CN105293976A

CN105293976A - Tubular pile and preparation method thereof

Info

Publication number: CN105293976A
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: 2016-02-03
Anticipated expiration: 2035-10-14
Also published as: CN105293976B

Abstract

The invention discloses a preparation method of a tubular pile. The preparation method includes the following steps of mixing and stirring concrete materials to form pile body concrete, arranging the stirred pile body concrete in a mold for prestress tension, conducting centrifugation on the pile body concrete on which prestress tension is conducted till the tubular pile is formed, detaching the mold, and conducting natural curing to obtain the prestress high-strength concrete tubular pile. The concrete raw materials contain super high-early strength polycarboxylate superplasticizer which is the compound shown as the formula (1) or (2). The preparation method of the tubular pile has the advantages of being easy to operate, safe in production and low in cost. The prepared tubular pile is smooth in inner wall, thin in mortar layer and not prone to softening pulp, demolding can be conducted within 7-10 hours, and the tubular pile can reach the factory strength within 3-5 days.

Description

A kind of pile tube and preparation method thereof

Technical field

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

Background technology

Over nearly 20 years, the production of conventional PHC piles (PHC pile tube) is all take second steam maintaining production technique, and just support and high-pressure curing, steam-cured pond and autoclave all need at substantial steam.But the mandatory enforcement of the new environmental law of country, a lot of 10 tons (containing 10 tons) following coal firing boilers all face environmental protection upgrading, want environmental impact assessment up to standard, finally will select to burn Sweet natural gas.This brings jumbo cost to increase by giving all pile tube manufacturers, according to statistics: fuel cost is 3.5-4.0 times of coal-fired cost; Combustion gas cost is 4.5-5.5 times of coal-fired cost, for conventional products D500-125 stake, about every mitron stake cost will increase 15-20 unit.So tubular pile industry " boiler crisis " can spread very soon and come, it by become each pile tube manufacturer must faced by a difficult problem.

At present, existing a lot of expert and the exempt from pressure steaming technique of people in the industry to PHC pile tube are explored and are studied, retain primary steam maintenance processes (namely, constant temperature 85 DEG C in curing pool, maintenance 6 hours), and in starting material, add the mixing material of silicon ash (94 grades) and breeze (S115 level), to improve concrete early strength.But the material costs such as silicon ash are higher, are not suitable for the pile tube Market Situation of present stage.

Summary of the invention

An object of the present invention is the preparation method solving Problems existing in existing PHC piles preparation process and provide a kind of pile tube, the preparation method of pile tube of the present invention can realize non-evaporating supporting and exempt from pressure steaming, have simple to operate, production safety, advantage with low cost.

The technical solution used in the present invention is: a kind of preparation method of pile tube, comprise the following steps: concrete material mix and blend is formed pile concrete, the pile concrete be stirred is loaded in mould, carry out prestressed stretch-draw, pile concrete after prestressed stretch-draw is carried out centrifugal, until pile tube is shaping, carry out demoulding natural curing subsequently, obtain described PHC piles; Described concrete material comprises ultra high early strength poly-carboxylic water reducer, and described ultra high early strength poly-carboxylic water reducer is the compound shown in formula (1) or formula (2);

The structural formula of the compound shown in described formula (1) is as follows:

The structural formula of the compound shown in described formula (2) is as follows:

Wherein a is the integer of 1 ~ 80, and b is the integer of 1 ~ 80, and c is the integer of 1 ~ 50; L is the integer of 1 ~ 50;

A is r is H or CH3;

B is

C is

M is

r ₂, R ₃and R ₄be alone C1-3 alkyl respectively; X is Cl, Br or I; M is the integer of 5 ~ 200, and n is the integer of 0 ~ 50, and z is the integer of 1 ~ 150.

In technique scheme, exempt from preparation technology, remove the twice vapor cure operation in former pile tube production technique from for of the present invention pair, do not need with steam, rely on natural condition to carry out maintenance completely, reduce production cost, improve production efficiency and production security.Natural curing refers under natural temperature condition (higher than 5 DEG C), takes to cover, waters water-wet, keeps out the wind, the maintenance measure such as insulation to concrete.

In technique scheme, exempt from the realization of preparation technology mainly owing to employing ultra high early strength poly-carboxylic water reducer for of the present invention pair.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, what namely adopt is long side chain, short main chain, molecular structure is designed to inverted T shape, present comb-type structure, such molecular structure can utilize severely sterically inhibition effect to ensure dissemination, and short main chain reduces the area coverage of water reducer at cement granules simultaneously, ensures the normal hydrated reaction of cement; What is more important, ultra high early strength poly-carboxylic water reducer of the present invention utilizes special catalyst to realize the regular aquation group polymeric monomer short with employing of polymer camber, utilizes synergistic effect, realizes super hardening effect.

