slump-loss is 20%；
Test group 3, can reach more than 72h the setting time of fresh concrete, protects and collapses 6～10h, and 6h collapses
Degree loss is 8%, and 10h slump-loss is 25%；
Test group 4, can reach more than 200h the setting time of fresh concrete, protects and collapses 10～16h, 10h
Slump-loss is 10%, and 16h slump-loss is 30%.
From result above, along with the raising of polycarboxylic acids super-slowly coagulating water reducer addition of the present invention, cement mortar
The setting time of body and guarantor progressively extend time of collapsing, and high addition (replaces high-efficiency water-reducing agent of poly-carboxylic acid weight
More than 30%), the later strength of concrete being had certain reinforced effects, intensity improves 10～15%.
Last institute is it should be noted that, above example is only in order to illustrate technical scheme rather than to this
The restriction of invention protection domain, although the present invention being explained in detail with reference to preferred embodiment, this area
It is to be appreciated by one skilled in the art that technical scheme can be modified or equivalent, and
Spirit and scope without departing from technical solution of the present invention.
Claims (8)
1. the preparation method of a polycarboxylic acids super-slowly coagulating water reducer, it is characterised in that described method includes following
Step:
(1) preparation of hydroxylated methyl glycidyl acrylate
In the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, add glycerol, metering system
Acid glycidyl ester, polymerization inhibitor and catalyst, rise high-temperature to 80～90 DEG C, isothermal reaction 4～6h, to obtain final product
Hydroxylated methyl glycidyl acrylate；
(2) preparation of polycarboxylic acids super-slowly coagulating water reducer
The hydroxylating first that addition water, chain-transferring agent, initiator, step (1) prepare in four-hole boiling flask
The poly-second of base glycidyl acrylate, Hydroxypropyl acrylate, methacrylic acid, maleic anhydride and methoxyl group two
Alcohol methacrylate macromer, is heated to 95 DEG C, reacts 6～8h, is cooled to less than 45 DEG C, adds 30wt%
Alkali liquor, the pH value of regulation system so that pH=7, obtain polycarboxylic acids super-slowly coagulating water reducer；
In described step (1), described glycerol with the mole ratio of glycidyl methacrylate is
1:0.95～1:0.5, the mole of described polymerization inhibitor is glycidyl methacrylate mole
0.02～0.06%, the mole of described catalyst is the 0.5～3% of glycidyl methacrylate mole；
Hydroxylated methyl glycidyl acrylate, Hydroxypropyl acrylate, metering system in described step (2)
The mol ratio of acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer is 1:1.5:1:0.5:
1, the mole of described chain-transferring agent and initiator is respectively hydroxylated methyl glycidyl acrylate, propylene
Acid hydroxypropyl acrylate, methacrylic acid, maleic anhydride and methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer always rub
The 1～5%, 0.5～5% of that amount.
2. the preparation method of polycarboxylic acids super-slowly coagulating water reducer as claimed in claim 1, it is characterised in that institute
State polymerization inhibitor in step (1) be hydroquinone, at least one in methyl ether phenol, diphenylamines；Described urge
Agent is pyridine, tetraalkylammonium salt, FeCl3In at least one.
3. the preparation method of polycarboxylic acids super-slowly coagulating water reducer as claimed in claim 1, it is characterised in that institute
State the chain-transferring agent in step (2) be in mercaptoethanol, TGA, mercaprol, mercaptopropionic acid extremely
Few one；Described initiator be Ammonium persulfate., potassium peroxydisulfate at least one.
4. the preparation method of polycarboxylic acids super-slowly coagulating water reducer as claimed in claim 2, it is characterised in that institute
Stating the water in step (2) is deionized water, and the volume of described water is the 0.3～0.5 of four-hole boiling flask volume；Described
Alkali liquor is NaOH solution.
5. the preparation method of polycarboxylic acids super-slowly coagulating water reducer as claimed in claim 1, it is characterised in that institute
Stating the methoxy polyethylene glycol methacrylate-styrene polymer polymeric monomer in step (2) uses following methods to be prepared from:
In the four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, add methoxy poly (ethylene glycol), resistance
Poly-agent and initiator, liter high-temperature, to 80～85 DEG C, until completely dissolved, disposably adds methacrylic acid,
It is continuously heating to 125～130 DEG C, isothermal reaction 10～12h, obtain methoxy polyethylene glycol methacrylate-styrene polymer
Polymeric monomer.
6. the preparation method of polycarboxylic acids super-slowly coagulating water reducer as claimed in claim 5, it is characterised in that institute
State mole is methoxy poly (ethylene glycol) mole the 0.02～0.06% of polymerization inhibitor, the poly-second of described methoxyl group two
The mole of alcohol and the mole of methacrylic acid are than for 1:1.2～2, the molecule of described methoxy poly (ethylene glycol)
Amount is 750～5000, and the mole of initiator is methoxy poly (ethylene glycol) and methacrylic acid integral molar quantity
0.5～2.5%；Described polymerization inhibitor is hydroquinone, at least one in methyl ether phenol, diphenylamines, described in draw
Sending out agent is benzoyl peroxide.
7. one kind use as arbitrary in claim 1～6 as described in the polycarboxylic acids super-slowly coagulating water reducer for preparing of method.
8. a polycarboxylic acids super-slowly coagulating water reducer as claimed in claim 7 purposes in concrete.
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| CN105348508B (en) * | 2015-10-14 | 2017-10-31 | 广东红墙新材料股份有限公司 | A kind of surface-active macromonomer, its preparation method and application |
| CN105294004B (en) * | 2015-10-14 | 2018-01-12 | 广东红墙新材料股份有限公司 | A kind of preparation method of pile tube |
| CN106380548B (en) * | 2016-08-27 | 2020-07-03 | 广东红墙新材料股份有限公司 | Application of water-retention-reduction-type polycarboxylate superplasticizer in preparation of recycled aggregate concrete |
| CN106279566B (en) * | 2016-08-27 | 2020-07-03 | 广东红墙新材料股份有限公司 | Water-retaining shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN107674135B (en) * | 2017-10-31 | 2019-08-20 | 安徽森普新型材料发展有限公司 | A kind of macromolecular retarder, preparation method and application |
| CN109399992A (en) * | 2018-12-04 | 2019-03-01 | 南京友西科技股份有限公司 | A kind of aqua retarder |
| CN110903050A (en) * | 2019-12-17 | 2020-03-24 | 安徽海螺新材料科技有限公司 | Preparation method of special regulator for concrete |
| CN113896448A (en) * | 2021-11-25 | 2022-01-07 | 十九冶成都建设有限公司 | Additive for ultra-large volume concrete |
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| CN103183819A (en) * | 2011-12-28 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Allyl sulfonic glycerin polyoxyethylene ether and preparation method thereof |
| CN103601417A (en) * | 2013-11-15 | 2014-02-26 | 江苏百瑞吉新材料有限公司 | Super retarder |
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| JP2003201160A (en) * | 2001-12-28 | 2003-07-15 | Sanko Colloid Kagaku Kk | Superretarder for mortar |
| JP4883901B2 (en) * | 2003-12-19 | 2012-02-22 | 株式会社日本触媒 | Cement admixture |
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| CN103183819A (en) * | 2011-12-28 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Allyl sulfonic glycerin polyoxyethylene ether and preparation method thereof |
| CN103601417A (en) * | 2013-11-15 | 2014-02-26 | 江苏百瑞吉新材料有限公司 | Super retarder |
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