CN105293976B

CN105293976B - A kind of pile tube and preparation method thereof

Info

Publication number: CN105293976B
Application number: CN201510666757.9A
Authority: CN
Inventors: 张小富; 赵利华; 李论; 白淑英
Original assignee: GUANGXI RED WALL NEW MATERIAL CO Ltd; GUANGDONG REDWALL NEW MATERIALS CO Ltd
Current assignee: GUANGXI RED WALL NEW MATERIAL CO Ltd; GUANGDONG REDWALL NEW MATERIALS CO Ltd
Priority date: 2015-10-14
Filing date: 2015-10-14
Publication date: 2017-10-31
Anticipated expiration: 2035-10-14
Also published as: CN105293976A

Abstract

The invention discloses a kind of preparation method of pile tube, comprise the following steps：Concrete material is mixed to form pile concrete, the pile concrete being stirred is fitted into mould, carry out prestressed stretch-draw, pile concrete after prestressed stretch-draw is centrifuged, until pile tube shaping, demoulding natural curing is then carried out, the PHC piles are produced；The concrete material includes ultra high early strength poly-carboxylic water reducer, and the ultra high early strength poly-carboxylic water reducer is the compound shown in formula (1) or formula (2).The preparation method of the pile tube of the present invention has simple to operate, production safety, advantage with low cost；Pile tube inner wall smooth produced by the present invention and screed is relatively thin, is difficult soft slurry, 7 10 hours collapsible dies reach intensity of dispatching from the factory in 35 days.

Description

A kind of pile tube and preparation method thereof

Technical field

The invention belongs to concrete tubular pile field, more particularly to a kind of pile tube and preparation method thereof.

Background technology

Over nearly 20 years, the production of conventional PHC piles (PHC pile tubes), is all to take second steam Maintaining production technique, is just supported and high-pressure curing, steam-cured pond and autoclave are required for expending a large amount of steam.But the new environmental law of country Mandatory implementation, many 10 tons (contain 10 tons) following coal-burning boilers all suffer from environmentally friendly upgrading, and it is up to standard to want environmental impact assessment, finally to select Select burning natural gas.This will bring jumbo cost to increase to all pile tube manufacturers, according to statistics：Fuel cost is coal-fired cost 3.5-4.0 times；Combustion gas cost is 4.5-5.5 times of coal-fired cost, by taking conventional products D500-125 as an example, per mitron stake into This will increase 15-20 members or so.So, tubular pile industry " boiler crisis " can spread quickly to come, and it will turn into the production of each pile tube The problem that producer must face.

At present, existing many experts and people in the industry are explored and studied to the pressure steaming technique of exempting from of PHC pile tubes, are retained Primary steam maintenance processes (that is, 85 DEG C of constant temperature, are conserved 6 hours in curing pool), and the addition silicon ash (94 grades) in raw material With the mixing material of miberal powder (S115 grades), to improve the early strength of concrete.But the material costs such as silicon ash are higher, be not suitable for Pile tube Market Situation at this stage.

The content of the invention

An object of the present invention is to solve to ask present in existing PHC piles preparation process Inscribe and provide a kind of preparation method of pile tube, the preparation method of pile tube of the invention can realize that non-evaporating support exempts from pressure steaming, with behaviour Make simple, production safety, advantage with low cost.

The technical solution adopted by the present invention is：A kind of preparation method of pile tube, comprises the following steps：Concrete material is mixed Close stirring and form pile concrete, the pile concrete being stirred is fitted into mould, prestressed stretch-draw is carried out, by prestressing force Pile concrete after drawing is centrifuged, until pile tube shaping, then carries out demoulding natural curing, produce the prestressed high-strength Spend concrete tubular pile；The concrete material includes ultra high early strength poly-carboxylic water reducer, and the ultra high early strength poly-carboxylic water reducer is formula Or the compound shown in formula (2) (1)；

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 R₄Point It is not 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, it is of the invention it is double exempt from preparation technology, remove the twice steam in former pile tube production technology from Conserve process, it is not necessary to use steam, fully rely on natural conditions and conserved, reduce production cost, improve production efficiency And production security.Natural curing refers under the conditions of natural temperature (be higher than 5 DEG C), concrete is taken covering, wetting of watering, The maintenance measure such as keep out the wind, be incubated.

In the above-mentioned technical solutions, double realizations for exempting from preparation technology of the invention are mainly due to having used the poly- carboxylic of super hardening Sour water reducer.The ultra high early strength poly-carboxylic water reducer of the present invention had both maintained the structure design reason of general rule high early strength poly-carboxylic water reducer Read, that is, use long side chain, short main chain, molecular structure is designed to inverted T shaped, comb-type structure, such molecular structure is presented Peptizaiton can be ensured using severely sterically inhibition effect, while short main chain reduces area coverage of the water reducer in cement granules, Ensure the normal hydrated reaction of cement；What is more important, ultra high early strength poly-carboxylic water reducer of the invention is real using special catalyst Show highly regular in macromolecule and use rush aquation group polymeric monomer, using synergistic effect, realize super hardening effect.