In technique scheme, described concrete material comprises cement, sand, rubble and water usually, and in order to realize super hardening, the present invention with the addition of admixture ultra high early strength poly-carboxylic water reducer.Do not limit concrete material at this, the concrete material used in prior art all can realize super hardening effect after adding ultra high early strength poly-carboxylic water reducer of the present invention.Such as, concrete material of the present invention can be: concrete material comprises cement, sand, rubble, water and admixture, and wherein admixture comprises ultra high early strength poly-carboxylic water reducer; Concrete reducing material of the present invention can be: concrete material comprises cement, sand, rubble, water, admixture and adulterant, and wherein admixture comprises ultra high early strength poly-carboxylic water reducer.

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

(1a) synthesis of methoxyl group hydroxyl PEG intermediate

To in the autoclave closed, inject mixture, epoxyhalopropane, the catalyzer of methyl alcohol, oxyethane or oxyethane and propylene oxide, stir, react 2-10h at 80-150 DEG C, obtain reaction product methoxyl group hydroxyl PEG intermediate;

Wherein, epoxyhalopropane is epoxy chloropropane, epoxy bromopropane or Epiiodohydrin; Its reaction formula is as follows:

(2a) synthesis of methoxyl group PEG surface-active macromonomer

Step 1a is added in reactor) middle methoxyl group hydroxyl PEG intermediate, olefin(e) acid, catalyzer and the stopper synthesized, stirs, reacts 3-15h, obtain reaction product methoxyl group PEG active intermediate at 70-170 DEG C;

Wherein, olefin(e) acid is vinylformic acid, methacrylic acid, maleic anhydride or methylene-succinic acid; Its reaction formula is as follows:

(3a) synthesis of surface-active macromonomer

Quaternization reactant and stopper is added in reactor, be warming up to 10-80 DEG C, slow dropping step 2a) in the quaternization reactant solution of methoxyl group PEG active intermediate of synthesis, after dropwising, under 10-80 DEG C of condition, continue insulation reaction 1-10h, obtain described surface-active macromonomer; Its reaction formula is as follows:

Wherein, described quarternary ammonium salt compound is N (R ₂r ₃r ₄), wherein R ₂, R ₃and R ₄be alone C1-3 alkyl respectively.

(4a) synthesis of the ultra high early strength poly-carboxylic water reducer shown in formula (1)

By step 3a) surface-active macromonomer that synthesizes, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, one in APEG, VPEG, HPEG and TPEG, water and molecular weight regulator mixing, be warming up to 85 ~ 95 DEG C, drip initiator, dropwise rear insulation, then be cooled to 45 ~ 50 DEG C, regulate pH to 7.0-8.0, obtain described ultra high early strength poly-carboxylic water reducer.

Preferably, methyl alcohol in described step (1a), the mol ratio of a kind of and epoxyhalopropane in the mixture of oxyethane and oxyethane and propylene oxide is methyl alcohol: the one in the mixture of oxyethane and oxyethane and propylene oxide: epoxyhalopropane=1:5 ~ 250:1 ~ 150; Described step 2a) in, the mol ratio of methoxyl group hydroxyl PEG intermediate and olefin(e) acid is 1:1.0 ~ 8.0; Described step 3a) in, the mol ratio of quaternization reactant and described methoxyl group PEG active intermediate is 0.2 ~ 2:1; In described step (4a), one in described methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, the mol ratio of a kind of and surface-active macromonomer in APEG, VPEG, HPEG and TPEG is the one in APEG, VPEG, HPEG and TPEG: the one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride: surface-active macromonomer=1 ~ 6.0:1.0:1.0 ~ 3.0.

Preferably, the catalyzer in described step (1a) is sodium hydride or sodium; Catalyzer in described step (2a) is at least one in methylsulfonic acid and p-methyl benzenesulfonic acid; Stopper in described step (2a), (3a) is Resorcinol or to methyl ether phenol; In described step (2a), the consumption of stopper is 0.002% ~ 0.010% of described methoxyl group hydroxyl PEG intermediate mole number, and in described step (3a), the consumption of stopper is 0.002% ~ 0.010% of described methoxyl group PEG surface-active macromonomer mole number; Described step (4a) middle-molecular-weihydroxyethyl conditioning agent is at least one in sulfhydryl compound and Virahol, the consumption of described molecular weight regulator is described surface-active macromonomer, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, 0.005 ~ 5% of a kind of total mole number in APEG, VPEG, HPEG and TPEG; Described sulfhydryl compound is 3-thiohydracrylic acid, Thiovanic acid, mercaptoethanol or rongalite; Initiator described in described step (4a) is the one in the aqueous solution of hydrogen peroxide, Potassium Persulphate, ammonium persulphate and benzoyl peroxide; The consumption of described initiator is described surface-active macromonomer, a kind of and 0.05% ~ 5% of a kind of total mole number in APEG, VPEG, HPEG and TPEG in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride; In described step (4a), the time for adding of described initiator is 1 ~ 10h, and described soaking time is 1 ~ 12h.

