CN105503011B - Purposes of the ultra high early strength poly-carboxylic water reducer in concrete prefabricated element is prepared - Google Patents

Purposes of the ultra high early strength poly-carboxylic water reducer in concrete prefabricated element is prepared Download PDF

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Publication number
CN105503011B
CN105503011B CN201510936696.3A CN201510936696A CN105503011B CN 105503011 B CN105503011 B CN 105503011B CN 201510936696 A CN201510936696 A CN 201510936696A CN 105503011 B CN105503011 B CN 105503011B
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ultra high
water reducer
early strength
high early
strength poly
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CN105503011A (en
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张小富
赵利华
白淑英
李论
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/05—Materials having an early high strength, e.g. allowing fast demoulding or formless casting
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a kind of preparation method of concrete prefabricated element, including：It is stripped after body natural curing to demoulding strength at the beginning of the prefabricated components that will be formed after the completion of concreting, continues natural curing afterwards, that is, obtains the prefabricated components；The concrete includes following components：Cement, gather materials, ultra high early strength poly-carboxylic water reducer and water, the ultra high early strength poly-carboxylic water reducer is formula (I) or the compound shown in (II).The invention also discloses concrete prefabricated element made from the preparation method as the concrete prefabricated element.By using ultra high early strength poly-carboxylic water reducer of the present invention in the method for the invention, promote hydrated cementitious, any increased activity admixture is not added, and optimised coagulation soil match ratio, the final striking time for causing prefabricated components is by 30 common 40h, 12 15h are shortened to, mould turn around time is accelerated, improves economic benefit.

Description

Purposes of the ultra high early strength poly-carboxylic water reducer in concrete prefabricated element is prepared
Technical field
The present invention relates to a kind of purposes of ultra high early strength poly-carboxylic water reducer, and in particular to a kind of ultra high early strength poly-carboxylic water reducer Purposes in concrete prefabricated element is prepared.
Background technology
Precast concrete is one of most important structure type of modern architecture, has and saves material and labour, carries High high construction efficiency, accelerating construction progress, the advantage such as product quality for improving architectural engineering.Said from the angle of environmental protection and energy-conservation, should It can be reduced environmental pollution with precast concrete technology, obtain larger economic benefit, precast concrete has in China Larger development prospect.
The method of construction of precast concrete, it is exactly by the prefabricated components of factorial praluction with construction machineries such as cranes (beam, plate, post etc.) is combined a kind of rapid construction technology of installation.Its construction is divided into two stages：First stage is in factory Make prefabricated components, second stage in-site installation.
It using concrete is stock in advance in building element made of factory that concrete prefabricated element, which is, including beam, plate, Post and construction and decoration accessory etc., assembled for job site, be the material base of building industrialization.Due to the standardization of component and fixed Type, prefabricated components save more material and artificial than the equivalent link that is produced with other construction methods, and product is by set Standard close inspection dispatches from the factory, and quality guarantee rate is high.
The characteristics of prefabricated components：
1st, structural behaviour is good, and structural mechanics can be effectively ensured by being made using batch production, and discreteness is small.
2nd, speed of application is fast, good product quality, and surface smoothness is high, can reach the decorative effect of clear-water concrete, make knot Structure is uniformly coordinated with building.
3rd, factorial praluction saves, and is advantageous to environmental protection, reduces the noise of site operation.
4th, fire protecting performance is good.
Typically it common are precast concrete floor plate, bridge concrete box girder, industrial premises concrete earth house Set a roof beam in place, culvert frame structure, basement process precast concrete pile etc..
Concrete structure is divided to cast-in-place and prefabricated two kinds, and beam, plate, pipe, stake etc. have prefabricated and cast-in-place form of construction work.It is prefabricated Part, beneficial to construction, can accelerate progress with batch production mass production.
Precast concrete will accomplish that outward appearance is beautiful, and first controls the match ratio of concrete, and sand coarse aggregate ratio can not be less than 40%；Second takes the small ratio of mud as far as possible, because concrete reclaimed water is fewer, the chance for producing bubble is fewer；3rd using early strong Type polycarboxylate water-reducer, with improve concrete strength and shorten mould turn around time, the 4th is the problem of vibrating, it is impossible to owed to shake but Can not cross to shake, this will be observed by rule of thumb.
The adaptability of polycarboxylic acid series additive and binder materials is good, and bleeding rate is low, and function of slump protection is excellent, is gone sightseeing outside component It is bright, fine and close, bubble is few, chloride ion content and alkali content are low, be highly suitable for prepare good endurance high performance high strength coagulation Soil.The concrete prepared using common high-performance polycarboxylic acids water reducing agent, setting time length, hydrated cementitious is slow, and gain in strength is slow, Mould turn around time is caused to be grown.
The content of the invention
A kind of concrete prefabricated element is provided it is an object of the invention to overcome the shortcomings of the prior art part Preparation method, by using ultra high early strength poly-carboxylic water reducer of the present invention in the method for the invention, promote cement water Change, do not add any increased activity admixture, and optimised coagulation soil match ratio, the final striking time for causing prefabricated components by Common 30-40h, shortens to 12-15h, accelerates mould turn around time, improves economic benefit.
To achieve the above object, the technical scheme taken：A kind of preparation method of concrete prefabricated element, methods described Comprise the following steps：It is stripped after body natural curing to demoulding strength at the beginning of the prefabricated components that will be formed after the completion of concreting, it After continue natural curing, that is, obtain the concrete prefabricated element；
The concrete includes following components：Cement, gather materials, ultra high early strength poly-carboxylic water reducer and water, the super hardening gather Carboxylic acid water reducer is the compound shown in formula (I) or (II)；
The structural formula of compound shown in the formula (I) is as follows：
The structural formula of compound shown in the formula (II) is as follows：
Wherein a is 1~80 integer, and b is 1~80 integer, and c is 1~50 integer；L be 1~50 it is whole Number；
A isR is H or CH3；
B is
C is
M is R2、R3With
R4It is respectively C alone1-3Alkyl；X-It is Cl-、Br-Or I-；M is 5~200 integer, n be 0~50 it is whole Number, z is 1~150 integer.
