CN105565718B - Application of the ultra high early strength poly-carboxylic water reducer in Prestressed concrete cylinder pipe - Google Patents

Application of the ultra high early strength poly-carboxylic water reducer in Prestressed concrete cylinder pipe Download PDF

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CN105565718B
CN105565718B CN201510945634.9A CN201510945634A CN105565718B CN 105565718 B CN105565718 B CN 105565718B CN 201510945634 A CN201510945634 A CN 201510945634A CN 105565718 B CN105565718 B CN 105565718B
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methoxyl group
synthesis
ultra high
early strength
parts
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CN105565718A (en
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张小富
赵利华
李论
白淑英
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WUHAN SUBO NEW BUILDING MATERIAL 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
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a kind of preparation method of Prestressed concrete cylinder pipe, including：Ring orientation prestress steel wire is wound on the outside of the concrete tube core with steel cylinder, then spray cement mortar protective course, that is, Prestressed concrete cylinder pipe is made；The concrete tube core by body at the beginning of the concrete formed after concreting tube core by carrying out natural curing to be formed；Wherein, the concrete includes cement, gathered materials, water and ultra high early strength poly-carboxylic water reducer, and the ultra high early strength poly-carboxylic water reducer is formula (1) or the compound shown in formula (2)；The invention also discloses Prestressed concrete cylinder pipe made from the preparation method as Prestressed concrete cylinder pipe.The Prestressed concrete cylinder pipe preparation method of the present invention can realize the steam curing conservation of exempting from of Prestressed concrete cylinder pipe, can also improve the intensity of Prestressed concrete cylinder pipe, while have the advantages of simple to operate, production safety, cost are cheap, energy-conserving and environment-protective.

Description

Application of the ultra high early strength poly-carboxylic water reducer in Prestressed concrete cylinder pipe
Technical field
The invention belongs to concrete application field, is related to ultra high early strength poly-carboxylic water reducer in Prestressed concrete cylinder pipe Application, a kind of more particularly to Prestressed concrete cylinder pipe and preparation method thereof.
Background technology
The production and application of Prestressed concrete cylinder pipe, so far existing more than 70 years history.Nineteen thirty-nine, nation of France received pipeline Company designs and has manufactured Prestressed concrete cylinder pipe (PCCP) first.The 1940s, America and Europe competitively developed PCCP, beautiful State is production and uses the most countries of PCCP, and so far, the U.S. uses PCCP28000km, and maximum caliber reaches 7600mm. In addition to the U.S., PCCP is used widely in more than the ten of America, Europe, Africa and Asia individual countries at present, is used in recent years Countries most PCCP is the Libya in Africa.
China develops production PCCP and started late, and just starts the 1980s to develop.Although China's production and application PCCP history only has more than 20 years, but due to the opportune time that at a time when national economy is fast-developing, urbanization process is accelerated, warp Independent research is crossed, introduces technology and is digested with equipment, product can domesticize completely.
PCCP manages the English of (Prestressed Concrete Cylinder Pipe) formula Prestressed concrete cylinder pipe Abbreviation, is the composite pipe being made up of compressor wire, steel cylinder, concrete, this tubing is in the concrete tube core with steel cylinder On, ring winding compressor wire is finally manufactured in the fine and close cement mortar protective course of outside spray.It is abundant and comprehensive Close ground played steel tension, easily seal and concrete resistance to compression, decay resistance, there is high leakproofness, high intensity and height Impervious characteristic.
PCCP pipes are divided into two kinds from structure type：One kind is lined Prestressed concrete cylinder pipe (PCCP-L), i.e., In steel cylinder inwall formation of concrete, ring orientation prestress steel wire is wound outside steel cylinder, then spray furnace protective layer and it is manufactured Tubing；One kind is embed-type Prestressed concrete cylinder pipe (PCCP-E), refers to steel cylinder and the inside and outside both sides concrete layer group of steel cylinder Ring orientation prestress steel wire is wound into tube core and on the outside of tube core concrete, then makes cement mortar protective course and manufactured pipe Son.
PCCP with lower part by being formed：
1. strong concrete tube core:It is the dominant structural moieties of pipeline, it is possible to provide smooth inner surface is with sharp current. Steel cylinder in the tube core plays antiseepage and provides endwise tensile strength, and can increase ring intensity.In PCCP-E type pipelines, Steel cylinder is embedded in concrete tube core, and in PCCP-L type pipelines, steel cylinder bag is in the outside of concrete tube core.Steel cylinder both ends connect steel System hold, socket change with elastomeric O-type rubber ring, it can provide sealing for the connection between Guan Yuguan and can make adjacent two tube hub pair Together.PCCP-E type pipe concretes are vertical in punching block to be poured, and is used for Large Diameter Pipeline PCCP pipes, the concrete of PCCP-L type pipes lean on from The heart pours or radially compacting pours in steel cylinder, is used for pipe with small pipe diameter PCCP pipes.
2. cold drawn compressor wire：With certain tension spiral wrap on tube core, produced on tube core uniform Compressive pre-stress, to compensate for the tension as caused by internal pressure and external load.Can be according to carrying out practically condition design steel wire diameter, precompressed Stress and a density is twined, with the optimum prestress needed for providing.
A 3. closely knit cement mortar protective course：High-tensile steel wires and tube core are protected, is allowed to from physical damage and outer Corrode on boundary.
4. steel is held, socket connector：The both ends of steel cylinder are welded in, are PCCP connector and seal.
PCCP pipes have following technology and economic traits：Design method is advanced, safety；Bear higher internal pressure and outer lotus Carry；Good impermeability and durability；Joint sealing is good；Corrosion resistance and good；Good water passing capacity；Installation rate is fast；Energy Enough resist certain thrust；PCCP semirigid joints are good to ground adaptability；Shock resistance is strong；All kinds of accessories and different can be made Type pipe；Construction costs and maintenance cost are low.
In traditional handicraft, it is necessary to pipe of concrete to being formed after concreting in the forming process of concrete tube core Just body carries out steam curing to core.Steam curing be divided into it is quiet stop, heat up, constant temperature, cooling four-stage, no less than 1 small between the quiet stopping time When；Programming rate is not more than 22 DEG C/h；Conservation system should make concrete material reach demoulding strength.Tube core concrete demoulding intensity PCCP-L pipes are not less than 30MPa, and PCCP-E pipes are not less than 20MPa.
PCCP-L pipes can be used and once conserved, and constant temperature maximum temperature is not higher than 85 DEG C；PCCP-E pipes use secondary method of curing, Reach demoulding strength for the first time, reach twine an intensity for the second time, highest curing temperature is no more than 60 DEG C.Steam curing not only operates Complexity, and time-consuming, high energy consumption, not environmentally.
The content of the invention
A kind of pre-stress steel cylinder coagulation is provided it is an object of the invention to overcome the shortcomings of the prior art part The preparation method of native pipe, Prestressed concrete cylinder pipe preparation method of the invention can realize exempting from for Prestressed concrete cylinder pipe Steam curing conservation, can also improve the intensity of Prestressed concrete cylinder pipe, while have simple to operate, production safety, cost be cheap, The advantages of energy-conserving and environment-protective.