In the above-mentioned technical solutions, the concrete material generally comprises cement, sand, rubble and water, super in order to realize Early strong, the present invention with the addition of additive ultra high early strength poly-carboxylic water reducer.Concrete material is not limited herein, in the prior art The concrete material used is added after the ultra high early strength poly-carboxylic water reducer of the present invention, and super hardening effect can be achieved.For example, this hair Bright concrete material can be：Concrete material includes cement, sand, rubble, water and additive, and wherein additive is comprising super High early strength poly-carboxylic water reducer；The present invention concrete reducing material can be：Concrete material comprising cement, sand, rubble, water, Additive and admixture, wherein additive include ultra high early strength poly-carboxylic water reducer.

Preferably, the ultra high early strength poly-carboxylic water reducer shown in the formula (1) is prepared from by following methods：

The synthesis of (1a) methoxyl group hydroxyl PEG intermediates

Into the autoclave of closing, mixture, the epoxy halogen of injection methanol, oxirane or oxirane and expoxy propane Propane, catalyst, are stirred, and are reacted 2-10h at 80-150 DEG C, are produced 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

Step 1a is added into reactor) middle methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and the polymerization inhibitor synthesized, 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 After the quaternization reactant solution of the methoxyl group PEG reactive intermediates of synthesis, completion of dropping, under the conditions of 10-80 DEG C, continue Insulation reaction 1-10h, 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 C1-3 alkyl alone respectively.

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 completion of dropping, is then cooled to 45~50 DEG C, pH is to 7.0-8.0 for regulation, obtains the ultra high early strength poly-carboxylic water reducer.

Preferably, one in the mixture of methanol in the step (1a), oxirane and oxirane and expoxy propane Plant and the mol ratio of epoxyhalopropane is 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) consumption of polymerization inhibitor for the methoxyl group hydroxyl PEG intermediate molal quantitys 0.002%~ 0.010%, in the step (3a) consumption 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 consumption 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 consumption 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 from by following methods：

The synthesis of (1b) methoxyl group hydroxyl PEG intermediates

The synthesis of (2b) methoxyl group PEG surface-active macromonomers

Step 1b is added into reactor) middle methoxyl group hydroxyl PEG intermediates, olefin(e) acid, catalyst and the polymerization inhibitor synthesized, Stir, react 3-15h at 70-170 DEG C, produce reaction product methoxyl group PEG reactive intermediates；

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 After the quaternization reactant solution of the methoxyl group PEG reactive intermediates of synthesis, completion of dropping, under the conditions of 10-80 DEG C, continue Insulation reaction 1-10h, produces the surface-active macromonomer；Its reaction equation is as follows:

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, In one kind in APEG, HPEG, VPEG and TPEG, 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, are added dropwise after initiator, completion of dropping and are incubated, then cool To 45~50 DEG C, pH is to 7.0-8.0 for regulation, obtains super hardening quaternary ammonium salt cationic cation polycarboxylate water-reducer.

Preferably, one in the mixture of methanol in the step (1b), oxirane and oxirane and expoxy propane 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 Plant=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) consumption of polymerization inhibitor for the methoxyl group hydroxyl PEG intermediate molal quantitys 0.002%~ 0.010%, in the step (3b) consumption 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 consumption 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 planted；The sulfhydryl compound is 3- mercaptopropionic acids, TGA, mercaptoethanol or hung white Block；During initiator described in the step (4a) is the aqueous solution of hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate and benzoyl peroxide One kind；The consumption 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 is 1~12h.

Preferably, the concrete material is included：Cement, sand, rubble, ultra high early strength poly-carboxylic water reducer and water.

Preferably, the solid volume of the folding of the ultra high early strength poly-carboxylic water reducer is the 0.1%~0.3% of cement weight.

Preferably, the concrete material proportioning is as follows：440~480 parts of cement, 660~700 parts of sand, a diameter of 5~ 1200~1400 parts of 25mm rubble, 10~15 parts of ultra high early strength poly-carboxylic water reducer, 105~125 parts of water.

It is highly preferred that the concrete material proportioning is as follows：450~470 parts of cement, 670~690 parts of sand, a diameter of 5 1250~1350 parts of~25mm rubble, 10~15 parts of ultra high early strength poly-carboxylic water reducer, 105~125 parts of water.

Most preferably, the proportioning of the raw material is as follows：460 parts of cement, 680 parts of sand, a diameter of 5~10mm rubble 396 parts, 924 parts of a diameter of 10~25mm rubble, 12.42 parts of ultra high early strength poly-carboxylic water reducer, 115 parts of water.

Preferably, in the rubble of a diameter of 5~25mm, 5~10mm rubble is 300~400 parts, 10~25mm's Rubble is 900~1000 parts.

It is highly preferred that in the rubble of a diameter of 5~25mm, 5~10mm rubble is 350~400 parts, 10~25mm Rubble be 900~950 parts.

Preferably, the modulus of fineness of the sand is 2.4~3.0；The crush values index of the rubble is less than 8%.

Preferably, the centrifugation is successively through low speed, low-medium speed, middling speed and high speed centrifugation step.

Present invention also offers pile tube made from the preparation method according to described pile tube.

Exempt from PHC piles made from preparation technology through double, inner wall smooth and screed is relatively thin is difficult Soft slurry；By reaching that the pile tube of 3-5 days carries out core pulling experiment to age, it can be found that centrifugation layering is not obvious, coarse-fine aggregate point Cloth is uniform, and the rare stomata of concrete compaction, 7-10 hours collapsible dies reach intensity of dispatching from the factory in 3-5 days.