Preferably, the ultra high early strength poly-carboxylic water reducer shown in the formula (I) is prepared by following methods：
(1a) is 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 and obtain reactive intermediate；Wherein described epoxyhalopropane is epoxy bromopropane, Epiiodohydrin With one kind in epoxychloropropane；Its reaction equation is as follows：
(2a) mixes quarternary ammonium salt compound with polymerization inhibitor, is slowly added to the reactive intermediate of step (1a) synthesis in temperature To react 1~10h 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 respectively C alone1-3Alkyl；
The surface-active macromonomer that (3a) synthesizes step (2a), in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride One kind, one kind in APEG, HPEG, VPEG and TPEG, water and molecular weight regulator mixing, are warming up to 85~95 DEG C, dropwise addition is drawn Agent is sent out, time for adding is 1~10h, is incubated after being added dropwise, and soaking time is 1~12h, is then cooled to 45~50 DEG C, is added Sodium hydroxide solution adjusts pH to 7.0-8.0, obtains the ultra high early strength poly-carboxylic water reducer shown in formula (I).
Preferably, in the step (1a) in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol one Kind, one kind in oxirane and the mixture of 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.
The mol ratio of quarternary ammonium salt compound and reactive intermediate is 0.2 in the step (2a):1~2:1.
Surface-active macromonomer in the step (3a), one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride with A kind of mol ratio in APEG, HPEG, VPEG and TPEG is cation quaternary ammonium salt PEO surface-active macromonomers：Methacrylic acid, third One kind in olefin(e) acid, itaconic acid and maleic anhydride：One kind=1.0~3.0 in APEG, HPEG, VPEG and TPEG：1~6.0： 1。
Preferably, catalyst is sodium hydride or sodium in the step (1a)；Polymerization inhibitor is to benzene two in the step (2a) Phenol or to methyl ether phenol, the dosage of the polymerization inhibitor is the 0.02%~0.08 of the reactive intermediate molal quantity；The step (3a) middle-molecular-weihydroxyethyl conditioning agent is at least one of sulfhydryl compound and isopropanol, and the dosage of the molecular weight regulator is institute State surface-active macromonomer, one kind and APEG, VPEG, HPEG and TPEG in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride In a kind of total mole number 0.005~5%；The time for adding of initiator is 2~3h in the step (3a)；The step Soaking time is 2~4h in (3a)；The mass concentration of sodium hydroxide solution is 30% in the step (3a)；The step (3a) Middle initiator is one kind in potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide, and the dosage of the initiator is institute State surface-active macromonomer, one kind and APEG, VPEG, HPEG and TPEG in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride In a kind of total mole number 0.05%~5%.Preferably, step (3a) the middle-molecular-weihydroxyethyl conditioning agent is 3- sulfydryls third At least one of acid, TGA, mercaptoethanol, sodium formaldehyde sulfoxylate and isopropanol.
Preferably, the ultra high early strength poly-carboxylic water reducer shown in the formula (II) is prepared by following methods：
(1b) is 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；Wherein described epoxyhalopropane is epoxy bromopropane, epoxy iodine third One kind in alkane and epoxychloropropane；Its reaction equation is as follows：
(2b) mixes quarternary ammonium salt compound with polymerization inhibitor, is slowly added to the reactive intermediate of step (1b) synthesis in temperature To react 1~10h 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 respectively C alone1-3Alkyl；
The surface-active macromonomer of (3b) step (2b) synthesis, one in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride Kind, one kind in APEG, VPEG, HPEG and TPEG, acrylamide, ALS and 2- acrylamide -2- methyl-prop sulphurs One kind in acid, water and molecular weight regulator mixing, are warming up to 85~95 DEG C, initiator are added dropwise, and time for adding is 1~10h, drop It is incubated after adding, soaking time is 1~12h, is then cooled to 45~50 DEG C, adds sodium hydroxide solution regulation pH to 7.0- 8.0, obtain the ultra high early strength poly-carboxylic water reducer shown in formula (II).
Preferably, in the step (1b) in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol one Kind, one kind in oxirane and the mixture of 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.
The mol ratio of quarternary ammonium salt compound and reactive intermediate is 0.2 in the step (2b):1~2:1.
Surface-active macromonomer in the step (3b), one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind and acrylamide, ALS and 2- acrylamide-2-methyl propane sulfonics in APEG, HPEG, VPEG and TPEG In a kind of mol ratio be the PEO surface-active macromonomers：One in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride Kind：One kind in APEG, HPEG, VPEG and TPEG：Acrylamide, ALS and 2- acrylamide -2- methyl-prop sulphurs One kind in acid==1.0~3.0：1~6.0：1：0.2~6.0.