The technical solution adopted by the present invention is：A kind of preparation method of Prestressed concrete cylinder pipe, including：With steel Winding ring orientation prestress steel wire on the outside of the concrete tube core of cylinder, then spray cement mortar protective course, that is, be made pre-stress steel cylinder Pipe of concrete；The concrete tube core carries out natural curing and shape by body at the beginning of the concrete tube core that will be formed after concreting Into；
Wherein, the raw material of the concrete includes cement, gathered materials, water and ultra high early strength poly-carboxylic water reducer, the super hardening Polycarboxylate water-reducer is the compound shown in formula (1) or formula (2)；
The structural formula of compound shown in the formula (1) is as follows：
The structural formula of compound shown in the formula (2) 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、R3And R4Respectively It is C1-3 alkyl alone；X is Cl, Br or I；M is 5~200 integer, and n is 0~50 integer, and z is 1~150 Integer.
In the above-mentioned technical solutions, the preparation method of Prestressed concrete cylinder pipe of the invention, with natural curing process It instead of the normal pressure steam curing process in former segment production technology, it is not necessary to steam, fully rely on natural conditions and conserved, drop Low production cost, improves production efficiency and production security.Natural curing refers under the conditions of natural temperature (be higher than 5 DEG C), take concrete covering, watering the maintenance measure such as soak, keep out the wind, being incubated.
In the above-mentioned technical solutions, in the present invention realization of natural curing mainly due to having used ultra high early strength poly-carboxylic to subtract Aqua.The ultra high early strength poly-carboxylic water reducer of the present invention had both maintained the Structural design idea of general rule high early strength poly-carboxylic water reducer, i.e., Using long side chain, short main chain, molecular structure is designed to inverted T shaped, and comb-type structure is presented, and such molecular structure can profit Ensure peptizaiton with severely sterically inhibition effect, while short main chain reduces area coverage of the water reducer in cement granules, ensures water The normal hydrated reaction of mud；What is more important, ultra high early strength poly-carboxylic water reducer of the invention realize high score using special catalyst Highly regular and use promotees aquation group polymeric monomer in son, using synergistic effect, realizes super hardening effect.
In the above-mentioned technical solutions, can be the same with former steam curing process in binder materials of the invention, using cement (preferably Ground, flyash can be added), it is not necessary to fill any other enhancing and blend material, the ultra high early strength poly-carboxylic by using the present invention subtracts Aqua, accelerate cement aquation, reach form removal and intensity of dispatching from the factory.
Preferably, the ultra high early strength poly-carboxylic water reducer shown in the formula (1) is prepared by following methods：
The synthesis of (1a) methoxyl group hydroxyl PEG intermediates
Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen Propane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin；Its reaction equation is as follows：
The synthesis of (2a) methoxyl group PEG surface-active macromonomers
Into reactor add step 1a) in synthesis methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and polymerization inhibitor, Stir, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid；Its reaction equation is as follows：
The synthesis of (3a) surface-active macromonomer
Quaternization reactant and polymerization inhibitor are added into reactor, 10-80 DEG C is warming up to, step 2a is slowly added dropwise) in The quaternization reactant solution of the methoxyl group PEG reactive intermediates of synthesis, after being added dropwise, under the conditions of 10-80 DEG C, continue Insulation reaction 1-10h, produce the surface-active macromonomer；Its reaction equation is as follows:
Wherein, the quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C1-3 alkyl alone.
The synthesis of ultra high early strength poly-carboxylic water reducer shown in (4a) formula (1)
By step 3a) surface-active macromonomer of synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, VPEG, HPEG and TPEG, water and molecular weight regulator mixing, are warming up to 85~95 DEG C, initiator are added dropwise, It is incubated after being added dropwise, is then cooled to 45~50 DEG C, is adjusted pH to 7.0-8.0, obtain the ultra high early strength poly-carboxylic water reducer.
Preferably, in the step (1a) in the mixture of methanol, oxirane and oxirane and expoxy propane one Kind and the mol ratio of epoxyhalopropane are methanol：One kind in the mixture of oxirane and oxirane and expoxy propane：Ring Oxygen halopropane=1:5~250:1~150；The step 2a) in, the mol ratio of methoxyl group hydroxyl PEG intermediates and olefin(e) acid is 1: 1.0~8.0；The step 3a) in, the mol ratio of quaternization reactant and the methoxyl group PEG reactive intermediates for 0.2~ 2：1；In the step (4a), one kind in the methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, VPEG, A kind of mol ratio of and surface-active macromonomer in HPEG and TPEG is one kind in APEG, VPEG, HPEG and TPEG：Metering system One kind in acid, acrylic acid, itaconic acid and maleic anhydride：Surface-active macromonomer=1~6.0:1.0:1.0~3.0.
Preferably, the catalyst in the step (1a) is sodium hydride or sodium；Catalyst in the step (2a) is first At least one of sulfonic acid and p-methyl benzenesulfonic acid；Polymerization inhibitor in the step (2a), (3a) is hydroquinones or to first Ether phenol；In the step (2a) dosage of polymerization inhibitor for the methoxyl group hydroxyl PEG intermediate molal quantitys 0.002%~ 0.010%, in the step (3a) dosage of polymerization inhibitor for the methoxyl group PEG surface-active macromonomer molal quantitys 0.002%~ 0.010%；Step (4a) the middle-molecular-weihydroxyethyl conditioning agent is at least one of sulfhydryl compound and isopropanol, the molecular weight The dosage of conditioning agent is the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, 0.005~5% of a kind of total mole number in VPEG, HPEG and TPEG；The sulfhydryl compound is 3- mercaptopropionic acids, sulfydryl Acetic acid, mercaptoethanol or sodium formaldehyde sulfoxylate；Initiator is hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate and mistake described in the step (4a) One kind in the aqueous solution of BP；The dosage of the initiator is the surface-active macromonomer, methacrylic acid, propylene 0.05% of a kind of total mole number in a kind of and APEG, VPEG, HPEG and TPEG in acid, itaconic acid and maleic anhydride~ 5%；In the step (4a), the time for adding of the initiator is 1~10h, and the soaking time is 1~12h.
Preferably, the ultra high early strength poly-carboxylic water reducer shown in the formula (2) is prepared by following methods：
The synthesis of (1b) methoxyl group hydroxyl PEG intermediates
Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen Propane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin；Its reaction equation is as follows：
The synthesis of (2b) methoxyl group PEG surface-active macromonomers
Into reactor add step 1b) in synthesis methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and polymerization inhibitor, Stir, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid；Its reaction equation is as follows：
The synthesis of (3b) surface-active macromonomer
Quaternization reactant and polymerization inhibitor are added into reactor, 10-80 DEG C is warming up to, step 2b is slowly added dropwise) in The quaternization reactant solution of the methoxyl group PEG reactive intermediates of synthesis, after being added dropwise, under the conditions of 10-80 DEG C, continue Insulation reaction 1-10h, produce the surface-active macromonomer；Its reaction equation is as follows:
Wherein, the quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C1-3 alkyl alone.