Relative to prior art, beneficial effects of the present invention are：

1) preparation method of pile tube of the invention eliminates primary steam maintenance and autoclave curing process, passes through completely Natural conditions progress oxygen shield, no at all steam, have saved the energy, have protected environment；

2) levigate quartz sand powder is not used in the binder materials used in the preparation method of pile tube of the invention, uses pure water Mud is produced；Because binder materials is striaght cement, so concrete cohesiveness is good, slump gradual loss is small, Workable, It is easy to operate；

If 3) using high-mark cement in the preparation method of pile tube of the invention, by selecting high performance additive super hardening Polycarboxylate water-reducer, produces high performance concrete, and not only concrete grade is high, and cracking resistance, anti-permeability performance strengthen；

4) the PHC pile tubes produced using the preparation method of the pile tube of the present invention, intensity stabilization, mean square deviation is less than common process The PHC pile tube mean square deviations of production are (double to exempt from mean square deviation：3.0-4.0MPa, common process mean square deviation：5.0-6.0MPa)；

5) strength of mould stripping after national regulations steam curing is 42-45MPa, using double PHC pile tubes for exempting from technique productions, early Phase strength development is rapid, and complete natural curing, 7-10 hours collapsible dies, intensity reaches 50-55MPa, and intensity can reach within 3 days 84-86MPa。

Brief description of the drawings

Fig. 1 is the transverse views of PHC piles made from embodiment 17；

Fig. 2 is longitudinal view of PHC piles made from embodiment 17.

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.

Embodiment 1

A kind of preparation method of pile tube, comprises the following steps：Concrete material is mixed to form pile concrete, will The raw material being stirred is fitted into mould, carry out prestressed stretch-draw, by after prestressed stretch-draw pile concrete carry out low speed, it is low in Speed, middling speed and high speed centrifugation, until pile tube shaping, then carries out demoulding natural curing, obtain prestressed high strength concrete pipe Stake；

The concrete material proportioning is as follows：430 parts of cement, 650 parts of sand, 1200 parts of a diameter of 5~25mm rubble, 10 parts of ultra high early strength poly-carboxylic water reducer, 105 parts of water；

Wherein, 5~10mm rubble is 300 parts, and 10~25mm rubble is 900 parts；

The ultra high early strength poly-carboxylic water reducer is prepared from by following methods：

1) in the autoclave of closing, be injected separately into 1.0mol methanol, 80mol oxirane, 60mol epoxychloropropane and 3g sodium hydrides, are stirred, and are reacted 10h at 100 DEG C, are produced reaction product methoxyl group hydroxyl PEG intermediates；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 15h at 110 DEG C, is produced 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 0.8mol steps 2) synthesis methoxyl group PEG reactive intermediates triethylamine solution (wherein, methoxyl group PEG reactive intermediates Molar concentration is 15%), after completion of dropping, 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, 0.5mol steps 3) synthesis surface-active macromonomer, 0.5mol methacrylic acids, 0.5mol APEG and 400ml deionized waters, it is described Molecular weight regulator is 3- mercaptopropionic acids, the consumption of the molecular weight regulator is the surface-active macromonomer, methacrylic acid and The 0.5% of APEG total mole numbers, is warming up to 85 DEG C, the aqueous solution of initiator is added dropwise, the initiator is that mass concentration is 10% Potassium peroxydisulfate, the consumption of the initiator is the surface-active macromonomer, the 5% of methacrylic acid and APEG total mole numbers, drop It is that insulation reaction 1h is cooled at 50 DEG C after 1h, completion of dropping between added-time, adds the NaOH solution that mass concentration is 30%, adjust PH=7.0 is saved, ultra high early strength poly-carboxylic water reducer is produced.

Embodiment 2

The concrete material proportioning is as follows：450 parts of cement, 700 parts of sand, 1300 parts of a diameter of 5~25mm rubble, 12 parts of ultra high early strength poly-carboxylic water reducer, 105 parts of water；

Wherein, 5~10mm rubble is 380 parts, and 10~25mm rubble is 920 parts；

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) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 10h at 110 DEG C, is produced reaction product methoxyl group PEG reactive intermediates；

3) 0.2molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, 20 DEG C are warming up to, slowly Be added dropwise the step 2 containing 1.0mol) synthesize methoxyl group PEG reactive intermediates N, N- dimethyl amines solution (wherein, methoxyl group The molar concentration of PEG reactive intermediates is 15%), after completion of dropping, under the conditions of 20 DEG C, continuation insulation reaction 10h produces 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, 2.0mol maleic anhydrides, 0.33mol HPEG and 600ml deionized waters, it is described Molecular weight regulator is TGA, and the consumption of the molecular weight regulator is the surface-active macromonomer, maleic anhydride and HPEG The 5% of total mole number, is warming up to 95 DEG C, the aqueous solution of initiator is added dropwise, the initiator is the over cure that mass concentration is 20% Sour ammonium, the consumption of the initiator is the 0.05% of the surface-active macromonomer, maleic anhydride and HPEG total mole numbers, time for adding For 10h, after completion of dropping, insulation reaction 12h is cooled at 45 DEG C, is added the NaOH solution that mass concentration is 30%, is adjusted pH =8.0, produce ultra high early strength poly-carboxylic water reducer.