Preferably, catalyst is sodium hydride or sodium in the step (1b)；Polymerization inhibitor is to benzene two in the step (2b) Phenol or to methyl ether phenol, the dosage of the polymerization inhibitor is the 0.02%~0.08 of the reactive intermediate molal quantity；The step (3b) middle-molecular-weihydroxyethyl conditioning agent is at least one of sulfhydryl compound and isopropanol, and the dosage of the molecular weight regulator is institute State surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, VPEG, HPEG and TPEG In it is a kind of with acrylamide, ALS and 2- acrylamide-2-methyl propane sulfonics in a kind of total mole number 0.005~5%；The time for adding of initiator is 2~3h in the step (3b)；In the step (3b) soaking time be 2~ 4h；The mass concentration of sodium hydroxide solution is 30% in the step (3b)；In the step (3b) initiator be potassium peroxydisulfate, One kind in ammonium persulfate, hydrogen peroxide and benzoyl peroxide, the dosage of the initiator are the surface-active macromonomer, methyl-prop One kind in olefin(e) acid, acrylic acid, itaconic acid and maleic anhydride, one kind in APEG, VPEG, HPEG and TPEG and acrylamide, 0.05%~5% of a kind of total mole number in ALS and 2- acrylamide-2-methyl propane sulfonics.Preferably, Step (3a) the middle-molecular-weihydroxyethyl conditioning agent be 3- mercaptopropionic acids, TGA, mercaptoethanol, sodium formaldehyde sulfoxylate and isopropanol in extremely Few one kind.
The structural formula of reactive intermediate of the present invention is as follows：
Wherein R1For H2C=CH-O-CH2CH2CH2CH2-、H2C=CHCH2-、Or
X is Cl, Br or I；
M is 5~200 integer, and n is 0~50 integer, and z is 1~150 integer.
The structural formula of surface-active macromonomer of the present invention is as follows：
Wherein R1For H2C=CH-O-CH2CH2CH2CH2-、H2C=CHCH2-、OrR2、R3And R4It is respectively C alone1-3Alkyl；X-For Cl-、Br-Or I-；
M is 5~200 integer, and n is 0~50 integer, and z is 1~150 integer.
Preferably, the demoulding strength is more than or equal to 30MPa.
Preferably, just body natural curing to the time of demoulding strength is 12~15h to the prefabricated components.
Preferably, the concrete also includes flyash.
Preferably, the weight of the ultra high early strength poly-carboxylic water reducer is the 1.1%~1.6% of the cement weight.
Preferably, the concrete includes the component of following parts by weight：375~405 parts of cement, gathers materials 1740~1775 Part, 135~145 parts of 5~8 parts of ultra high early strength poly-carboxylic water reducer and water.
Preferably, the concrete also includes 80~120 parts of flyash.It is highly preferred that the concrete is including following The component of parts by weight：380~400 parts of cement, gather materials 1748~1768 parts, 90~115 parts of flyash, ultra high early strength poly-carboxylic diminishing 136~142 parts of 5~7 parts of agent and water.It is highly preferred that the concrete includes the component of following parts by weight：390 parts of cement, gathers materials 1758 parts, 110 parts of flyash, 138 parts of 6 parts of ultra high early strength poly-carboxylic water reducer and water.
Preferably, the mixture to gather materials for sand and stone.It is highly preferred that the weight of the sand and stone ratio is 715： 1025~1040：735.Sand of the present invention is preferably：River sand, sand in 2nd area, modulus of fineness 2.8；Stone of the present invention Preferably：5-20 continuous grading rubbles.
Cement of the present invention is preferably PII42.5R cement.
Present invention also offers a kind of concrete prefabricated element, the concrete prefabricated element uses method system described above It is standby to form.
Present invention also offers purposes of the ultra high early strength poly-carboxylic water reducer in concrete prefabricated element is prepared, the super morning Strength poly-carboxylic water reducer is the compound shown in formula (I) or (II)；
The structural formula of compound shown in the formula (I) is as follows：
The structural formula of compound shown in the formula (II) is as follows：
Wherein a is 1~80 integer, and b is 1~80 integer, and c is 1~50 integer；L be 1~50 it is whole Number；
A isR be H or CH3；
B is
C is
M is R2、R3With
R4It is respectively C alone1-3Alkyl；X-It is Cl-、Br-Or I-；M is 5~200 integer, n be 0~50 it is whole Number, z is 1~150 integer.
The beneficial effects of the present invention are：It is and existing the invention provides a kind of preparation method of concrete prefabricated element Technology is compared, and has advantages below：
1st, ultra high early strength poly-carboxylic water reducer of the present invention is used in preparation method of the present invention, accelerates hydrated cementitious, is saved The about energy, shortens mould service life；
2nd, ultra high early strength poly-carboxylic water reducer of the present invention, concrete workability and adhesive aggregation are used in preparation method of the present invention Property improve, compact and uniform structure, concrete anticracking, anti-permeability performance enhancing.
3rd, ultra high early strength poly-carboxylic water reducer of the present invention is used in preparation method of the present invention, concrete strength is stable, Variance is less than prefabricated component mean square deviation (the common polycarboxylate water-reducer technique mean square deviation of common process production：8-15MPa, super hardening Polycarboxylate water-reducer mean square deviation：4-8MPa)；
4th, for C50 prefabricated components, strength of mould stripping requirement reaches more than 30MPa (including 30MPa), it is necessary to which watering is supported naturally 30-36 hours are protected, using ultra high early strength poly-carboxylic water reducer of the present invention, only need so watering maintenance 12-15 hours naturally, you can reach Strength of mould stripping (more than the 60% of design strength).
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.
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.VPEG of the present invention:4- hydroxy butyl vinyl ether APEOs；APEG：Allyl alcohol polyethenoxy ether； HPEG：Isobutene alcohol APEO；TPEG：Isoamyl alcohol polyoxyethylene ether.