Preferably, the ultra high early strength poly-carboxylic water reducer shown in described formula (2) is prepared from by following methods:

(1b) synthesis of methoxyl group hydroxyl PEG intermediate

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

Step 1b is added in reactor) middle methoxyl group hydroxyl PEG intermediate, olefin(e) acid, catalyzer and the stopper synthesized, stirs, reacts 3-15h, obtain reaction product methoxyl group PEG active intermediate at 70-170 DEG C;

(3b) synthesis of surface-active macromonomer

Quaternization reactant and stopper is added in reactor, be warming up to 10-80 DEG C, slow dropping step 2b) in the quaternization reactant solution of methoxyl group PEG active intermediate of synthesis, after dropwising, under 10-80 DEG C of condition, continue insulation reaction 1-10h, obtain described surface-active macromonomer; Its reaction formula is as follows:

(4b) synthesis of the ultra high early strength poly-carboxylic water reducer shown in formula (2)

By step 3b) surface-active macromonomer that synthesizes, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, one in APEG, HPEG, VPEG and TPEG, one in acrylamide, 2-acrylamide-2-methyl propane sulfonic and sodium allyl sulfonate, water and molecular weight regulator mixing, be warming up to 85 ~ 95 DEG C, drip initiator, dropwise rear insulation, then 45 ~ 50 DEG C are cooled to, regulate pH to 7.0-8.0, obtain super hardening quaternary ammonium salt cationic positively charged ion polycarboxylate water-reducer.

Preferably, methyl alcohol in described step (1b), one in the mixture of oxyethane and oxyethane and propylene oxide, the mol ratio of epoxyhalopropane is methyl alcohol: the one in the mixture of oxyethane and oxyethane and propylene oxide: epoxyhalopropane=1:5 ~ 250:1 ~ 150, described step 2b) in, the mol ratio of methoxyl group hydroxyl PEG intermediate and olefin(e) acid is 1:1.0 ~ 8.0, described step 3b) in, the mol ratio of quaternization reactant and described methoxyl group PEG active intermediate is 0.2 ~ 2:1, methacrylic acid described in described step (4b), vinylformic acid, one in methylene-succinic acid and maleic anhydride, APEG, HPEG, one in VPEG and TPEG, surface-active macromonomer and acrylamide, a kind of mol ratio in 2-acrylamide-2-methyl propane sulfonic and sodium allyl sulfonate is methacrylic acid, vinylformic acid, one in methylene-succinic acid and maleic anhydride: APEG, HPEG, one in VPEG and TPEG: surface-active macromonomer: acrylamide, one=1 ~ 6.0:1.0:1.0 ~ 3.0:0.2 ~ 6.0 in 2-acrylamide-2-methyl propane sulfonic and sodium allyl sulfonate.

Preferably, the catalyzer in described step (1b) is sodium hydride or sodium; Catalyzer in described step (2b) is at least one in methylsulfonic acid and p-methyl benzenesulfonic acid; Stopper in described step (2b), (3b) is Resorcinol or to methyl ether phenol; In described step (2b), the consumption of stopper is 0.002% ~ 0.010% of described methoxyl group hydroxyl PEG intermediate mole number, and in described step (3b), the consumption of stopper is 0.002% ~ 0.010% of described methoxyl group PEG surface-active macromonomer mole number; Described step (4b) middle-molecular-weihydroxyethyl conditioning agent is at least one in sulfhydryl compound and Virahol, the consumption of described molecular weight regulator is described surface-active macromonomer, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, 0.005 ~ 5% of a kind of total mole number in a kind of and acrylamide in APEG, VPEG, HPEG and TPEG, 2-acrylamide-2-methyl propane sulfonic and sodium allyl sulfonate; Described sulfhydryl compound is 3-thiohydracrylic acid, Thiovanic acid, mercaptoethanol or rongalite; Initiator described in described step (4a) is the one in the aqueous solution of hydrogen peroxide, Potassium Persulphate, ammonium persulphate and benzoyl peroxide; The consumption of described initiator is described surface-active macromonomer, a kind of and 0.05% ~ 5% of a kind of total mole number in a kind of and acrylamide in APEG, VPEG, HPEG and TPEG, 2-acrylamide-2-methyl propane sulfonic and sodium allyl sulfonate in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride; In described step (4a), the time for adding of described initiator is 1 ~ 10h, and described soaking time is 1 ~ 12h.

Preferably, described concrete material comprises: cement, sand, rubble, ultra high early strength poly-carboxylic water reducer and water.

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

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

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

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

Preferably, described diameter is in the rubble of 5 ~ 25mm, and the rubble of 5 ~ 10mm is 300 ~ 400 parts, and the rubble of 10 ~ 25mm is 900 ~ 1000 parts.

More preferably, described diameter is in the rubble of 5 ~ 25mm, and the rubble of 5 ~ 10mm is 350 ~ 400 parts, and the rubble of 10 ~ 25mm is 900 ~ 950 parts.

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

Preferably, described centrifugal successively through low speed, low-medium speed, middling speed and high speed centrifugation step.

Present invention also offers the pile tube obtained according to the preparation method of described pile tube.

Through two PHC piles of exempting from preparation technology and obtaining, inner wall smooth and screed is thinner, not easily soft slurry; Through experiment of loosing core to the pile tube reaching 3-5 days the length of time, can find that centrifugal layering is not obvious, coarse-fine aggregate is evenly distributed, the rare pore of concrete compaction, and 7-10 hour collapsible die reaches intensity of dispatching from the factory in 3-5 days.