Embodiment 3

The concrete material proportioning is as follows：The concrete material proportioning is as follows：500 parts of cement, 750 parts of sand, directly Footpath is 5~25mm 1350 parts of rubble, 14 parts of ultra high early strength poly-carboxylic water reducer, 120 parts of water；

Wherein, 5~10mm rubble is 400 parts, and 10~25mm rubble is 950 parts；

1) in the autoclave of closing, be injected separately into 1mol methanol, 200mol oxirane, 150mol epoxychloropropane and 2g sodium hydrides, are stirred, and are reacted 10h at 80 DEG C, are produced reaction product methoxyl group hydroxy intermediate；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 5h at 110 DEG C, is produced 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 0.75mol steps 2) synthesis methoxyl group PEG reactive intermediates tripropyl amine (TPA) solution (wherein, methoxyl group PEG reactive intermediates Molar concentration is 10%), after completion of dropping, 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, 0.7mol steps 3) synthesis surface-active macromonomer, 1.0mol acrylic acid, 0.35molTPEG and 500ml deionized waters, the molecule Amount conditioning agent is mercaptoethanol, and the consumption of the molecular weight regulator is the surface-active macromonomer, acrylic acid and TPEG total moles Several 5%, is warming up to 90 DEG C, the aqueous solution of initiator is added dropwise, the initiator is the hydrogen peroxide that mass concentration is 15%, described The consumption of initiator is the 0.8% of the surface-active macromonomer, acrylic acid and TPEG total mole numbers, and time for adding is 2.5h, is added dropwise After finishing, insulation reaction 3h is cooled at 50 DEG C, is added the NaOH solution that mass concentration is 30%, is adjusted pH=7.5, produce Ultra high early strength poly-carboxylic water reducer.

Embodiment 4

Wherein, 5~10mm rubble is 380 parts, and 10~25mm rubble is 920 parts；

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, are stirred, and are reacted 10h at 80 DEG C, are produced in reaction product methoxyl group hydroxyl Mesosome；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, reaction product methoxyl group PEG reactive intermediates are produced；

3) 0.8molN, N- dimethyl propylamines and 0.01g hydroquinones are added into glass flask, 80 DEG C are warming up to, slowly Be added dropwise the step 2 containing 0.5mol) synthesize methoxyl group PEG reactive intermediates N, N- dimethyl propylenes amine aqueous solution (wherein, methoxyl group The molar concentration of PEG reactive intermediates is 15%), after completion of dropping, under the conditions of 80 DEG C, continuation insulation reaction 3h produces 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, 1.0mol itaconic acids, 0.17mol TPEG and 500ml deionized waters, described point Son amount conditioning agent is sodium formaldehyde sulfoxylate, and the consumption of the molecular weight regulator is the surface-active macromonomer, itaconic acid and TPEG total moles Several 2.5%, is warming up to 90 DEG C, the aqueous solution of initiator is added dropwise, the initiator is the benzoyl peroxide that mass concentration is 15% Formyl, the consumption of the initiator is the 1% of the surface-active macromonomer, itaconic acid and TPEG total mole numbers, and time for adding is After 2.5h, completion of dropping, insulation reaction 3h is cooled at 50 DEG C, is added the NaOH solution that mass concentration is 30%, is adjusted pH= 7.5, produce ultra high early strength poly-carboxylic water reducer.

Embodiment 5

The concrete material proportioning is as follows：The concrete material proportioning is as follows：500 parts of cement, 750 parts of sand, directly Footpath is 5~25mm 1400 parts of rubble, 14 parts of ultra high early strength poly-carboxylic water reducer, 120 parts of water；

Wherein, 5~10mm rubble is 400 parts, and 10~25mm rubble is 1000 parts；

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, are stirred, and are reacted 2h at 150 DEG C, are produced reaction product methoxyl group hydroxyl PEG intermediates；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 3h at 170 DEG C, is produced reaction product methoxyl group PEG reactive intermediates；

3) 0.35molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, 50 DEG C are warming up to, delayed It is slow that the step 2 containing 0.7mol is added dropwise) N of methoxyl group PEG reactive intermediates that synthesizes, N- dimethyl amines solution (wherein, methoxyl group The molar concentration of PEG reactive intermediates is 15%), after completion of dropping, under the conditions of 50 DEG C, continuation insulation reaction 5h produces 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, 1.0mol methacrylic acids, 0.5mol APEG and 400ml deionized waters, it is described Molecular weight regulator is 3- mercaptopropionic acids, the consumption of the molecular weight regulator is the surface-active macromonomer, methacrylic acid and The 2% of APEG total mole numbers, is warming up to 85 DEG C, the aqueous solution of initiator is added dropwise, the initiator is that mass concentration is 10% Potassium peroxydisulfate, the consumption of the initiator is the 1.5% of the surface-active macromonomer, methacrylic acid and APEG total mole numbers, drop It is that insulation reaction 2h is cooled at 50 DEG C after 2h, completion of dropping between added-time, adds the NaOH solution that mass concentration is 30%, adjust PH=7.0 is saved, ultra high early strength poly-carboxylic water reducer is produced.