The synthesis of ultra high early strength poly-carboxylic water reducer shown in (4b) formula (2)
By step 3b) surface-active macromonomer of synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, HPEG, VPEG and TPEG, in acrylamide, 2- acrylamide-2-methyl propane sulfonics and ALS One kind, water and molecular weight regulator mixing are warming up to 85~95 DEG C, initiator are added dropwise, is incubated after being added dropwise, then cools To 45~50 DEG C, pH to 7.0-8.0 is adjusted, obtains super hardening quaternary ammonium salt cationic cation polycarboxylate water-reducer.
Preferably, in the step (1b) in the mixture of methanol, oxirane and oxirane and expoxy propane one Kind, the mol ratio of epoxyhalopropane is methanol：One kind in the mixture of oxirane and oxirane and expoxy propane：Epoxy Halopropane=1:5~250:1~150；The step 2b) in, the mol ratio of methoxyl group hydroxyl PEG intermediates and olefin(e) acid is 1: 1.0~8.0；The step 3b) in, the mol ratio of quaternization reactant and the methoxyl group PEG reactive intermediates for 0.2~ 2：1；One kind described in the step (4b) in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, One kind in VPEG and TPEG, surface-active macromonomer and acrylamide, 2- acrylamide-2-methyl propane sulfonics and ALS In a kind of mol ratio be methacrylic acid, acrylic acid, itaconic acid and maleic anhydride in one kind：APEG, HPEG, VPEG and One kind in TPEG：Surface-active macromonomer：One in acrylamide, 2- acrylamide-2-methyl propane sulfonics and ALS Kind=1~6.0:1.0:1.0~3.0：0.2~6.0.
Preferably, the catalyst in the step (1b) is sodium hydride or sodium；Catalyst in the step (2b) is first At least one of sulfonic acid and p-methyl benzenesulfonic acid；Polymerization inhibitor in the step (2b), (3b) is hydroquinones or to first Ether phenol；In the step (2b) dosage of polymerization inhibitor for the methoxyl group hydroxyl PEG intermediate molal quantitys 0.002%~ 0.010%, in the step (3b) dosage of polymerization inhibitor for the methoxyl group PEG surface-active macromonomer molal quantitys 0.002%~ 0.010%；Step (4b) the middle-molecular-weihydroxyethyl conditioning agent is at least one of sulfhydryl compound and isopropanol, the molecular weight The dosage of conditioning agent is the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, One in a kind of and acrylamide, 2- acrylamide-2-methyl propane sulfonics and ALS in VPEG, HPEG and TPEG The 0.005~5% of the total mole number of kind；The sulfhydryl compound is 3- mercaptopropionic acids, TGA, mercaptoethanol or hung white Block；Initiator is in the aqueous solution of hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate and benzoyl peroxide described in the step (4a) One kind；The dosage of the initiator is the surface-active macromonomer, in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride It is a kind of with APEG, VPEG, HPEG and TPEG in one kind and acrylamide, 2- acrylamide-2-methyl propane sulfonics and allyl 0.05%~5% of a kind of total mole number in base sodium sulfonate；In the step (4a), the time for adding of the initiator is 1~10h, the soaking time are 1~12h.
Concrete formation in the concrete tube core is in steel cylinder inner side or the inside and outside both sides of steel cylinder.The concrete tube core In concrete formation on the inside of the steel cylinder when, obtained Prestressed concrete cylinder pipe is lined Prestressed concrete cylinder pipe (PCCP-L)；Concrete formation in the concrete tube core is when steel cylinder inside and outside both sides, obtained prestress steel cylinder concrete Manage as embed-type Prestressed concrete cylinder pipe (PCCP-E).Both Prestressed concrete cylinder pipes are applied to the present invention.
Preferably, the concrete also includes flyash.The addition of flyash can not only be reduced mixed with replacing partial cement The cost of soil, environmental protection are coagulated, and the performances such as the workability of concrete can be improved.
Preferably, the weight of the ultra high early strength poly-carboxylic water reducer is 2.4%-the 3.5% of cement weight.
Preferably, the concrete includes the component of following parts by weight：Cement 380-420 parts, 1750-1900 parts of gathering materials, Ultra high early strength poly-carboxylic water reducer 10-14 parts and water 140-160 parts.It is highly preferred that the mixing gathered materials for rubble and sand Thing, wherein, sand is 700-750 parts, and rubble is 1180-1130 parts.
It is highly preferred that the concrete also includes the flyash of 50-80 parts.
Preferably, the concrete includes the component of following parts by weight：Cement 385-415 parts, 1800-1865 parts of gathering materials, Ultra high early strength poly-carboxylic water reducer 10.5-13.6 parts and water 143-158 parts.It is highly preferred that described gather materials for rubble and sand Mixture, wherein, sand is 710-740 parts, and rubble is 1090-1125 parts.It is highly preferred that the concrete also includes 60-75 The flyash of part.
Most preferably, the concrete includes the component of following parts by weight：395 parts of cement, 725 parts of sand, rubble 1125 70 parts of part, 150 parts of water, 11 parts of ultra high early strength poly-carboxylic water reducer and flyash；Wherein, sand and rubble gather materials to be described.
Present invention also offers prestress steel cylinder concrete made from the preparation method according to Prestressed concrete cylinder pipe Pipe.
Present invention also offers application of the ultra high early strength poly-carboxylic water reducer in Prestressed concrete cylinder pipe, the super morning Strength poly-carboxylic water reducer is the compound shown in formula (1) or formula (2)；
The structural formula of compound shown in the formula (1) is as follows：
The structural formula of compound shown in the formula (2) 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、R3And R4Respectively It is C1-3 alkyl alone；X is Cl, Br or I；M is 5~200 integer, and n is 0~50 integer, and z is 1~150 Integer.
Relative to prior art, beneficial effects of the present invention are：
1) preparation method of Prestressed concrete cylinder pipe of the invention uses ultra high early strength poly-carboxylic water reducer, eliminates steaming Vapour conserves process, is conserved completely by natural conditions, can save the energy, environmental protection；
2) due to exempting steam curing, concrete inner structure development is uniform, fine and close, cracking resistance, anti-permeability performance enhancing.
3) managed using the PCCP of non-evaporating technique, intensity stabilization, mean square deviation is less than the PCCP pipe mean square deviations of common process production (non-evaporating technique PCCP pipe mean square deviations：3.5-5.0MPa common process PCCP pipe mean square deviations：6.0-8.0.0MPa)；
4) C50PCCP is managed, and the strength of mould stripping after usual steam curing is 20-30MPa, using the pre- of non-evaporating foster technique productions Stress cylinder concrete pipe, 8-10h collapsible dies, form removal is by force up to 33-36MPa.
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.It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention, following reality NM specific experiment method in example is applied, is generally carried out according to normal experiment method.VPEG of the present invention:4- hydroxyl butyl second Alkene ether APEO；APEG：Allyl alcohol polyethenoxy ether；HPEG：Isobutene alcohol APEO；TPEG：Prenol APEO.For convenience of description, the Prestressed concrete cylinder pipe in following examples is lined pre-stress steel cylinder Pipe of concrete (PCCP-L).It should be appreciated that embed-type Prestressed concrete cylinder pipe (PCCP-E) is equally applicable to this hair Bright, compared with PCCP-L pipes, it is only that shaping position of the concrete on steel cylinder is different, does not interfere with super hardening in the present invention The performance of the effect of water reducer, in PCCP-E pipes, it can equally realize the natural curing of the first body of concrete tube core.