Relative to prior art, beneficial effect of the present invention is:

1) preparation method of pile tube of the present invention eliminates primary steam maintenance and autoclave curing operation, carries out oxygen completely and protects, do not use steam, saved the energy, protected environment by natural condition;

2) do not re-use levigate quartz sand powder in the gelling material used in the preparation method of pile tube of the present invention, produce with plain cement; Because gelling material is plain cement, so concrete cohesiveness is good, slump gradual loss is little, and good workability is easy to operate;

3) if in the preparation method of pile tube of the present invention use cement of high index, by selecting high performance additive ultra high early strength poly-carboxylic water reducer, produce high performance concrete, not only concrete grade is high, and cracking resistance, anti-permeability performance strengthen;

4) use the PHC pile tube that the preparation method of pile tube of the present invention produces, intensity stabilization, square root of the variance is less than the PHC pile tube square root of the variance (two exempt from square root of the variance: 3.0-4.0MPa, ordinary process square root of the variance: 5.0-6.0MPa) that ordinary process is produced;

5) strength of mould stripping after national regulations vapor cure is 42-45MPa, adopts two PHC pile tube of exempting from explained hereafter, and rapidly, complete natural curing, 7-10 hour collapsible die, intensity reaches 50-55MPa, and within 3 days, intensity can reach 84-86MPa in early strength development.

Accompanying drawing explanation

Fig. 1 is the transverse views of the PHC piles that embodiment 17 obtains;

Fig. 2 is longitudinal view of the PHC piles that embodiment 17 obtains.

Embodiment

For better the object, technical solutions and advantages of the present invention being described, below in conjunction with specific embodiment, the invention will be further described.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention, NM specific experiment method in the following example, conveniently experimental technique carries out usually.VPEG:4-hydroxy butyl vinyl ether Soxylat A 25-7 of the present invention; APEG: allyl alcohol polyethenoxy ether; HPEG: isobutene alcohol Soxylat A 25-7; TPEG: isopentenol polyoxyethylene ether.

Embodiment 1

A kind of preparation method of pile tube, comprise the following steps: concrete material mix and blend is formed pile concrete, the raw material be stirred is loaded in mould, carry out prestressed stretch-draw, pile concrete after prestressed stretch-draw is carried out low speed, low-medium speed, middling speed and high speed centrifugation, until pile tube is shaping, carries out demoulding natural curing subsequently, obtain PHC piles;

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

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

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

1) in the autoclave closed, inject 1.0mol methyl alcohol, 80mol oxyethane, 60mol epoxy chloropropane and 3g sodium hydride respectively, stir, react 10h at 100 DEG C, obtain reaction product methoxyl group hydroxyl PEG intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 0.9mol methoxyl group hydroxyl PEG intermediate, 0.9mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 15h at 110 DEG C, obtain reaction product surface-active macromonomer;

3) in glass flask, 1.6mol triethylamine and 0.01g Resorcinol is added, be warming up to 80 DEG C, slow dropping is containing 0.8mol step 2) triethylamine solution of methoxyl group PEG active intermediate that synthesizes is (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 5h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.5mol step 3) surface-active macromonomer that synthesizes, 0.5mol methacrylic acid, 0.5molAPEG and 400ml deionized water, described molecular weight regulator is 3-thiohydracrylic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, 0.5% of methacrylic acid and APEG total mole number, be warming up to 85 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 10% Potassium Persulphate, the consumption of described initiator is described surface-active macromonomer, 5% of methacrylic acid and APEG total mole number, time for adding is 1h, after dropwising, insulation reaction 1h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 2

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

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

1) in the autoclave closed, inject 1mol methyl alcohol, 5mol oxyethane, 1mol epoxy chloropropane and 2g sodium hydride respectively, stir, react 10h at 80 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 1.0mol methoxyl group hydroxy intermediate, 8.0mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.2molN is added, N-dimethyl amine and 0.01g Resorcinol, be warming up to 20 DEG C, slow dropping is containing 1.0mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl amine solution (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 20 DEG C of conditions, continue insulation reaction 10h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 1.0mol step 3) surface-active macromonomer that synthesizes, 2.0mol maleic anhydride, 0.33molHPEG and 600ml deionized water, described molecular weight regulator is Thiovanic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, 5% of maleic anhydride and HPEG total mole number, be warming up to 95 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 20% ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, 0.05% of maleic anhydride and HPEG total mole number, time for adding is 10h, after dropwising, insulation reaction 12h, at being cooled to 45 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=8.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 3