Embodiment 1
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 12 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 30MPa, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：370 parts of cement, 715 parts of sand, 1025 parts of stone, flyash 80 Part, 135 parts of 5 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol prenols, 1g sodium hydrides, 25mol oxirane, and 5mol epoxy chlorine are injected in the autoclave of closing Propane, nitrogen is passed through, stirred, 80 DEG C of reaction 10h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
1mol triethylamines and hydroquinones are added in flask, are warming up to 10 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate triethylamine solution, the dosage of the hydroquinones is the 0.02% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 10 DEG C, continue insulation reaction 10h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 1mol steps (2) surface-active macromonomer, 1mol methacrylic acids, 1.0mol APEG and 400ml deionized waters, the molecule Amount conditioning agent is 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is the surface-active macromonomer, methacrylic acid and APEG The 0.005% of total mole number, 85 DEG C are warming up to, are added dropwise the aqueous solution of initiator, the initiator is potassium peroxydisulfate, the initiation The dosage of agent is the 0.05% of the surface-active macromonomer, methacrylic acid and APEG total mole numbers, time for adding 1h, is dripped Bi Hou, insulation reaction 1h, it is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust pH=7.0, produce super High early strength poly-carboxylic water reducer.
Embodiment 2
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 15 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 35MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：405 parts of cement, 735 parts of sand, 1040 parts of stone, flyash 120 Part, 145 parts of 8 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol isobutene alcohols, 4g sodium hydrides, 500mol oxirane, 250mol epoxies third are injected in the autoclave of closing Alkane, and 750mol epoxy bromopropanes, stirring, 150 DEG C of reaction 2h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
2mol trimethylamines and hydroquinones are added in flask, are warming up to 80 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate trimethylamine solution, the dosage of the hydroquinones is the 0.03% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 80 DEG C, continue insulation reaction 1h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 1.0mol steps (2) surface-active macromonomer, 6mol acrylic acid, 1mol HPEG and 600ml deionized waters, the molecular weight adjusts Section agent is TGA, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid and HPEG total mole numbers 5%, 95 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is ammonium persulfate, and the dosage of the initiator is described 5%, time for adding 10h of surface-active macromonomer, acrylic acid and HPEG total mole numbers, after being added dropwise, insulation reaction 12h, drop At warm to 45 DEG C, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 3
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 13 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 33.5MPa.The demoulding, continues natural curing, produces concrete prefabricated element afterwards.
The concrete includes the component of following parts by weight：380 parts of cement, 720 parts of sand, 1028 parts of stone, flyash 90 Part, 136 parts of 5.5 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol allyl alcohols, 2g 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
3mol tripropyl amine (TPA)s and hydroquinones are added in flask, are warming up to 40 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate tripropyl amine (TPA) solution, the dosage of the hydroquinones is the 0.04% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 40 DEG C, continue insulation reaction 8h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 1mol steps (2) surface-active macromonomer, 3mol acrylic acid, 1mol TPEG and 500ml deionized waters, the molecular-weight adjusting Agent is mercaptoethanol, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid and TPEG total mole numbers 1%, 90 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is benzoyl peroxide, and the dosage of the initiator is 0.1%, time for adding 5h of the surface-active macromonomer, acrylic acid and TPEG total mole numbers, after being added dropwise, insulation reaction 6h, it is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust pH=7.5, produce ultra high early strength poly-carboxylic diminishing Agent.
Embodiment 4
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 12 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 33MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：400 parts of cement, 730 parts of sand, 1038 parts of stone, flyash 115 Part, 142 parts of 7 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol 4- hydroxy butyl vinyl ethers, 2g sodium hydrides, 50mol oxirane, 5mol are injected in the autoclave of closing Expoxy propane and 500mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 4mol N, N- dimethyl amines and to methyl ether phenol add flask in, be warming up to 50 DEG C, be slowly added dropwise containing The N of the reactive intermediate of 5mol steps (1) synthesis, N- dimethyl amine solution, the dosage to methyl ether phenol is the work Property intermediate molal quantity 0.05%, after being added dropwise, under the conditions of 50 DEG C, continue insulation reaction 7h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 3mol steps (2) surface-active macromonomer, 6mol methacrylic acids, 1.0mol VPEG and 400ml deionized waters, the molecule Amount conditioning agent is isopropanol, and the dosage of the molecular weight regulator is always rubbed for the surface-active macromonomer, methacrylic acid and VPEG The 3.5% of your number, is warming up to 85 DEG C, is added dropwise the aqueous solution of initiator, and the initiator is hydrogen peroxide, the dosage of the initiator For the 3% of the surface-active macromonomer, methacrylic acid and VPEG total mole numbers, time for adding 7h, after being added dropwise, insulation is anti- 8h is answered, is cooled at 50 DEG C, the NaOH solution that mass concentration is 30% is added, adjusts pH=7.0, produce ultra high early strength poly-carboxylic and subtract Aqua.
Embodiment 5
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 15 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 35MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：390 parts of cement, 728 parts of sand, 1030 parts of stone, flyash 110 Part, 138 parts of 6 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
The injection 5mol allyl alcohols in the autoclave of closing, 2g sodium, 900mol oxirane, 150mol expoxy propane, and 150mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 5mol N, N- diethyl methyl amines and to methyl ether phenol add flask in, be warming up to 60 DEG C, be slowly added dropwise containing The N of the reactive intermediate of 5mol steps (1) synthesis, N- diethyl methyl amine solution, the dosage to methyl ether phenol is the work Property intermediate molal quantity 0.06%, after being added dropwise, under the conditions of 60 DEG C, continue insulation reaction 6h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 3mol steps (2) surface-active macromonomer, 1mol acrylic acid, 1mol HPEG and 600ml deionized waters, the molecular-weight adjusting Agent is TGA, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid and HPEG total mole numbers 1.2%, 95 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is ammonium persulfate, and the dosage of the initiator is institute The 2% of surface-active macromonomer, acrylic acid and HPEG total mole numbers is stated, time for adding 9h, after being added dropwise, insulation reaction 10h, is dropped At warm to 45 DEG C, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 6
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 14 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 34MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：405 parts of cement, 715 parts of sand, 1025 parts of stone, flyash 80 Part, 135 parts of 5 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol prenols, 1g sodium hydrides, 50mol 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
6mol triethylamines and hydroquinones are added in flask, are warming up to 70 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate triethylamine solution, the dosage of the hydroquinones is the 0.07% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 70 DEG C, continue insulation reaction 4h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 2mol steps (2) surface-active macromonomer, 1mol methacrylic acids, 1.0mol APEG, 0.2mol acrylamides and 400ml are gone Ionized water, the molecular weight regulator are 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is the surface-active macromonomer, first The 0.5% of base acrylic acid, acrylamide and APEG total mole numbers, is warming up to 85 DEG C, the aqueous solution of initiator, the initiation is added dropwise Agent is potassium peroxydisulfate, and the dosage of the initiator is the surface-active macromonomer, methacrylic acid, acrylamide and APEG total moles Several 0.05%, time for adding 2h, after being added dropwise, insulation reaction 2h, it is cooled at 50 DEG C, it is 30% to add mass concentration NaOH solution, adjust pH=7.0, produce ultra high early strength poly-carboxylic water reducer.