Embodiment 1
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：380 parts of cement, 50 parts of flyash, 700 parts of sand are broken 140 parts of 1080 parts of stone, 10 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) in the autoclave of closing, be injected separately into 1.0mol methanol, 80mol oxirane, 60mol epoxychloropropane and 3g sodium hydrides, stir, react 10h at 100 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.9mol methoxyl group hydroxyl PEG intermediates, 0.9mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene Diphenol, stir, react 15h at 110 DEG C, produce reaction product surface-active macromonomer；
3) 1.6mol triethylamines and 0.01g hydroquinones are added into glass flask, 80 DEG C is warming up to, is slowly added dropwise and contains Triethylamine solution (wherein, the methoxyl group PEG reactive intermediates of the methoxyl group PEG reactive intermediates of 0.8mol steps 2) synthesis Molar concentration is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 5h, produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 0.5mol steps 3) synthesis, 0.5mol methacrylic acids, 0.5mol APEG and 400ml deionized waters, it is described Molecular weight regulator is 3- mercaptopropionic acids, the dosage of the molecular weight regulator is the surface-active macromonomer, methacrylic acid and The 0.5% of APEG total mole numbers, 85 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is that mass concentration is 10% Potassium peroxydisulfate, the dosage of the initiator is the surface-active macromonomer, the 5% of methacrylic acid and APEG total mole numbers, drop It is 1h between added-time, after being added dropwise, insulation reaction 1h, is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust PH=7.0 is saved, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 2
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：395 parts of cement, 70 parts of flyash, 725 parts of sand are broken 150 parts of 1125 parts of stone, 11 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) in the autoclave of closing, 1mol methanol, 5mol oxirane, 1mol epoxychloropropane and 2g hydrogen are injected separately into Change sodium, stir, react 10h at 80 DEG C, produce reaction product methoxyl group hydroxy intermediate；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 1.0mol methoxyl groups hydroxy intermediate, 8.0mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 10h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.2molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, is warming up to 20 DEG C, slowly The N of the methoxyl group PEG reactive intermediates of the synthesis of the step 2) containing 1.0mol, N- dimethyl amine solution (wherein, methoxyl groups is added dropwise The molar concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 20 DEG C, to continue insulation reaction 10h, produce institute State surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 1.0mol steps 3) synthesis, 2.0mol maleic anhydrides, 0.33mol HPEG and 600ml deionized waters, it is described Molecular weight regulator is TGA, and the dosage of the molecular weight regulator is the surface-active macromonomer, maleic anhydride and HPEG The 5% of total mole number, 95 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is the over cure that mass concentration is 20% Sour ammonium, the dosage of the initiator are the 0.05% of the surface-active macromonomer, maleic anhydride and HPEG total mole numbers, time for adding For 10h, after being added dropwise, insulation reaction 12h, 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 3
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：400 parts of cement, 65 parts of flyash, 725 parts of sand are broken 150 parts of 1105 parts of stone, 12 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) in the autoclave of closing, be injected separately into 1mol methanol, 200mol oxirane, 150mol epoxychloropropane and 2g sodium hydrides, stir, react 10h at 80 DEG C, produce reaction product methoxyl group hydroxy intermediate；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 1.0mol methoxyl groups hydroxy intermediate, 4.5mol maleic anhydrides, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 5h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.75mol tripropyl amine (TPA)s and 0.01g hydroquinones are added into glass flask, 80 DEG C is warming up to, is slowly added dropwise and contains Tripropyl amine (TPA) solution (wherein, the methoxyl group PEG reactive intermediates of the methoxyl group PEG reactive intermediates of 0.75mol steps 2) synthesis Molar concentration is 10%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 2h, produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 0.7mol steps 3) synthesis, 1.0mol acrylic acid, 0.35molTPEG and 500ml deionized waters, the molecule Amount conditioning agent is mercaptoethanol, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid and TPEG total moles Several 5%, 90 DEG C are warming up to, the aqueous solution of initiator are added dropwise, the initiator is the hydrogen peroxide that mass concentration is 15%, described The dosage of initiator is 0.8%, time for adding 2.5h of the surface-active macromonomer, acrylic acid and TPEG total mole numbers, is added dropwise After, insulation reaction 3h, 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 water reducer.
Embodiment 4
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：420 parts of cement, 80 parts of flyash, 750 parts of sand are broken 160 parts of 1130 parts of stone, 14 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) in the autoclave of closing, 1.0mol methanol, 100mol oxirane and 50mol expoxy propane are injected separately into Mixture, 100mol epoxy bromopropanes and 1g sodium hydrides, stir, react 10h at 80 DEG C, produce in reaction product methoxyl group hydroxyl Mesosome；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.7mol methoxyl groups hydroxy intermediate, 2.8mol acrylic acid, 1g methanesulfonic acids and the 0.01g hydroquinones of rapid 1) middle synthesis, stirring, 10h is reacted at 80 DEG C, produces reaction product methoxyl group PEG reactive intermediates；
3) 0.8molN, N- dimethyl propylamines and 0.01g hydroquinones are added into glass flask, is warming up to 80 DEG C, slowly The N of the methoxyl group PEG reactive intermediates of the synthesis of the step 2) containing 0.5mol, N- dimethyl propylene amine aqueous solution (wherein, methoxyl groups is added dropwise The molar concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 3h, produce institute State surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 0.5mol steps 3) synthesis, 1.0mol itaconic acids, 0.17mol TPEG and 500ml deionized waters, described point Son amount conditioning agent is sodium formaldehyde sulfoxylate, and the dosage of the molecular weight regulator is the surface-active macromonomer, itaconic acid and TPEG total moles Several 2.5%, 90 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is the benzoyl peroxide that mass concentration is 15% Formyl, the dosage of the initiator are the 1% of the surface-active macromonomer, itaconic acid and TPEG total mole numbers, and time for adding is 2.5h, after being added dropwise, insulation reaction 3h, 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 water reducer.