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

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

1) in the autoclave closed, inject 1mol methyl alcohol, 200mol oxyethane, 150mol epoxy chloropropane and 2g sodium hydride respectively, stir, react 10h at 80 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 1.0mol methoxyl group hydroxy intermediate, 4.5mol maleic anhydride, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 5h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.75mol tripropyl amine and 0.01g Resorcinol is added, be warming up to 80 DEG C, slow dropping is containing 0.75mol step 2) the tripropyl amine solution of methoxyl group PEG active intermediate that synthesizes is (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 10%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 2h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.7mol step 3) surface-active macromonomer that synthesizes, 1.0mol vinylformic acid, 0.35molTPEG and 500ml deionized water, described molecular weight regulator is mercaptoethanol, the consumption of described molecular weight regulator is described surface-active macromonomer, 5% of vinylformic acid and TPEG total mole number, be warming up to 90 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 15% hydrogen peroxide, the consumption of described initiator is described surface-active macromonomer, 0.8% of vinylformic acid and TPEG total mole number, time for adding is 2.5h, after dropwising, insulation reaction 3h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.5, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 4

1) in the autoclave closed, inject the mixture of 1.0mol methyl alcohol, 100mol oxyethane and 50mol propylene oxide, 100mol epoxy bromopropane and 1g sodium hydride respectively, stir, react 10h at 80 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 0.7mol methoxyl group hydroxy intermediate, 2.8mol vinylformic acid, 1g methylsulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 80 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.8molN is added, N-dimethyl propylamine and 0.01g Resorcinol, be warming up to 80 DEG C, slow dropping is containing 0.5mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl propylene amine aqueous solution (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 3h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.5mol step 3) surface-active macromonomer that synthesizes, 1.0mol methylene-succinic acid, 0.17molTPEG and 500ml deionized water, described molecular weight regulator is rongalite, the consumption of described molecular weight regulator is described surface-active macromonomer, 2.5% of methylene-succinic acid and TPEG total mole number, be warming up to 90 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 15% benzoyl peroxide, the consumption of described initiator is described surface-active macromonomer, 1% of methylene-succinic acid and TPEG total mole number, time for adding is 2.5h, after dropwising, insulation reaction 3h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.5, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 5

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

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

1) in the autoclave closed, inject the mixture of 1.0mol methyl alcohol, 90mol oxyethane and 20mol propylene oxide, 75mol epoxy chloropropane and 2.5g sodium hydride respectively, stir, react 2h at 150 DEG C, obtain reaction product methoxyl group hydroxyl PEG intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) in the 0.8mol methoxyl group hydroxyl PEG intermediate of synthesis, 4.8mol methylene-succinic acid, 1.5g methylsulfonic acid and 0.01g be to methyl ether phenol, stir, react 3h at 170 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.35molN is added, N-dimethyl amine and 0.01g Resorcinol, be warming up to 50 DEG C, slow dropping is containing 0.7mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl amine solution (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 50 DEG C of conditions, continue insulation reaction 5h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.5mol step 3) surface-active macromonomer that synthesizes, 1.0mol methacrylic acid, 0.5molAPEG and 400ml deionized water, described molecular weight regulator is 3-thiohydracrylic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, 2% of methacrylic acid and APEG total mole number, be warming up to 85 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 10% Potassium Persulphate, the consumption of described initiator is described surface-active macromonomer, 1.5% of methacrylic acid and APEG total mole number, time for adding is 2h, after dropwising, insulation reaction 2h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 6

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

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

1) in the autoclave closed, inject the mixture of 0.8mol methyl alcohol, 80mol oxyethane and 16mol propylene oxide, 24mol epoxy chloropropane and 4g sodium hydride respectively, stir, react 8h at 120 DEG C, obtain reaction product methoxyl group hydroxyl PEG intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 0.6mol methoxyl group hydroxyl PEG intermediate, 1.8mol methacrylic acid, 4g methylsulfonic acid and the 0.01g Resorcinol synthesized, stir, react 4h at 170 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.5mol tripropyl amine and 0.01g Resorcinol is added, be warming up to 60 DEG C, slow dropping is containing 0.5mol step 2) the tripropyl amine solution of methoxyl group PEG active intermediate that synthesizes is (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 10%), after dropwising, under 60 DEG C of conditions, continue insulation reaction 5h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.6mol step 3) the described surface-active macromonomer that synthesizes, 1.5mol vinylformic acid, 0.3molVPEG and 600ml deionized water, described molecular weight regulator is Thiovanic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, 1.5% of vinylformic acid and HPEG total mole number, be warming up to 95 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 20% ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, 0.5% of vinylformic acid and HPEG total mole number, time for adding is 3h, after dropwising, insulation reaction 4h, at being cooled to 45 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=8.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 7

1) in the autoclave closed, inject 1.0mol methyl alcohol, 80mol oxyethane, 60mol epoxy chloropropane and 3g sodium hydride respectively, stir, react 2h at 150 DEG C, obtain reaction product methoxyl group hydroxyl PEG intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 0.9mol methoxyl group hydroxyl PEG intermediate, 1.05mol methacrylic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 3h at 170 DEG C, obtain reaction product surface-active macromonomer;

3) in glass flask, 0.16mol triethylamine and 0.01g Resorcinol is added, be warming up to 80 DEG C, slow dropping is containing 0.8mol step 2) triethylamine solution of methoxyl group PEG active intermediate that synthesizes is (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 2h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.7mol step 3) surface-active macromonomer that synthesizes, 0.7mol vinylformic acid, 0.7molTPEG, 0.14mol acrylamide and 500ml deionized water, described molecular weight regulator is mercaptoethanol, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 1% of acrylamide and TPEG total mole number, be warming up to 90 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 15% benzoyl peroxide, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 5% of acrylamide and TPEG total mole number, time for adding is 10h, after dropwising, insulation reaction 3h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.5, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 8