Embodiment 6

The concrete material proportioning is as follows：The concrete material proportioning is as follows：460 parts of cement, 680 parts of sand, directly Footpath is 5~25mm 1320 parts of rubble, 12.42 parts of ultra high early strength poly-carboxylic water reducer, 115 parts of water；

Wherein, 5~10mm rubble is 396 parts, and 10~25mm rubble is 924 parts；

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, are stirred, and are reacted 8h at 120 DEG C, are produced reaction product methoxyl group hydroxyl PEG Intermediate；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 4h at 170 DEG C, is produced 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 0.5mol steps 2) synthesis methoxyl group PEG reactive intermediates tripropyl amine (TPA) solution (wherein, methoxyl group PEG reactive intermediates Molar concentration is 10%), after completion of dropping, 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, 0.6mol steps 3) synthesis the surface-active macromonomer, 1.5mol acrylic acid, 0.3mol VPEG and 600ml deionized waters, it is described Molecular weight regulator is TGA, and the consumption of the molecular weight regulator is that the surface-active macromonomer, acrylic acid and HPEG are total The 1.5% of molal quantity, is warming up to 95 DEG C, the aqueous solution of initiator is added dropwise, the initiator is the over cure that mass concentration is 20% Sour ammonium, the consumption of the initiator is the 0.5% of the surface-active macromonomer, acrylic acid and HPEG total mole numbers, and time for adding is After 3h, completion of dropping, insulation reaction 4h is cooled at 45 DEG C, is added the NaOH solution that mass concentration is 30%, is adjusted pH= 8.0, produce ultra high early strength poly-carboxylic water reducer.

Embodiment 7

Wherein, 5~10mm rubble is 400 parts, and 10~25mm rubble is 950 parts；

1) in the autoclave of closing, be injected separately into 1.0mol methanol, 80mol oxirane, 60mol epoxychloropropane and 3g sodium hydrides, are stirred, and are reacted 2h at 150 DEG C, are produced reaction product methoxyl group hydroxyl PEG intermediates；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 3h at 170 DEG C, is produced 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 0.8mol steps 2) synthesis methoxyl group PEG reactive intermediates triethylamine solution (wherein, methoxyl group PEG reactive intermediates Molar concentration is 15%), after completion of dropping, 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, 0.7mol steps 3) synthesis surface-active macromonomer, 0.7mol acrylic acid, 0.7mol TPEG, 0.14mol acrylamide and 500ml Deionized water, the molecular weight regulator is mercaptoethanol, and the consumption 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, and the aqueous solution of initiator is added dropwise, and the initiator is matter Measure the benzoyl peroxide that concentration is 15%, the consumption of the initiator is the surface-active macromonomer, acrylic acid, acrylamide and The 5% of TPEG total mole numbers, after time for adding is 10h, completion of dropping, insulation reaction 3h is cooled at 50 DEG C, adds quality dense The NaOH solution for 30% is spent, pH=7.5 is adjusted, produces ultra high early strength poly-carboxylic water reducer.

Embodiment 8

Wherein, 5~10mm rubble is 396 parts, and 10~25mm rubble is 924 parts；

Wherein described ultra high early strength poly-carboxylic water reducer is prepared from by following methods：

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 15h at 70 DEG C, is produced reaction product methoxyl group PEG reactive intermediates；

3) 2.0molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, 80 DEG C are warming up to, slowly Be added dropwise the step 2 containing 1.0mol) synthesize methoxyl group PEG reactive intermediates N, N- dimethyl amines solution (wherein, methoxyl group The molar concentration of PEG reactive intermediates is 15%), after completion of dropping, under the conditions of 80 DEG C, continuation insulation reaction 2h produces 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, 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 consumption 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, 95 DEG C, drop are warming up to Plus the aqueous solution of initiator, the initiator is the ammonium persulfate that mass concentration is 20%, and the consumption of the initiator is described Surface-active macromonomer, acrylic acid, the 0.1% of 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, time for adding is 3h, After completion of dropping, insulation reaction 4h is cooled at 45 DEG C, is added the NaOH solution that mass concentration is 30%, is adjusted pH=8.0, Produce ultra high early strength poly-carboxylic water reducer；

Embodiment 9

Wherein, 5~10mm rubble is 396 parts, and 10~25mm rubble is 924 parts；

1) in the autoclave of closing, be injected separately into 1mol methanol, 200mol oxirane, 150mol epoxychloropropane and 2g sodium hydrides, are stirred, and are reacted 8h at 110 DEG C, are produced reaction product methoxyl group hydroxy intermediate；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 10h at 110 DEG C, is produced 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 0.75mol steps 2) synthesis methoxyl group PEG reactive intermediates tripropyl amine (TPA) solution (wherein, methoxyl group PEG reactive intermediates Molar concentration is 10%), after completion of dropping, 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, 0.5mol steps 3) synthesis surface-active macromonomer, 0.75mol methacrylic acids, 0.25mol VPEG, 0.25mol 2- acryloyls 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 Consumption is the 3% of the surface-active macromonomer, methacrylic acid, 2- acrylamide-2-methyl propane sulfonics and VPEG total mole numbers, drop It is that insulation reaction 2h is cooled at 50 DEG C after 2h, completion of dropping between added-time, adds the NaOH solution that mass concentration is 30%, adjust PH=7.0 is saved, ultra high early strength poly-carboxylic water reducer is produced.