Embodiment 5
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：395 parts of cement, 70 parts of flyash, 725 parts of sand are broken 150 parts of 1125 parts of stone, 11 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) in the autoclave of closing, 1.0mol methanol, 90mol oxirane and 20mol expoxy propane are injected separately into Mixture, 75mol epoxychloropropane and 2.5g sodium hydrides, stir, react 2h at 150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.8mol methoxyl group hydroxyl PEG intermediates, 4.8mol itaconic acids, 1.5g methanesulfonic acids and the 0.01g of rapid 1) middle synthesis are to methyl ether benzene Phenol, stir, react 3h at 170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.35molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, is warming up to 50 DEG C, is delayed The N of the slow methoxyl group PEG reactive intermediates that the synthesis of the step 2) containing 0.7mol is added dropwise, N- dimethyl amine solution (wherein, methoxyl groups The molar concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 50 DEG C, to continue insulation reaction 5h, produce institute State surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 0.5mol steps 3) synthesis, 1.0mol methacrylic acids, 0.5mol APEG and 400ml deionized waters, it is described Molecular weight regulator is 3- mercaptopropionic acids, the dosage of the molecular weight regulator is the surface-active macromonomer, methacrylic acid and The 2% of APEG total mole numbers, 85 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is that mass concentration is 10% Potassium peroxydisulfate, the dosage of the initiator are the 1.5% of the surface-active macromonomer, methacrylic acid and APEG total mole numbers, drop It is 2h between added-time, after being added dropwise, insulation reaction 2h, is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust PH=7.0 is saved, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 6
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：385 parts of cement, 60 parts of flyash, 710 parts of sand are broken 143 parts of 1090 parts of stone, 10.5 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) in the autoclave of closing, 0.8mol methanol, 80mol oxirane and 16mol expoxy propane are injected separately into Mixture, 24mol epoxychloropropane and 4g sodium hydrides, stir, react 8h at 120 DEG C, produce reaction product methoxyl group hydroxyl PEG Intermediate；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.6mol methoxyl group hydroxyl PEG intermediates, 1.8mol methacrylic acids, 4g methanesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 4h at 170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.5mol tripropyl amine (TPA)s and 0.01g hydroquinones are added into glass flask, 60 DEG C is warming up to, is slowly added dropwise and contains Tripropyl amine (TPA) solution (wherein, the methoxyl group PEG reactive intermediates of the methoxyl group PEG reactive intermediates of 0.5mol steps 2) synthesis Molar concentration is 10%), after being added dropwise, under the conditions of 60 DEG C, to continue insulation reaction 5h, produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 0.6mol steps 3) synthesis, 1.5mol acrylic acid, 0.3mol VPEG and 600ml deionized waters, it is described Molecular weight regulator is TGA, and the dosage of the molecular weight regulator is that the surface-active macromonomer, acrylic acid and HPEG are total The 1.5% of molal quantity, 95 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is the over cure that mass concentration is 20% Sour ammonium, the dosage of the initiator are the 0.5% of the surface-active macromonomer, acrylic acid and HPEG total mole numbers, and time for adding is 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 7
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：380 parts of cement, 50 parts of flyash, 700 parts of sand are broken 140 parts of 1080 parts of stone, 10 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) in the autoclave of closing, be injected separately into 1.0mol methanol, 80mol oxirane, 60mol epoxychloropropane and 3g sodium hydrides, stir, react 2h at 150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.9mol methoxyl group hydroxyl PEG intermediates, 1.05mol methacrylic acids, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis Hydroquinones, stir, react 3h at 170 DEG C, produce reaction product surface-active macromonomer；
3) 0.16mol triethylamines and 0.01g hydroquinones are added into glass flask, 80 DEG C is warming up to, is slowly added dropwise and contains Triethylamine solution (wherein, the methoxyl group PEG reactive intermediates of the methoxyl group PEG reactive intermediates of 0.8mol steps 2) synthesis Molar concentration is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 2h, produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer, 0.7mol acrylic acid, 0.7mol TPEG, 0.14mol acrylamides and the 500ml of 0.7mol steps 3) synthesis Deionized water, the molecular weight regulator are mercaptoethanol, and the dosage of the molecular weight regulator is the surface-active macromonomer, third The 1% of olefin(e) acid, acrylamide and TPEG total mole numbers, is warming up to 90 DEG C, the aqueous solution of initiator is added dropwise, the initiator is matter Measure the benzoyl peroxide that concentration is 15%, the dosage of the initiator is the surface-active macromonomer, acrylic acid, acrylamide and The 5% of TPEG total mole numbers, time for adding 10h, after being added dropwise, insulation reaction 3h, it is cooled at 50 DEG C, it is dense adds quality The NaOH solution for 30% is spent, pH=7.5 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 8
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：395 parts of cement, 70 parts of flyash, 725 parts of sand are broken 150 parts of 1125 parts of stone, 11 parts of ultra high early strength poly-carboxylic water reducer and water；
Wherein described ultra high early strength poly-carboxylic water reducer is prepared by following methods：
1) in the autoclave of closing, 1mol methanol, 5mol oxirane, 1mol epoxychloropropane and 2g hydrogen are injected separately into Change sodium, stir, react 10h at 80 DEG C, produce reaction product methoxyl group hydroxy intermediate；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 1.0mol methoxyl groups hydroxy intermediate, 8.0mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 15h at 70 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 2.0molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, is warming up to 80 DEG C, slowly The N of the methoxyl group PEG reactive intermediates of the synthesis of the step 2) containing 1.0mol, N- dimethyl amine solution (wherein, methoxyl groups is added dropwise The molar concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 2h, produce institute State surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 1.0mol steps 3) synthesis, 2.0mol acrylic acid, 0.33mol HPEG, 2.0mol 2- acrylamide -2- first Base propane sulfonic acid and 600ml deionized waters, the molecular weight regulator are TGA, and the dosage of the molecular weight regulator is institute The 5% of surface-active macromonomer, acrylic acid, 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers is stated, is warming up to 95 DEG C, drop Add the aqueous solution of initiator, the initiator is the ammonium persulfate that mass concentration is 20%, and the dosage of the initiator is described Surface-active macromonomer, acrylic acid, 0.1%, time for adding 3h of 2- acrylamide-2-methyl propane sulfonics 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 water reducer.