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

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 1.0mol methoxyl group hydroxy intermediate, 8.0mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 15h at 70 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 2.0molN is added, N-dimethyl amine and 0.01g Resorcinol, be warming up to 80 DEG C, slow dropping is containing 1.0mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl amine solution (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 2h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 1.0mol step 3) surface-active macromonomer that synthesizes, 2.0mol vinylformic acid, 0.33molHPEG, 2.0mol2-acrylamide-2-methyl propane sulfonic and 600ml deionized water, described molecular weight regulator is Thiovanic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 5% of 2-acrylamide-2-methyl propane sulfonic and HPEG total mole number, be warming up to 95 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 20% ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 0.1% of 2-acrylamide-2-methyl propane sulfonic and HPEG total mole number, time for adding is 3h, after dropwising, insulation reaction 4h, at being cooled to 45 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=8.0, obtain ultra high early strength poly-carboxylic water reducer,

Embodiment 9

1) in the autoclave closed, inject 1mol methyl alcohol, 200mol oxyethane, 150mol epoxy chloropropane and 2g sodium hydride respectively, stir, react 8h at 110 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 1.0mol methoxyl group hydroxy intermediate, 4.5mol maleic anhydride, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.75mol tripropyl amine and 0.01g Resorcinol is added, be warming up to 50 DEG C, slow dropping is containing 0.75mol step 2) the tripropyl amine solution of methoxyl group PEG active intermediate that synthesizes is (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 10%), after dropwising, under 50 DEG C of conditions, continue insulation reaction 5h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.5mol step 3) surface-active macromonomer that synthesizes, 0.75mol methacrylic acid, 0.25molVPEG, 0.25mol2-acrylamide-2-methyl propane sulfonic and 400ml deionized water, described molecular weight regulator is Virahol, the consumption of described molecular weight regulator is described surface-active macromonomer, methacrylic acid, 0.05% of 2-acrylamide-2-methyl propane sulfonic and VPEG total mole number, be warming up to 85 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 10% hydrogen peroxide, the consumption of described initiator is described surface-active macromonomer, methacrylic acid, 3% of 2-acrylamide-2-methyl propane sulfonic and VPEG total mole number, time for adding is 2h, after dropwising, insulation reaction 2h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 10

1) in the autoclave closed, inject the mixture of 1.0mol methyl alcohol, 100mol oxyethane and 50mol propylene oxide, 100mol epoxy chloropropane and 1g sodium hydride respectively, stir, react 10h at 80 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 0.7mol methoxyl group hydroxy intermediate, 0.75mol vinylformic acid, 1g methylsulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 80 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 2.5molN is added, N-dimethyl propylamine and 0.01g Resorcinol, be warming up to 60 DEG C, slow dropping is containing 0.5mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl propylene amine aqueous solution (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 60 DEG C of conditions, continue insulation reaction 6h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.5mol step 3) surface-active macromonomer that synthesizes, 1.2mol methacrylic acid, 0.25molAPEG, 0.75mol acrylamide and 400ml deionized water, described molecular weight regulator is 3-thiohydracrylic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, methacrylic acid, 2% of acrylamide and APEG total mole number, be warming up to 85 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 10% Potassium Persulphate, the consumption of described initiator is described surface-active macromonomer, methacrylic acid, 1.5% of acrylamide and APEG total mole number, time for adding is 2h, after dropwising, insulation reaction 2h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 11

1) in the autoclave closed, inject the mixture of 1.0mol methyl alcohol, 60mol oxyethane and 20mol propylene oxide, 2mol epoxy bromopropane and 4g sodium hydride respectively, stir, react 10h at 110 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 0.6mol methoxyl group hydroxy intermediate, 1.2mol maleic anhydride, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.8mol triethylamine and 0.01g Resorcinol is added, be warming up to 80 DEG C, slow dropping is containing 0.6mol step 2) triethylamine solution of methoxyl group PEG active intermediate that synthesizes is (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 12%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 2h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.6mol step 3) surface-active macromonomer that synthesizes, 1.2mol maleic anhydride, 0.6molTPEG, 1.8mol acrylamide and 500ml deionized water, described molecular weight regulator is rongalite, the consumption of described molecular weight regulator is described surface-active macromonomer, maleic anhydride, 1.8% of acrylamide and TPEG total mole number, be warming up to 90 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 15% benzoyl peroxide, the consumption of described initiator is described surface-active macromonomer, maleic anhydride, 4% of acrylamide and TPEG total mole number, time for adding is 2.5h, after dropwising, insulation reaction 3h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.5, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 12