Embodiment 7
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 12 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 33MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：405 parts of cement, 735 parts of sand, 1040 parts of stone, flyash 120 Part, 145 parts of 5 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol isobutene alcohols, 4g sodium hydrides, 500mol oxirane, 250mol epoxies third are injected in the autoclave of closing Alkane, and 750mol epoxy bromopropanes, stirring, 150 DEG C of reaction 2h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
7mol trimethylamines and hydroquinones are added in flask, are warming up to 80 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate trimethylamine solution, the dosage of the hydroquinones is the 0.08% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 80 DEG C, continue insulation reaction 1h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 2mol steps (2) surface-active macromonomer, 4mol acrylic acid, 1mol HPEG, 1mol 2- acrylamide-2-methyl propane sulfonics With 600ml deionized waters, the molecular weight regulator is sodium formaldehyde sulfoxylate, and the dosage of the molecular weight regulator is big single for the activity Body, acrylic acid, the 0.1% of 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, are warming up to 95 DEG C, and initiator is added dropwise The aqueous solution, the initiator is ammonium persulfate, and the dosage of the initiator is the surface-active macromonomer, acrylic acid, 2- propylene The 5% of acid amides -2- methyl propane sulfonic acids and HPEG total mole numbers, time for adding 3h, after being added dropwise, insulation reaction 4h, cooling To at 45 DEG C, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 8
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 13 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 33.5MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：375 parts of cement, 715 parts of sand, 1025 parts of stone, flyash 80 Part, 135 parts of 8 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol allyl alcohols, 2g sodium hydrides, 1000mol oxirane, and 400mol epoxies are injected in the autoclave of closing Iodopropane, stirring, 100 DEG C of reaction 5h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
8mol tripropyl amine (TPA)s and hydroquinones are added in flask, are warming up to 30 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate tripropyl amine (TPA) solution, the dosage of the hydroquinones is the 0.07% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 30 DEG C, continue insulation reaction 10h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 2mol steps (2) surface-active macromonomer, 6mol acrylic acid, 1mol TPEG and 500ml deionized waters, the molecular-weight adjusting Agent is mercaptoethanol, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid and TPEG total mole numbers 0.01%, 90 DEG C are warming up to, is added dropwise the aqueous solution of initiator, the initiator is benzoyl peroxide, the use of the initiator Measure as the 1% of the surface-active macromonomer, acrylic acid and TPEG total mole numbers, time for adding 1h, after being added dropwise, insulation reaction 12h, it is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust pH=7.5, produce ultra high early strength poly-carboxylic and subtract Aqua.
Embodiment 9
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 12 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 33MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：375 parts of cement, 735 parts of sand, 1040 parts of stone, flyash 120 Part, 145 parts of 8 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
The injection 5mol 4- hydroxy butyl vinyl ethers in the autoclave of closing, 2g sodium hydrides, 60mol oxirane, 200mol expoxy propane and 500mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 9mol N, N- dimethyl amines and to methyl ether phenol add flask in, be warming up to 20 DEG C, be slowly added dropwise containing The N of the reactive intermediate of 5mol steps (1) synthesis, N- dimethyl amine solution, the dosage to methyl ether phenol is the work Property intermediate molal quantity 0.06%, after being added dropwise, under the conditions of 20 DEG C, continue insulation reaction 10h, produce active big single Body.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 3mol steps (2) surface-active macromonomer, 6mol methacrylic acids, 1.0mol VPEG, 6mol 2- acrylamide -2- methyl-props Sulfonic acid and 400ml deionized waters, the molecular weight regulator are isopropanol, and the dosage of the molecular weight regulator is the activity Polymeric monomer, methacrylic acid, the 3.5% of 2- acrylamide-2-methyl propane sulfonics and VPEG total mole numbers, 85 DEG C are warming up to, drop Add the aqueous solution of initiator, the initiator is potassium peroxydisulfate, and the dosage of the initiator is the surface-active macromonomer, methyl-prop 3%, time for adding 10h of olefin(e) acid, 2- acrylamide-2-methyl propane sulfonics and VPEG total mole numbers, after being added dropwise, insulation 1h is reacted, is cooled at 50 DEG C, the NaOH solution that mass concentration is 30% is added, adjusts pH=7.0, produce ultra high early strength poly-carboxylic Water reducer.