Embodiment 9
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：400 parts of cement, 65 parts of flyash, 725 parts of sand are broken 150 parts of 1105 parts of stone, 12 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) in the autoclave of closing, be injected separately into 1mol methanol, 200mol oxirane, 150mol epoxychloropropane and 2g sodium hydrides, stir, react 8h at 110 DEG C, produce reaction product methoxyl group hydroxy intermediate；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 1.0mol methoxyl groups hydroxy intermediate, 4.5mol maleic anhydrides, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 10h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.75mol tripropyl amine (TPA)s and 0.01g hydroquinones are added into glass flask, 50 DEG C is warming up to, is slowly added dropwise and contains Tripropyl amine (TPA) solution (wherein, the methoxyl group PEG reactive intermediates of the methoxyl group PEG reactive intermediates of 0.75mol steps 2) synthesis Molar concentration is 10%), after being added dropwise, under the conditions of 50 DEG C, to continue insulation reaction 5h, produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer, 0.75mol methacrylic acids, 0.25molVPEG, the 0.25mol 2- acryloyls of 0.5mol steps 3) synthesis Amine -2- methyl propane sulfonic acids and 400ml deionized waters, the molecular weight regulator are isopropanol, the use of the molecular weight regulator Measure as the 0.05% of the surface-active macromonomer, methacrylic acid, 2- acrylamide-2-methyl propane sulfonics and VPEG total mole numbers, 85 DEG C are warming up to, the aqueous solution of initiator is added dropwise, the initiator is the hydrogen peroxide that mass concentration is 10%, the initiator Dosage is the 3% of the surface-active macromonomer, methacrylic acid, 2- acrylamide-2-methyl propane sulfonics and VPEG total mole numbers, is dripped It is 2h between added-time, after being added dropwise, insulation reaction 2h, is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust PH=7.0 is saved, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 10
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：420 parts of cement, 80 parts of flyash, 750 parts of sand are broken 160 parts of 1130 parts of stone, 14 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) in the autoclave of closing, 1.0mol methanol, 100mol oxirane and 50mol expoxy propane are injected separately into Mixture, 100mol epoxychloropropane and 1g sodium hydrides, stir, react 10h at 80 DEG C, produce in reaction product methoxyl group hydroxyl Mesosome；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.7mol methoxyl groups hydroxy intermediate, 0.75mol acrylic acid, 1g methanesulfonic acids and the 0.01g hydroquinones of rapid 1) middle synthesis, are stirred Mix, react 10h at 80 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 2.5molN, N- dimethyl propylamines and 0.01g hydroquinones are added into glass flask, is warming up to 60 DEG C, slowly The N of the methoxyl group PEG reactive intermediates of the synthesis of the step 2) containing 0.5mol, N- dimethyl propylene amine aqueous solution (wherein, methoxyl groups is added dropwise The molar concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 60 DEG C, to continue insulation reaction 6h, produce institute State surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 0.5mol steps 3) synthesis surface-active macromonomer, 1.2mol methacrylic acids, 0.25mol APEG, 0.75mol acrylamides and 400ml deionized waters, the molecular weight regulator are 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is big for the activity Monomer, methacrylic acid, the 2% of acrylamide and APEG total mole numbers, are warming up to 85 DEG C, the aqueous solution of initiator, institute are added dropwise It is the potassium peroxydisulfate that mass concentration is 10% to state initiator, and the dosage of the initiator is the surface-active macromonomer, metering system 1.5%, time for adding 2h of acid, acrylamide and APEG total mole numbers, after being added dropwise, insulation reaction 2h, are cooled to 50 At DEG C, the NaOH solution that mass concentration is 30% is added, pH=7.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 11
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：395 parts of cement, 70 parts of flyash, 725 parts of sand are broken 150 parts of 1125 parts of stone, 11 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) in the autoclave of closing, 1.0mol methanol, 60mol oxirane and 20mol expoxy propane are injected separately into Mixture, 2mol epoxy bromopropanes and 4g sodium hydrides, stir, react 10h at 110 DEG C, produce in reaction product methoxyl group hydroxyl Mesosome；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.6mol methoxyl groups hydroxy intermediate, 1.2mol maleic anhydrides, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 10h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.8mol triethylamines and 0.01g hydroquinones are added into glass flask, 80 DEG C is warming up to, is slowly added dropwise and contains Triethylamine solution (wherein, the methoxyl group PEG reactive intermediates of the methoxyl group PEG reactive intermediates of 0.6mol steps 2) synthesis Molar concentration is 12%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 2h, produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, Surface-active macromonomer, 1.2mol maleic anhydrides, 0.6mol TPEG, 1.8mol acrylamides and the 500ml of 0.6mol steps 3) synthesis Deionized water, the molecular weight regulator are sodium formaldehyde sulfoxylate, and the dosage of the molecular weight regulator is the surface-active macromonomer, Malaysia The 1.8% of acid anhydrides, acrylamide and TPEG total mole numbers, is warming up to 90 DEG C, the aqueous solution of initiator is added dropwise, the initiator is Mass concentration is 15% benzoyl peroxide, and the dosage of the initiator is the surface-active macromonomer, maleic anhydride, acryloyl The 4% of amine and TPEG total mole numbers, time for adding 2.5h, after being added dropwise, insulation reaction 3h, it is cooled at 50 DEG C, adds Mass concentration is 30% NaOH solution, adjusts pH=7.5, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 12
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：415 parts of cement, 75 parts of flyash, 740 parts of sand are broken 158 parts of 1125 parts of stone, 13.6 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) in the autoclave of closing, it is injected separately into the mixed of 1mol methanol, 165mol oxirane and 35mol expoxy propane Compound, 1.2mol epoxy bromopropanes and 3g sodium hydrides, stir, react 8h at 100 DEG C, produce among reaction product methoxyl group hydroxyl Body；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.9mol methoxyl groups hydroxy intermediate, 4.5mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 10h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.4mol trimethylamines and 0.01g hydroquinones are added into glass flask, is warming up to 75 DEG C, be slowly added dropwise containing (wherein, methoxyl group PEG reactive intermediates rub the trimethylamine solution of the methoxyl group reactive intermediate of 0.75mol steps 2) synthesis Your concentration is 5%), after being added dropwise, under the conditions of 75 DEG C, to continue insulation reaction 6h, produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The surface-active macromonomer of 0.7mol steps 3) synthesis, 1.0mol itaconic acids, 0.25mol HPEG, 0.7mol 2- acrylamide -2- first Base propane sulfonic acid and 600ml deionized waters, the molecular weight regulator are TGA, and the dosage of the molecular weight regulator is institute The 1.5% of surface-active macromonomer, itaconic acid, ALS and HPEG total mole numbers is stated, 95 DEG C is warming up to, initiator is added dropwise The aqueous solution, the initiator are the ammonium persulfate that mass concentration is 20%, the dosage of the initiator is the surface-active macromonomer, 0.5%, time for adding 3h of itaconic acid, 2- acrylamide-2-methyl propane sulfonics 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 super hardening and gather Carboxylic acid water reducer.
Embodiment 13
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：380 parts of cement, 50 parts of flyash, 700 parts of sand are broken 140 parts of 1080 parts of stone, 10 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) in the autoclave of closing, 1mol methanol, 5mol oxirane, 1mol epoxychloropropane and 2g hydrogen are injected separately into Change sodium, stir, react 9h at 110 DEG C, produce reaction product methoxyl group hydroxy intermediate；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 1.0mol methoxyl groups hydroxy intermediate, 6.0mol acrylic acid, 3g p-methyl benzenesulfonic acids and the 0.01g of rapid 1) middle synthesis are to benzene two Phenol, stir, react 10h at 110 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 1.5molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, is warming up to 80 DEG C, slowly The N of the methoxyl group PEG reactive intermediates of the synthesis of the step 2) containing 1.0mol, N- dimethyl amine solution (wherein, methoxyl groups is added dropwise The molar concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 3h, produce institute State surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, 1.0mol steps 3) synthesis surface-active macromonomer, 1.0mol acrylic acid, 1.0mol HPEG, 0.2mol ALSs and 600ml deionized waters, the molecular weight regulator are TGA, and the dosage of the molecular weight regulator is big single for the activity Body, acrylic acid, the 5% of 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, are warming up to 95 DEG C, initiator are added dropwise The aqueous solution, the initiator are the ammonium persulfate that mass concentration is 20%, the dosage of the initiator is the surface-active macromonomer, 5%, time for adding 3h of acrylic acid, 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, after being added dropwise, protect Temperature reaction 4h, is cooled at 45 DEG C, adds the NaOH solution that mass concentration is 30%, adjusts pH=8.0, produce the poly- carboxylic of super hardening Sour water reducer.