1) in the autoclave closed, inject the mixture of 1mol methyl alcohol, 165mol oxyethane and 35mol propylene oxide, 1.2mol epoxy bromopropane and 3g sodium hydride respectively, stir, react 8h at 100 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 0.9mol methoxyl group hydroxy intermediate, 4.5mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.4mol Trimethylamine 99 and 0.01g Resorcinol is added, be warming up to 75 DEG C, slow dropping contains 0.75mol step 2) trimethylamine solution of methoxyl group active intermediate that synthesizes is (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 5%), after dropwising, under 75 DEG C of conditions, continue insulation reaction 6h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.7mol step 3) surface-active macromonomer that synthesizes, 1.0mol methylene-succinic acid, 0.25molHPEG, 0.7mol2-acrylamide-2-methyl propane sulfonic and 600ml deionized water, described molecular weight regulator is Thiovanic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, methylene-succinic acid, 1.5% of sodium allyl sulfonate and HPEG total mole number, be warming up to 95 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 20% ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, methylene-succinic acid, 0.5% of 2-acrylamide-2-methyl propane sulfonic and HPEG total mole number, time for adding is 3h, after dropwising, insulation reaction 4h, at being cooled to 45 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=8.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 13

1) in the autoclave closed, inject 1mol methyl alcohol, 5mol oxyethane, 1mol epoxy chloropropane and 2g sodium hydride respectively, stir, react 9h at 110 DEG C, obtain reaction product methoxyl group hydroxy intermediate;

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) middle 1.0mol methoxyl group hydroxy intermediate, 6.0mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 1.5molN is added, N-dimethyl amine and 0.01g Resorcinol, be warming up to 80 DEG C, slow dropping is containing 1.0mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl amine solution (wherein, the volumetric molar concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 3h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 1.0mol step 3) surface-active macromonomer that synthesizes, 1.0mol vinylformic acid, 1.0molHPEG, 0.2mol sodium allyl sulfonate and 600ml deionized water, described molecular weight regulator is Thiovanic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 5% of 2-acrylamide-2-methyl propane sulfonic and HPEG total mole number, be warming up to 95 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 20% ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 5% of 2-acrylamide-2-methyl propane sulfonic and HPEG total mole number, time for adding is 3h, after dropwising, insulation reaction 4h, at being cooled to 45 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=8.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 14

3) in glass flask, 1.0molN is added, N-dimethyl propylamine and 0.01g Resorcinol, be warming up to 80 DEG C, slow dropping is containing 0.5mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl propylene amine aqueous solution (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 3h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.5mol step 3) described surface-active macromonomer, 1.0mol methacrylic acid, 0.17molAPEG, 1.0mol sodium allyl sulfonate and 400ml deionized water, described molecular weight regulator is 3-thiohydracrylic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, methacrylic acid, 0.5% of sodium allyl sulfonate and APEG total mole number, be warming up to 85 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 10% Potassium Persulphate, the consumption of described initiator is described surface-active macromonomer, methacrylic acid, 0.5% of sodium allyl sulfonate and APEG total mole number, time for adding is 2h, after dropwising, insulation reaction 2h, at being cooled to 50 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=7.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 15

2) to in 500ml tetra-mouthfuls of glass flask of agitator, thermometer, reflux condensing tube, Dropping feeder, add step 1) in the 0.8mol methoxyl group hydroxyl PEG intermediate of synthesis, 3.2mol methylene-succinic acid, 1.5g methylsulfonic acid and 0.01g be to methyl ether phenol, stir, react 10h at 120 DEG C, obtain reaction product methoxyl group PEG active intermediate;

3) in glass flask, 0.7molN is added, N-dimethyl amine and 0.01g Resorcinol, be warming up to 80 DEG C, slow dropping is containing 0.7mol step 2) N of methoxyl group PEG active intermediate that synthesizes, N-dimethyl amine solution (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 3h, obtain described surface-active macromonomer;

4) agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, 0.6mol step 3) described surface-active macromonomer, 1.5mol vinylformic acid, 0.3molHPEG, 1.0mol sodium allyl sulfonate and 600ml deionized water, described molecular weight regulator is Thiovanic acid, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 5% of sodium allyl sulfonate and HPEG total mole number, be warming up to 95 DEG C, drip the aqueous solution of initiator, described initiator to be mass concentration be 20% ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 5% of sodium allyl sulfonate and HPEG total mole number, time for adding is 3h, after dropwising, insulation reaction 4h, at being cooled to 45 DEG C, add the NaOH solution that mass concentration is 30%, regulate pH=8.0, obtain ultra high early strength poly-carboxylic water reducer.

Embodiment 16

Test the intensity in the age not same period of PHC piles obtained in embodiment 1 ~ 15, test result sees the following form.

Table 1 concrete different larval instar strength development situation

Embodiment 17

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

1.1 raw-materially select

(1) cement: select PII52.5 ^rsilicate cement, specific surface area 320m ²/ kg.

The chemical composition (%) of table 2 cement

SiO ₂	Al ₂O ₃	MgO	CaO	Fe ₂O ₃	Loss on ignition
						23.82	3.37	4.85	61.20	4.32	2.44

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

Table 3 admixture homogeneity index

Project	Index	Project	Index
				Outward appearance	Safran liquid	Density (g/cm ³)	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, fineness modulus 2.6.