Embodiment 10
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 12 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 33MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：380 parts of cement, 730 parts of sand, 1038 parts of stone, flyash 115 Part, 142 parts of 5.5 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
The injection 5mol allyl alcohols in the autoclave of closing, 2g sodium, 900mol oxirane, 150mol expoxy propane, and 150mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 10molN, N- diethyl methyl amines and to methyl ether phenol add flask in, be warming up to 50 DEG C, be slowly added dropwise containing The N of the reactive intermediate of 5mol steps (1) synthesis, N- diethyl methyl amine solution, the dosage to methyl ether phenol is the work Property intermediate molal quantity 0.05%, after being added dropwise, under the conditions of 50 DEG C, continue insulation reaction 8h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 3mol steps (2) surface-active macromonomer, 3mol acrylic acid, 1mol HPEG, 3mol acrylamides and 600ml deionized waters, institute It is TGA to state molecular weight regulator, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid, acryloyl The 1.2% of amine and HPEG total mole numbers, 95 DEG C are warming up to, are added dropwise the aqueous solution of initiator, the initiator is ammonium persulfate, institute The dosage for stating initiator is the 0.1% of the surface-active macromonomer, acrylic acid, acrylamide and HPEG total mole numbers, time for adding For 3h, after being added dropwise, insulation reaction 4h, it is cooled at 45 DEG C, adds the NaOH solution that mass concentration is 30%, adjust pH= 8.0, produce ultra high early strength poly-carboxylic water reducer.
Embodiment 11
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 15 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 35MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：400 parts of cement, 720 parts of sand, 1028 parts of stone, flyash 90 Part, 136 parts of 5.5 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol prenols, 1g sodium hydrides, 50mol 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
9mol triethylamines and hydroquinones are added in flask, are warming up to 60 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate triethylamine solution, the dosage of the hydroquinones is the 0.04% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 60 DEG C, continue insulation reaction 7h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 3mol steps (2) surface-active macromonomer, 5mol methacrylic acids, 1.0mol APEG, 5mol ALSs and 400ml Deionized water, the molecular weight regulator are 3- mercaptopropionic acids, the dosage of the molecular weight regulator is the surface-active macromonomer, The 0.005% of methacrylic acid, ALS and APEG total mole numbers, is warming up to 85 DEG C, the aqueous solution of initiator is added dropwise, The initiator is hydrogen peroxide, the dosage of the initiator is the surface-active macromonomer, methacrylic acid, ALS and The 0.5% of APEG total mole numbers, time for adding 2h, after being added dropwise, insulation reaction 2h, it is cooled at 50 DEG C, adds quality Concentration is 30% NaOH solution, adjusts pH=7.0, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 12
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 15 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 35MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：380 parts of cement, 720 parts of sand, 1028 parts of stone, flyash 90 Part, 136 parts of 7 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol isobutene alcohols, 4g sodium hydrides, 500mol oxirane, 250mol epoxies third are injected in the autoclave of closing Alkane, and 750mol epoxy bromopropanes, stirring, 150 DEG C of reaction 2h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
8mol trimethylamines and hydroquinones are added in flask, are warming up to 70 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate trimethylamine solution, the dosage of the hydroquinones is the 0.03% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 70 DEG C, continue insulation reaction 3h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 1mol steps (2) surface-active macromonomer, 4mol acrylic acid, 1mol HPEG, 3mol ALSs and 600ml deionizations Water, the molecular weight regulator are TGA, the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid, The 5% of ALS and HPEG total mole numbers, 95 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator was Ammonium sulfate, the dosage of the initiator is the surface-active macromonomer, acrylic acid, ALS and HPEG total mole numbers 5%, time for adding 3h, after being added dropwise, insulation reaction 4h, it is cooled at 45 DEG C, adds the NaOH that mass concentration is 30% Solution, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 13
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 15 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 35MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：400 parts of cement, 720 parts of sand, 1028 parts of stone, flyash 90 Part, 136 parts of 7 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol allyl alcohols, 2g 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
7mol tripropyl amine (TPA)s and hydroquinones are added in flask, are warming up to 80 DEG C, is slowly added dropwise and is closed containing 5mol steps (1) Into reactive intermediate tripropyl amine (TPA) solution, the dosage of the hydroquinones is the 0.02% of the reactive intermediate molal quantity, After being added dropwise, under the conditions of 80 DEG C, continue insulation reaction 2h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 1.0mol steps (2) surface-active macromonomer, 3mol acrylic acid, 1mol VPEG and 600ml deionized waters, the molecular weight are adjusted Section agent is TGA, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid and HPEG total mole numbers 0.05%, 95 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is ammonium persulfate, and the dosage of the initiator is 0.5%, time for adding 3h of the surface-active macromonomer, acrylic acid and HPEG total mole numbers, after being added dropwise, insulation reaction 4h, it is cooled at 45 DEG C, adds the NaOH solution that mass concentration is 30%, adjust pH=8.0, produce ultra high early strength poly-carboxylic diminishing Agent.
Embodiment 14
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 15 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 35MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：390 parts of cement, 720 parts of sand, 1028 parts of stone, flyash 90 Part, 136 parts of 6 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
The injection 5mol 4- hydroxy butyl vinyl ethers in the autoclave of closing, 2g sodium hydrides, 60mol oxirane, 200mol expoxy propane and 500mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 6mol N, N- dimethyl amines and to methyl ether phenol add flask in, be warming up to 80 DEG C, be slowly added dropwise containing The N of the reactive intermediate of 5mol steps (1) synthesis, N- dimethyl amine solution, the dosage to methyl ether phenol is the work Property intermediate molal quantity 0.04%, after being added dropwise, under the conditions of 80 DEG C, continue insulation reaction 3h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 2mol steps (2) surface-active macromonomer, 2mol acrylic acid, 1mol TPEG, 2mol ALSs and 500ml deionizations Water, the molecular weight regulator are mercaptoethanol, the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid, The 1% of ALS and TPEG total mole numbers, 90 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator was BP, the dosage of the initiator is the surface-active macromonomer, acrylic acid, ALS and TPEG total mole numbers 0.1%, time for adding 2.5h, after being added dropwise, insulation reaction 3h, be cooled at 50 DEG C, add mass concentration be 30% NaOH solution, adjust pH=7.5, produce ultra high early strength poly-carboxylic water reducer.