Embodiment 14
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：395 parts of cement, 70 parts of flyash, 725 parts of sand are broken 150 parts of 1125 parts of stone, 11 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) in the autoclave of closing, 1.0mol methanol, 100mol oxirane and 50mol expoxy propane are injected separately into Mixture, 100mol epoxychloropropane and 1g sodium hydrides, stir, react 10h at 80 DEG C, produce in reaction product methoxyl group hydroxyl Mesosome；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.7mol methoxyl groups hydroxy intermediate, 0.75mol acrylic acid, 1g methanesulfonic acids and the 0.01g hydroquinones of rapid 1) middle synthesis, are stirred Mix, react 10h at 80 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 1.0molN, N- dimethyl propylamines and 0.01g hydroquinones are added into glass flask, is warming up to 80 DEG C, slowly The N of the methoxyl group PEG reactive intermediates of the synthesis of the step 2) containing 0.5mol, N- dimethyl propylene amine aqueous solution (wherein, methoxyl groups is added dropwise The Mole percent specific concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 3h, Produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The 0.5mol steps 3) surface-active macromonomer, 1.0mol methacrylic acids, 0.17mol APEG, 1.0mol ALSs and 400ml deionized waters, the molecular weight regulator are 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is big for the activity Monomer, methacrylic acid, the 0.5% of ALS and APEG total mole numbers, are warming up to 85 DEG C, the water-soluble of initiator are added dropwise Liquid, the initiator are the potassium peroxydisulfate that mass concentration is 10%, and the dosage of the initiator is the surface-active macromonomer, methyl 0.5%, time for adding 2h of acrylic acid, ALS and APEG total mole numbers, after being added dropwise, insulation reaction 2h, It is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjust pH=7.0, produce ultra high early strength poly-carboxylic water reducer.
Embodiment 15
A kind of preparation method of Prestressed concrete cylinder pipe, including：Wound on the outside of the concrete tube core with steel cylinder Ring orientation prestress steel wire, then spray cement mortar protective course, that is, be made Prestressed concrete cylinder pipe；The concrete tube core By the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
Wherein, the concrete includes the component of following parts by weight：400 parts of cement, 65 parts of flyash, 725 parts of sand are broken 150 parts of 1105 parts of stone, 12 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) in the autoclave of closing, 1.0mol methanol, 90mol oxirane and 20mol expoxy propane are injected separately into Mixture, 75mol epoxychloropropane and 2.5g sodium hydrides, stir, react 2h at 150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
2) to agitator, thermometer, reflux condensing tube, Dropping feeder tetra- mouthfuls of glass flasks of 500ml in, add step 0.8mol methoxyl group hydroxyl PEG intermediates, 3.2mol itaconic acids, 1.5g methanesulfonic acids and the 0.01g of rapid 1) middle synthesis are to methyl ether benzene Phenol, stir, react 10h at 120 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
3) 0.7molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, is warming up to 80 DEG C, slowly The N of the methoxyl group PEG reactive intermediates of the synthesis of the step 2) containing 0.7mol, N- dimethyl amine solution (wherein, methoxyl groups is added dropwise The Mole percent specific concentration of PEG reactive intermediates is 15%), after being added dropwise, under the conditions of 80 DEG C, to continue insulation reaction 3h, Produce the surface-active macromonomer；
4) in the 1000ml four-hole boiling flasks equipped with agitator, thermometer and reflux condensing tube, addition molecular weight regulator, The 0.6mol steps 3) surface-active macromonomer, 1.5mol acrylic acid, 0.3mol HPEG, 1.0mol ALSs and 600ml Deionized water, the molecular weight regulator are TGA, and the dosage of the molecular weight regulator is the surface-active macromonomer, third The 5% of olefin(e) acid, ALS and HPEG total mole numbers, is warming up to 95 DEG C, the aqueous solution of initiator, the initiator is added dropwise The ammonium persulfate for being 20% for mass concentration, the dosage of the initiator is the surface-active macromonomer, acrylic acid, allyl sulphonic acid The 5% of sodium and HPEG total mole numbers, time for adding 3h, after being added dropwise, insulation reaction 4h, it is cooled at 45 DEG C, adds matter The NaOH solution that concentration is 30% is measured, pH=8.0 is adjusted, produces ultra high early strength poly-carboxylic water reducer.
Embodiment 16
The intensity in the age not same period of the concrete in concrete tube core in embodiment 1~15 is tested, test result It see the table below.
The concrete different larval instar intensity (unit of table 1：MPa)
Age 8-10h 7d 28d
Intensity 33-36 54-57 62-73
Curing condition It is natural It is natural It is natural
Comparative example
Prestressed concrete cylinder pipe in comparative example 1~15 uses the preparation side of traditional Prestressed concrete cylinder pipe Method is made, and the difference of itself and the preparation method of the Prestressed concrete cylinder pipe in embodiment 1~15 is：At the beginning of concrete tube core Maintenance before the body demoulding is carried out using steam curing process, and the preparation method of the present invention is carried out using natural curing process；Wherein, steam It is as shown in the table to support process conditions：
The steam curing process condition of table 2
The intensity in the age not same period of the concrete in concrete tube core in comparative example 1~15 is tested, test result It see the table below.
The concrete different larval instar intensity (unit of table 3：MPa)
Pass through the data result in table 1 and table 3：Nature is employed in the maintenance process of concrete tube core of the present invention to support Shield substitutes steam-cured mode, and under identical curing time, the intensity of obtained concrete is higher.