Embodiment 10

Wherein, 5~10mm rubble is 396 parts, and 10~25mm rubble is 924 parts；

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, are stirred, and are reacted 10h at 80 DEG C, are produced in reaction product methoxyl group hydroxyl Mesosome；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, 10h is reacted 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, 60 DEG C are warming up to, slowly Be added dropwise the step 2 containing 0.5mol) synthesize methoxyl group PEG reactive intermediates N, N- dimethyl propylenes amine aqueous solution (wherein, methoxyl group The molar concentration of PEG reactive intermediates is 15%), after completion of dropping, under the conditions of 60 DEG C, continuation insulation reaction 6h produces 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 acrylamide and 400ml deionized waters, the molecular weight regulator is 3- mercaptopropionic acids, and the consumption of the molecular weight regulator is big for the activity Monomer, methacrylic acid, the 2% of acrylamide and APEG total mole numbers, are warming up to 85 DEG C, and the aqueous solution of initiator, institute is added dropwise It is the potassium peroxydisulfate that mass concentration is 10% to state initiator, and the consumption of the initiator is the surface-active macromonomer, metering system The 1.5% of acid, acrylamide and APEG total mole numbers, after time for adding is 2h, completion of dropping, insulation reaction 2h is 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

Wherein, 5~10mm rubble is 396 parts, and 10~25mm rubble is 924 parts；

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, are stirred, and are reacted 10h at 110 DEG C, are produced in reaction product methoxyl group hydroxyl Mesosome；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 10h at 110 DEG C, is produced 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 0.6mol steps 2) synthesis methoxyl group PEG reactive intermediates triethylamine solution (wherein, methoxyl group PEG reactive intermediates Molar concentration is 12%), after completion of dropping, 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, 0.6mol steps 3) synthesis surface-active macromonomer, 1.2mol maleic anhydrides, 0.6mol TPEG, 1.8mol acrylamide and 500ml Deionized water, the molecular weight regulator is sodium formaldehyde sulfoxylate, and the consumption 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, and the aqueous solution of initiator is added dropwise, and the initiator is Mass concentration is 15% benzoyl peroxide, and the consumption of the initiator is the surface-active macromonomer, maleic anhydride, acryloyl The 4% of amine and TPEG total mole numbers, after time for adding is 2.5h, completion of dropping, insulation reaction 3h is cooled at 50 DEG C, is added Mass concentration is 30% NaOH solution, adjusts pH=7.5, produces ultra high early strength poly-carboxylic water reducer.

Embodiment 12

Wherein, 5~10mm rubble is 396 parts, and 10~25mm rubble is 924 parts；

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, are stirred, and are reacted 8h at 100 DEG C, are produced in the middle of reaction product methoxyl group hydroxyl Body；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 10h at 110 DEG C, is produced reaction product methoxyl group PEG reactive intermediates；

3) 0.4mol trimethylamines and 0.01g hydroquinones are added into glass flask, 75 DEG C are warming up to, be slowly added dropwise containing 0.75mol steps 2) (wherein, methoxyl group PEG reactive intermediates rub for the trimethylamine solution of methoxyl group reactive intermediate of synthesis Your concentration is 5%), after completion of dropping, 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, 0.7mol steps 3) synthesis surface-active macromonomer, 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 consumption 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 are warming up to, initiator is added dropwise The aqueous solution, the initiator is the ammonium persulfate that mass concentration is 20%, the consumption of the initiator is the surface-active macromonomer, The 0.5% of itaconic acid, 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, after time for adding is 3h, completion of dropping, Insulation reaction 4h, is cooled at 45 DEG C, adds the NaOH solution that mass concentration is 30%, adjusts pH=8.0, produces super hardening and gathers Carboxylic acid water reducer.

Embodiment 13

Wherein, 5~10mm rubble is 300 parts, and 10~25mm rubble is 900 parts；

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) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 10h at 110 DEG C, is produced reaction product methoxyl group PEG reactive intermediates；

3) 1.5molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, 80 DEG C are warming up to, slowly Be added dropwise the step 2 containing 1.0mol) synthesize methoxyl group PEG reactive intermediates N, N- dimethyl amines solution (wherein, methoxyl group The molar concentration of PEG reactive intermediates is 15%), after completion of dropping, under the conditions of 80 DEG C, continuation insulation reaction 3h produces 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 ALS and 600ml deionized waters, the molecular weight regulator is TGA, and the consumption 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, and initiator is added dropwise The aqueous solution, the initiator is the ammonium persulfate that mass concentration is 20%, the consumption of the initiator is the surface-active macromonomer, The 5% of acrylic acid, 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, after time for adding is 3h, completion of dropping, is protected 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

Wherein, 5~10mm rubble is 400 parts, and 10~25mm rubble is 950 parts；

3) 1.0molN, N- dimethyl propylamines and 0.01g hydroquinones are added into glass flask, 80 DEG C are warming up to, slowly Be added dropwise the step 2 containing 0.5mol) synthesize methoxyl group PEG reactive intermediates N, N- dimethyl propylenes amine aqueous solution (wherein, methoxyl group The Mole percent specific concentration of PEG reactive intermediates is 15%), after completion of dropping, 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, 0.5mol steps 3) surface-active macromonomer, 1.0mol methacrylic acids, 0.17mol APEG, 1.0mol ALS and 400ml deionized waters, the molecular weight regulator is 3- mercaptopropionic acids, and the consumption of the molecular weight regulator is big for the activity Monomer, methacrylic acid, the 0.5% of ALS and APEG total mole numbers, are warming up to 85 DEG C, and the water-soluble of initiator is added dropwise Liquid, the initiator is the potassium peroxydisulfate that mass concentration is 10%, and the consumption of the initiator is the surface-active macromonomer, methyl The 0.5% of acrylic acid, ALS and APEG total mole numbers, after time for adding is 2h, completion of dropping, 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