Embodiment 15
A kind of embodiment of the preparation method of concrete prefabricated element of the present invention, the described method comprises the following steps：
Body at the beginning of concreting is obtained into prefabricated components in a mold, by body natural curing 15 hours at the beginning of the prefabricated components Afterwards, demoulding strength reaches 35MPa, the demoulding, continues natural curing afterwards, produces concrete prefabricated element.
The concrete includes the component of following parts by weight：390 parts of cement, 735 parts of sand, 1038 parts of stone, flyash 115 Part, 142 parts of 6 parts of ultra high early strength poly-carboxylic water reducer and water.
The ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1), the synthesis of reactive intermediate
5mol allyl alcohols, 2g sodium hydrides, 900mol oxirane, 150mol epoxies third are injected in the autoclave of closing Alkane, and 250mol Epiiodohydrins, stirring, 90 DEG C of reaction 8h, produce reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 5molN, N- diethyl methyl amines and to methyl ether phenol add flask in, be warming up to 80 DEG C, be slowly added dropwise containing The N of the reactive intermediate of 5mol steps (1) synthesis, N- diethyl methyl amine solution, the dosage to methyl ether phenol is the work Property intermediate molal quantity 0.08%, after being added dropwise, under the conditions of 80 DEG C, continue insulation reaction 1h, produce surface-active macromonomer.
3) synthesis of ultra high early strength poly-carboxylic water reducer
In the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 1mol steps (2) surface-active macromonomer, 1mol acrylic acid, 1mol HPEG, 1mol ALSs and 600ml deionizations Water, the molecular weight regulator are TGA, the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid, The 0.1% of ALS and HPEG total mole numbers, 95 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is Ammonium persulfate, the dosage of the initiator is the surface-active macromonomer, acrylic acid, ALS and HPEG total mole numbers 2%, time for adding 3h, after being added dropwise, insulation reaction 4h, it is cooled at 45 DEG C, adds the NaOH that mass concentration is 30% Solution, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 16
The setting time of concrete in embodiment 1~15 is detected, testing result is：Presetting period is 4-5h, Final setting time is 7-8h, and demoulding time is 12-15 hours.
The intensity in the age not same period of obtained prefabricated components in embodiment 1~15 is tested, test result see the table below.
The concrete different larval instar intensity (unit of table 1：MPa)
Comparative example
Using existing common polycarboxylate water-reducer prefabricated components, specific prefabricated components preparation side are prepared as water reducer Method includes：Body at the beginning of the prefabricated components that will be formed after the completion of concreting carries out natural curing.
It is stripped after reaching demoulding strength, continues natural curing afterwards, that is, obtains the prefabricated components；Wherein, demoulding strength For 30-33MPa.
In addition to water reducer is common polycarboxylate water-reducer, the concrete material used in comparative example 1~15 is the same as embodiment 1 Concrete material in~15.
The setting time and demoulding time of concrete in comparative example 1~15 are detected, testing result is：When pre-hardening Between be 10-12h, final setting time 15-20h, demoulding time is 36 hours.
The intensity in the age not same period of obtained section of jurisdiction in comparative example 1~15 is tested, test result see the table below.
The concrete different larval instar intensity (unit of table 2：MPa)
Age 36h 7d 28d
Intensity 30-33 40-45 55-60
Curing condition It is natural It is natural It is natural
Pass through the data result in Tables 1 and 2：The prefabricated components preparation method of the present invention is using of the present invention Ultra high early strength poly-carboxylic water reducer is substituted under existing common polycarboxylate water-reducer, under identical curing time, obtained prefabricated structure The intensity of part is higher.Prepared and mixed using ultra high early strength poly-carboxylic water reducer of the present invention in concrete prefabricated element preparation process of the present invention Solidifying soil, conserved using watering naturally, due to the rush cement aquation of super hardening water reducer of the present invention, concrete strength hair Exhibition is fast, and curing time is short, and mould turn around time is short, good in economic efficiency.