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 1. preparation method of Prestressed concrete cylinder pipe, it is characterised in that：Including：In the concrete tube core with steel cylinder Outside winds ring orientation prestress steel wire, then spray cement mortar protective course, that is, Prestressed concrete cylinder pipe is made；It is described mixed Native tube core is coagulated by the way that body at the beginning of the concrete formed after concreting tube core is carried out into natural curing to be formed；
    Wherein, the concrete includes cement, gathered materials, water and ultra high early strength poly-carboxylic water reducer, the ultra high early strength poly-carboxylic diminishing Agent is the compound shown in formula (1) or formula (2)；
    The structural formula of compound shown in the formula (1) is as follows：
    The structural formula of compound shown in the formula (2) 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 R4It is only respectively From for C1-3 alkyl；X is Cl, Br or I；M isInteger, n isInteger, z is Integer；
    Ultra high early strength poly-carboxylic water reducer shown in the formula (1) is prepared by following methods：
    The synthesis of (1a) methoxyl group hydroxyl PEG intermediates
    Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen third Alkane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
    Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin；Its reaction equation is as follows：
    The synthesis of (2a) methoxyl group PEG surface-active macromonomers
    Into reactor add step 1a) in synthesis methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and polymerization inhibitor, stir Mix, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
    Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid；Its reaction equation is as follows：
    The synthesis of (3a) surface-active macromonomer
    Quaternization reactant and polymerization inhibitor are added into reactor, 10-80 DEG C is warming up to, step 2a is slowly added dropwise) in synthesize Methoxyl group PEG reactive intermediates quaternization reactant solution, after being added dropwise, under the conditions of 10-80 DEG C, continue to be incubated 1-10h is reacted, produces the surface-active macromonomer；Its reaction equation is as follows:
    Wherein, the quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C1-3 alkyl alone；
    The synthesis of ultra high early strength poly-carboxylic water reducer shown in (4a) formula (1)
    By step 3a) surface-active macromonomer of synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, VPEG, HPEG and TPEG, water and molecular weight regulator mixing, are warming up to 85~95 DEG C, initiator are added dropwise, It is incubated after being added dropwise, is then cooled to 45~50 DEG C, is adjusted pH to 7.0-8.0, obtain the ultra high early strength poly-carboxylic water reducer；
    Ultra high early strength poly-carboxylic water reducer shown in the formula (2) is prepared by following methods：
    The synthesis of (1b) methoxyl group hydroxyl PEG intermediates
    Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen third Alkane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
    Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin；Its reaction equation is as follows：
    The synthesis of (2b) methoxyl group PEG surface-active macromonomers
    Into reactor add step 1b) in synthesis methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and polymerization inhibitor, stir Mix, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
    Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid；Its reaction equation is as follows：
    The synthesis of (3b) surface-active macromonomer
    Quaternization reactant and polymerization inhibitor are added into reactor, 10-80 DEG C is warming up to, step 2b is slowly added dropwise) in synthesize Methoxyl group PEG reactive intermediates quaternization reactant solution, after being added dropwise, under the conditions of 10-80 DEG C, continue to be incubated 1-10h is reacted, produces the surface-active macromonomer；Its reaction equation is as follows:
    Wherein, the quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C1-3 alkyl alone；
    The synthesis of ultra high early strength poly-carboxylic water reducer shown in (4b) formula (2)
    By step 3b) surface-active macromonomer of synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, HPEG, VPEG and TPEG, in acrylamide, 2- acrylamide-2-methyl propane sulfonics and ALS One kind, water and molecular weight regulator mixing are warming up to 85~95 DEG C, initiator are added dropwise, is incubated after being added dropwise, then cools To 45~50 DEG C, pH to 7.0-8.0 is adjusted, obtains super hardening quaternary ammonium salt cationic cation polycarboxylate water-reducer.
  2. 2. the method as described in claim 1, it is characterised in that：The concrete also includes flyash.
  3. 3. the method as described in claim 1, it is characterised in that：The weight of the ultra high early strength poly-carboxylic water reducer is cement weight 2.4%-3.5%.
  4. 4. the method as described in claim 1, it is characterised in that：The concrete includes the component of following parts by weight：Cement 380-420 parts, 1750-1900 parts of gathering materials, ultra high early strength poly-carboxylic water reducer 10-14 parts and water 140-160 parts.
  5. 5. method as claimed in claim 4, it is characterised in that：The concrete also includes the flyash of 50-80 parts.
  6. 6. the method as described in claim 1, it is characterised in that：The concrete includes the component of following parts by weight：Cement 385-415 parts, 1800-1865 parts of gathering materials, ultra high early strength poly-carboxylic water reducer 10.5-13.6 parts and water 143-158 parts.
  7. 7. method as claimed in claim 6, it is characterised in that：The concrete also includes the flyash of 60-75 parts.
  8. 8. method as claimed in claim 6, it is characterised in that：The mixture to gather materials for sand and rubble, wherein sand 710-740 parts, rubble 1091-1125 parts.
  9. 9. Prestressed concrete cylinder pipe made from the method as described in any claim in claim 1~8.
  10. 10. application of the ultra high early strength poly-carboxylic water reducer in Prestressed concrete cylinder pipe, the ultra high early strength poly-carboxylic water reducer For the compound shown in formula (1) or formula (2)；
    The structural formula of compound shown in the formula (1) is as follows：
    The structural formula of compound shown in the formula (2) 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 R4It is only respectively From for C1-3 alkyl；X is Cl, Br or I；M isInteger, n isInteger, z is Integer；
    Ultra high early strength poly-carboxylic water reducer shown in the formula (1) is prepared by following methods：
    The synthesis of (1a) methoxyl group hydroxyl PEG intermediates
    Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen third Alkane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
    Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin；Its reaction equation is as follows：
    The synthesis of (2a) methoxyl group PEG surface-active macromonomers
    Into reactor add step 1a) in synthesis methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and polymerization inhibitor, stir Mix, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
    Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid；Its reaction equation is as follows：
    The synthesis of (3a) surface-active macromonomer
    Quaternization reactant and polymerization inhibitor are added into reactor, 10-80 DEG C is warming up to, step 2a is slowly added dropwise) in synthesize Methoxyl group PEG reactive intermediates quaternization reactant solution, after being added dropwise, under the conditions of 10-80 DEG C, continue to be incubated 1-10h is reacted, produces the surface-active macromonomer；Its reaction equation is as follows:
    Wherein, the quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C1-3 alkyl alone；
    The synthesis of ultra high early strength poly-carboxylic water reducer shown in (4a) formula (1)
    By step 3a) surface-active macromonomer of synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, VPEG, HPEG and TPEG, water and molecular weight regulator mixing, are warming up to 85~95 DEG C, initiator are added dropwise, It is incubated after being added dropwise, is then cooled to 45~50 DEG C, is adjusted pH to 7.0-8.0, obtain the ultra high early strength poly-carboxylic water reducer；
    Ultra high early strength poly-carboxylic water reducer shown in the formula (2) is prepared by following methods：
    The synthesis of (1b) methoxyl group hydroxyl PEG intermediates
    Into the autoclave of closing, injection methanol, oxirane or the mixture of oxirane and expoxy propane, epoxy halogen third Alkane, catalyst, stir, react 2-10h at 80-150 DEG C, produce reaction product methoxyl group hydroxyl PEG intermediates；
    Wherein, epoxyhalopropane is epoxychloropropane, epoxy bromopropane or Epiiodohydrin；Its reaction equation is as follows：
    The synthesis of (2b) methoxyl group PEG surface-active macromonomers
    Into reactor add step 1b) in synthesis methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and polymerization inhibitor, stir Mix, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；
    Wherein, olefin(e) acid is acrylic acid, methacrylic acid, maleic anhydride or itaconic acid；Its reaction equation is as follows：
    The synthesis of (3b) surface-active macromonomer
    Quaternization reactant and polymerization inhibitor are added into reactor, 10-80 DEG C is warming up to, step 2b is slowly added dropwise) in synthesize Methoxyl group PEG reactive intermediates quaternization reactant solution, after being added dropwise, under the conditions of 10-80 DEG C, continue to be incubated 1-10h is reacted, produces the surface-active macromonomer；Its reaction equation is as follows:
    Wherein, the quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C1-3 alkyl alone；
    The synthesis of ultra high early strength poly-carboxylic water reducer shown in (4b) formula (2)
    By step 3b) surface-active macromonomer of synthesis, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, One kind in APEG, HPEG, VPEG and TPEG, in acrylamide, 2- acrylamide-2-methyl propane sulfonics and ALS One kind, water and molecular weight regulator mixing are warming up to 85~95 DEG C, initiator are added dropwise, is incubated after being added dropwise, then cools To 45~50 DEG C, pH to 7.0-8.0 is adjusted, obtains super hardening quaternary ammonium salt cationic cation polycarboxylate water-reducer.
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