Wherein, 5~10mm rubble is 396 parts, and 10~25mm rubble is 924 parts；

2) into agitator, thermometer, reflux condensing tube, tetra- mouthfuls of glass flasks of 500ml of Dropping feeder, step is added 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, is stirred, and is reacted 10h at 120 DEG C, is produced reaction product methoxyl group PEG reactive intermediates；

3) 0.7molN, N- dimethyl amines and 0.01g hydroquinones are added into glass flask, 80 DEG C are warming up to, slowly Be added dropwise the step 2 containing 0.7mol) synthesize methoxyl group PEG reactive intermediates N, N- dimethyl amines solution (wherein, methoxyl group The Mole percent specific concentration of PEG reactive intermediates is 15%), after completion of dropping, 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, 0.6mol steps 3) surface-active macromonomer, 1.5mol acrylic acid, 0.3mol HPEG, 1.0mol ALS and 600ml Deionized water, the molecular weight regulator is TGA, and the consumption 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, and the aqueous solution of initiator, the initiator is added dropwise The ammonium persulfate for being 20% for mass concentration, the consumption of the initiator is the surface-active macromonomer, acrylic acid, allyl sulphonic acid The 5% of sodium and HPEG total mole numbers, after time for adding is 3h, completion of dropping, insulation reaction 4h 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

Intensity to the age not same period of obtained PHC piles in embodiment 1~15 is tested, Test result see the table below.

The concrete different larval instar strength development situation of table 1

Embodiment 17

The contrast test of ultra high early strength poly-carboxylic water reducer and naphthalene water reducer

The selection of 1.1 raw material

(1) cement：From P II52.5^RPortland cement, specific surface area 320m²/kg。

The chemical composition (%) of the cement of table 2

SiO₂	Al₂O₃	MgO	CaO	Fe₂O₃	Loss on ignition
						23.82	3.37	4.85	61.20	4.32	2.44

(2) additive：From the ultra high early strength poly-carboxylic water reducer in embodiment 1~15.

The additive homogeneity index of table 3

Project	Index	Project	Index
				Outward appearance	Crocus liquid	Density (g/cm³)	1.017(25℃)
PH value	4.63	Chloride ion content (%)	0.01
				Total alkali content (%)	0.18	Sodium sulphate content (%)	0.17
Solids content (%)	7.55

(3) sand：River sand, modulus of fineness 2.6.

(4) rubble：5~25mm of granite, crush values index 8%.

1.2 contents of the test and analysis

Under the conditions of natural curing, concrete can reach more than 45MPa in 7-10 hours with form removal, concrete strength, After the age of concrete is full 3-5 days, intensity can reach design strength (80MPa) more than 100%, meet PHC Standards.

1.2.1 the contrast test of ultra high early strength poly-carboxylic water reducer and naphthalene water reducer

1.2.1.1 the mix Design of table 4

Raw material	Cement	Sand	Stone	Additive	Water
						Consumption (kg/m³)	440	710	1320	10.12	110

Proportioning mixes raw material more than, and the raw material being stirred is fitted into mould, carries out prestressed stretch-draw, will Pile concrete after prestressed stretch-draw carries out low speed, low-medium speed, middling speed and high speed centrifugation, until pile tube shaping, with laggard Row demoulding natural curing, obtains PHC piles；It is respectively ultra high early strength poly-carboxylic water reducer and naphthalene to additive During based water reducer, under conditions of natural curing, the intensity of PHC pile tubes during different larval instar is tested, and test result is seen below Table.

1.2.1.2 the concrete strength of table 5 contrasts (unit：MPa) volume is the same, and folding solid content is all 0.18%

As can be seen from Table 5, using ultra high early strength poly-carboxylic, concrete can realize early strong, 10 hours intensity of natural curing Reach more than 50MPa, can safe form removal, when the age of concrete to 3-5 days, intensity reach design strength (80MPa) 100% with On, PHC pile tube Standards are met, can be dispatched from the factory safely.After dispatching from the factory, concrete strength also was continuing to increase, to 28 day age, Concrete strength even can be close to C100.And using naphthalene water reducer, then intensity is formed slowly.

1.3 pairs are exempted from a maintenance processes

Any fuel is no longer needed, the full temperature and humidity condition by the Nature, band mould natural curing in 24 hours, in sand after form removal Timing water drenching in pond and autoclave, to ensure efficiently accomplishing for hydrated cementitious early stage process.Enter outdoor stockyard after 3 days, it is full 7 days After can dispatch from the factory.

1.4 pile tube performance comparisions

Using polycarboxylic admixture produce PHC pile tubes, amount of water significantly reduce (in the case where water reducer volume is constant, Folk prescription concrete water amount can reduce more than 15kg), on the premise of slump and workability is not changed, the ratio of mud It can control below 0.25, the remaining slurry poured out after tubular pile centrifugal is few, inner wall smooth and screed is relatively thin is difficult soft slurry.By Reach that the pile tube of 7 days carries out core pulling experiment to age, it can be found that centrifugation layering is not obvious, coarse-fine aggregate is evenly distributed, coagulation The closely knit rare stomata of soil, as depicted in figs. 1 and 2.