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 preparation method of concrete prefabricated element, it is characterised in that the described method comprises the following steps：Concrete is poured It is stripped after first body natural curing to the demoulding strength of prefabricated components formed after the completion of building, continues natural curing afterwards, that is, obtain institute State concrete prefabricated element；
The concrete includes following components：Cement, gather materials, ultra high early strength poly-carboxylic water reducer and water, the ultra high early strength poly-carboxylic Water reducer is the compound shown in formula (I) or (II)；
The structural formula of compound shown in the formula (I) is as follows：
The structural formula of compound shown in the formula (II) is as follows：
Wherein a isInteger, b isInteger, c isInteger；L isIt is whole Number；
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 isInteger, z isInteger；
Ultra high early strength poly-carboxylic water reducer shown in the formula (I) is prepared by following methods：
(1a) is 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, is added catalyst, is 80~150 DEG C of bars in temperature Reacted 2~10 hours under part and obtain reactive intermediate；Wherein described epoxyhalopropane is epoxy bromopropane, Epiiodohydrin and ring One kind in oxygen chloropropane；Its reaction equation is as follows：
(2a) mixes quarternary ammonium salt compound with polymerization inhibitor, be slowly added to step (1a) synthesis reactive intermediate temperature be 10 1~10h is reacted under the conditions of~80 DEG C, obtains the surface-active macromonomer；Its reaction equation is as follows：
The quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C alone1-3Alkyl；
The surface-active macromonomer that (3a) synthesizes step (2a), one in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride Kind, one kind in APEG, HPEG, VPEG and TPEG, water and molecular weight regulator mix, and are warming up to 85~95 DEG C, are added dropwise and trigger Agent, time for adding are 1~10h, are incubated after being added dropwise, and soaking time is 1~12h, are then cooled to 45~50 DEG C, add hydrogen Sodium hydroxide solution adjusts pH to 7.0-8.0, obtains the ultra high early strength poly-carboxylic water reducer shown in formula (I)；
Ultra high early strength poly-carboxylic water reducer shown in the formula (II) is prepared by following methods：
(1b) is 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, is added catalyst, is 80~150 DEG C of bars in temperature Reacted 2~10 hours under part, obtain reactive intermediate；Wherein described epoxyhalopropane be epoxy bromopropane, Epiiodohydrin and One kind in epoxychloropropane；Its reaction equation is as follows：
(2b) mixes quarternary ammonium salt compound with polymerization inhibitor, be slowly added to step (1b) synthesis reactive intermediate temperature be 10 1~10h is reacted under the conditions of~80 DEG C, obtains the surface-active macromonomer；Its reaction equation is as follows：
The quarternary ammonium salt compound is N (R2R3R4), and wherein R2, R3 and R4 are respectively C alone1-3Alkyl；
The surface-active macromonomer of (3b) step (2b) synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, VPEG, HPEG and TPEG, in acrylamide, ALS and 2- acrylamide-2-methyl propane sulfonics One kind, water and molecular weight regulator mixing are warming up to 85~95 DEG C, initiator are added dropwise, time for adding is 1~10h, is dripped It is incubated after finishing, soaking time is 1~12h, is then cooled to 45~50 DEG C, adds sodium hydroxide solution regulation pH to 7.0-8.0, Obtain the ultra high early strength poly-carboxylic water reducer shown in formula (II).
2. according to the method for claim 1, it is characterised in that the demoulding strength is more than or equal to 30MPa.
3. according to the method for claim 1, it is characterised in that the prefabricated components just body natural curing to demoulding strength Time is 12~15h.
4. preparation method according to claim 1, it is characterised in that the concrete also includes flyash.
5. preparation method according to claim 1, it is characterised in that the weight of the ultra high early strength poly-carboxylic water reducer is institute State the 1.1%~1.6% of cement weight.
6. preparation method according to claim 1, it is characterised in that the concrete includes the component of following parts by weight： 375~405 parts of cement, gather materials 1740~1775 parts, 135~145 parts of 5~8 parts of ultra high early strength poly-carboxylic water reducer and water.
7. preparation method according to claim 6, it is characterised in that the concrete also includes 80~120 parts of fine coal Ash.
8. preparation method according to claim 1, it is characterised in that the mixture to gather materials for sand and stone.
It is 9. a kind of using the concrete prefabricated element prepared such as any methods describeds of claim 1-8.
10. purposes of the ultra high early strength poly-carboxylic water reducer in concrete prefabricated element is prepared, it is characterised in that the super hardening gathers Carboxylic acid water reducer is the compound shown in formula (I) or (II)；
The structural formula of compound shown in the formula (I) is as follows：
The structural formula of compound shown in the formula (II) is as follows：
Wherein a isInteger, b isInteger, c isInteger；L isIt is whole Number；
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 isInteger, z isInteger；
Ultra high early strength poly-carboxylic water reducer shown in the formula (I) is prepared by following methods：
(1a) is 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, is added catalyst, is 80~150 DEG C of bars in temperature Reacted 2~10 hours under part and obtain reactive intermediate；Wherein described epoxyhalopropane is epoxy bromopropane, Epiiodohydrin and ring One kind in oxygen chloropropane；Its reaction equation is as follows：
(2a) mixes quarternary ammonium salt compound with polymerization inhibitor, be slowly added to step (1a) synthesis reactive intermediate temperature be 10 1~10h is reacted under the conditions of~80 DEG C, obtains the surface-active macromonomer；Its reaction equation is as follows：
The quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C alone1-3Alkyl；
The surface-active macromonomer that (3a) synthesizes step (2a), one in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride Kind, one kind in APEG, HPEG, VPEG and TPEG, water and molecular weight regulator mix, and are warming up to 85~95 DEG C, are added dropwise and trigger Agent, time for adding are 1~10h, are incubated after being added dropwise, and soaking time is 1~12h, are then cooled to 45~50 DEG C, add hydrogen Sodium hydroxide solution adjusts pH to 7.0-8.0, obtains the ultra high early strength poly-carboxylic water reducer shown in formula (I)；
Ultra high early strength poly-carboxylic water reducer shown in the formula (II) is prepared by following methods：
(1b) is 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, is added catalyst, is 80~150 DEG C of bars in temperature Reacted 2~10 hours under part, obtain reactive intermediate；Wherein described epoxyhalopropane be epoxy bromopropane, Epiiodohydrin and One kind in epoxychloropropane；Its reaction equation is as follows：
(2b) mixes quarternary ammonium salt compound with polymerization inhibitor, be slowly added to step (1b) synthesis reactive intermediate temperature be 10 1~10h is reacted under the conditions of~80 DEG C, obtains the surface-active macromonomer；Its reaction equation is as follows：
The quarternary ammonium salt compound is N (R2R3R4), and wherein R2, R3 and R4 are respectively C alone1-3Alkyl；
The surface-active macromonomer of (3b) step (2b) synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, VPEG, HPEG and TPEG, in acrylamide, ALS and 2- acrylamide-2-methyl propane sulfonics One kind, water and molecular weight regulator mixing are warming up to 85~95 DEG C, initiator are added dropwise, time for adding is 1~10h, is dripped It is incubated after finishing, soaking time is 1~12h, is then cooled to 45~50 DEG C, adds sodium hydroxide solution regulation pH to 7.0-8.0, Obtain the ultra high early strength poly-carboxylic water reducer shown in formula (II).
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