Embodiment 18

The contrast test of ultra high early strength poly-carboxylic water reducer and conventional early-strength water reducer

2.1 mix Design

The mix Design of table 6

	Cement	Silicon ash	Sand	Rubble	Water reducer^@	Water	Folk prescription weight
								Consumption (kg)	435	----	690	1330	10.44	110	2565kg/m³

Note:Cement China Resources P II42.5^R；Water reducer：Ultra high early strength poly-carboxylic water reducer and routine in embodiment 1~15 is early Strong type water reducer

2.2 prepare PHC pile tubes using double techniques of exempting from

Raw material is mixed according to above concrete proportioning, the raw material being stirred is fitted into mould, prestressing force is carried out Tensioning, low speed, low-medium speed, middling speed and high speed centrifugation are carried out by the pile concrete after prestressed stretch-draw, until pile tube shaping, Demoulding natural curing is then carried out, PHC piles are obtained；Natural curing condition refers to：Outdoor natural temperature, Intensity is up to standard after daily water drenching 3-5 times, 3 days in three day age dispatches from the factory, it is not necessary to continue water drenching.

2.3 concrete different larval instar strength development situations

The intensity to the age not same period using PHC pile tubes made from ultra high early strength poly-carboxylic water reducer is tested respectively, together When contrasted with the intensity of concrete tubular pile different larval instar made from the conventional early-strength carboxylic acid water reducer of daily production and application, As a result it see the table below.

The concrete different larval instar intensity (unit of table 8：MPa)

Curing time	1d	3d	7d
				Daily production (conventional early-strength)	45.8	70.3	82.0
Ultra high early strength poly-carboxylic water reducer	65-72	80-82	85-88

As a result show：Relative to conventional early-strength, ultra high early strength poly-carboxylic water reducer of the invention improves concrete early stage Intensity.

2.4 economic comparison

Pile tube is double to exempt from technique, and during using conventional early strong carboxylic acid water reducer, initially formula uses 52.5 cement, (folk prescription cement Consumption 440kg, 370 yuan/ton of cement unit price)；During using ultra high early strength poly-carboxylic water reducer, cement (the folk prescription water of China Resources 42.5 is used Mud consumption 435kg, 320 yuan/ton of cement unit price), and it is better.

So that Ф is 500-125 as an example, every meter of stake cement cost is as follows：

Pearl water 52.5:0.1472m^3/Rice × 0.440 ton/m³× 370 yuan/ton=23.96 yuan/meter

China Resources 42.5：0.1472m^3/Rice × 0.435 ton/m³× 320 yuan/ton=20.49 yuan/meter

Per mitron, stake can reduce by 3.47 yuan of cost.

3.5 are exempted from steam cost and are compared using steam with double：

So that Ф is 500-125 as an example

Use steam：Folk prescription concrete water mud (China Resources) 300kg, emery dust 135kg, 140 yuan/ton of emery dust unit price.It is double to exempt from Steam：Folk prescription concrete water mud (China Resources) 435kg, emery dust without.

Material cost increase：Yuan/meter of 20.49-16.91 yuan/meters of yuan/meter=3.58.

Steam cost is reduced：Fuel cost saves 5.0 yuan/meter (empirical data, Ge Jia factories are slightly different).

Totle drilling cost also reduces 1.42 yuan/meter, and produces simple, without the management cost of boiler and autoclave.

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

1. a kind of preparation method of pile tube, it is characterised in that：Comprise the following steps：Concrete material is mixed to form pile body Concrete, the pile concrete being stirred is fitted into mould, prestressed stretch-draw is carried out, by the pile body coagulation after prestressed stretch-draw Soil is centrifuged, until pile tube shaping, then carries out demoulding natural curing, produce the PHC piles； The concrete material includes ultra high early strength poly-carboxylic water reducer, and the ultra high early strength poly-carboxylic water reducer is shown in formula (1) or formula (2) Compound；

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 is R is H or CH₃；

B is

C is

M is R₂、R₃And R₄It is alone respectively C1-3 alkyl；X is Cl, Br or I；M isInteger, n isInteger, z isIt is whole Number.

2. the preparation method of pile tube as claimed in claim 1, it is characterised in that：The concrete material is included：Cement, sand Son, rubble, ultra high early strength poly-carboxylic water reducer and water.

3. the preparation method of pile tube as claimed in claim 2, it is characterised in that：The folding of the ultra high early strength poly-carboxylic water reducer is consolidated Volume is the 0.1%~0.3% of cement weight.

4. the preparation method of pile tube as claimed in claim 1, it is characterised in that：The concrete material proportioning is as follows：Cement 440~480 parts, 660~700 parts of sand, 1200~1400 parts of a diameter of 5~25mm rubble, ultra high early strength poly-carboxylic water reducer 10~15 parts, 105~125 parts of water.

5. the preparation method of pile tube according to claim 4, it is characterised in that：In the rubble of a diameter of 5~25mm, 5~10mm rubble is 300~400 parts, and 10~25mm rubble is 900~1000 parts.

6. the preparation method of pile tube according to claim 5, it is characterised in that：The proportioning of the raw material is as follows：Cement 460 Part, 680 parts of sand, 396 parts of a diameter of 5~10mm rubble, 924 parts of a diameter of 10~25mm rubble, ultra high early strength poly-carboxylic 12.42 parts of water reducer, 115 parts of water.

7. the preparation method of pile tube according to claim 4, it is characterised in that：The modulus of fineness of the sand be 2.4~ 3.0；The crush values index of the rubble is less than 8%.

8. the preparation method of pile tube according to claim 1, it is characterised in that：It is described centrifugation successively through low speed, low-medium speed, Middling speed and high speed centrifugation step.

9. pile tube made from the preparation method of the pile tube according to any claim in claim 1~8.