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

1.2 contents of the test and analysis

Under natural curing condition, concrete can form removal in 7-10 hour, and concrete strength reaches more than 45MPa, and when after full 3-5 days of the age of concrete, intensity can reach design strength (80MPa) more than 100%, meets PHC stake Standard.

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

1.2.1.1 table 4 mix Design

Starting material	Cement	Sand	Stone	Admixture	Water
						Consumption (kg/m ³)	440	710	1320	10.12	110

According to above proportioning by raw material mix and blend, the raw material be stirred is loaded in mould, carry out prestressed stretch-draw, pile concrete after prestressed stretch-draw is carried out low speed, low-medium speed, middling speed and high speed centrifugation, until pile tube is shaping, carry out demoulding natural curing subsequently, obtain PHC piles; Respectively to admixture be ultra high early strength poly-carboxylic water reducer and naphthalene water reducer time, under the condition of natural curing, the intensity of PHC pile tube during different larval instar is tested, and test result sees the following form.

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

As can be seen from Table 5, use ultra high early strength poly-carboxylic, concrete can realize early strong, natural curing 10 hours intensity reaches more than 50MPa, can safe form removal, when the age of concrete is to 3-5 days, intensity reaches design strength (80MPa) more than 100%, meet PHC pile tube Standard, can dispatch from the factory safely.After dispatching from the factory, concrete strength also increases in continuation, and to the 28 day length of time, concrete strength even can close to C100.Then strength derived value is slow to use naphthalene water reducer.

Exempt from a maintenance processes for 1.3 pairs

No longer need any fuel, the full temperature and humidity condition by the Nature, is with mould natural curing in 24 hours, after form removal in husky pond and autoclave timing trickle, to ensure effectively completing of hydrated cementitious process in early stage.3 days laggard enter outdoor stockyard, full can to dispatch from the factory after 7 days.

1.4 pile tube Performance comparision

Polycarboxylic admixture is used to produce PHC pile tube, amount of water obviously reduces (when water reducer volume is constant, the folk prescription the reinforcement of concrete water yield can reduce more than 15kg), under the prerequisite not changing slump and workability, water cement ratio can control below 0.25, the remaining slurry poured out after tubular pile centrifugal is few, inner wall smooth and screed is thinner, not easily soft slurry.Through experiment of loosing core to the pile tube reaching 7 days the length of time, can find that centrifugal layering is not obvious, coarse-fine aggregate is evenly distributed, the rare pore of concrete compaction, as depicted in figs. 1 and 2.

Embodiment 18

the simultaneous test of ultra high early strength poly-carboxylic water reducer and conventional early-strength type water reducer

2.1 mix Design

Table 6 mix Design

	Cement	Silicon ash	Sand	Rubble	Water reducer	Water	Folk prescription weight
								Consumption (kg)	435	----	690	1330	10.44	110	2565kg/m ³

Note: cement China Resources PII42.5 ^r; Water reducer: the ultra high early strength poly-carboxylic water reducer in embodiment 1 ~ 15 and conventional early-strength type water reducer

2.2 utilizations pair are exempted from technique and are prepared PHC pile tube

According to above concrete proportioning by raw material mix and blend, the raw material be stirred is loaded in mould, carry out prestressed stretch-draw, pile concrete after prestressed stretch-draw is carried out low speed, low-medium speed, middling speed and high speed centrifugation, until pile tube is shaping, carry out demoulding natural curing subsequently, obtain PHC piles; Natural curing condition refers to: outdoor natural temperature, in the three day length of time every day trickle 3-5 time, after 3 days, intensity is up to standard dispatches from the factory, and does not need to continue trickle.

2.3 concrete different larval instar strength development situations

Test the intensity in the age not same period of the PHC pile tube using ultra high early strength poly-carboxylic water reducer to obtain respectively, the intensity of the concrete tubular pile different larval instar simultaneously obtained with the conventional early-strength type carboxylic acid water reducer of daily production and application contrasts, and the results are shown in following table.

Table 8 concrete different larval instar intensity (unit: MPa)

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

Result shows: relative to conventional early-strength type, ultra high early strength poly-carboxylic water reducer of the present invention improves early age strength of concrete.

2.4 economic comparison

Pile tube is two exempts from technique, when using conventional early strong carboxylic acid water reducer, and initial formula use 52.5 cement, (single cement consumption 440kg, cement unit price 370 yuan/ton); When using ultra high early strength poly-carboxylic water reducer, use China Resources 42.5 cement (single cement consumption 435kg, cement unit price 320 yuan/ton), and effect is better.

For Ф 500-125 stake, every meter of stake cement cost is as follows:

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

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

Every mitron stake can reduce costs 3.47 yuan.

3.5 use steam and two non-evaporating vapour cost compare:

For Ф 500-125 stake

Use steam: folk prescription the reinforcement of concrete cement (China Resources) 300kg, sand powder 135kg, sand powder unit price 140 yuan/ton.Two non-evaporating vapour: folk prescription the reinforcement of concrete cement (China Resources) 435kg, sand powder need not.

Material cost increases: 20.49 yuan/meter-16.91 yuan/meters=3.58 yuan/meter.

Steam cost reduces: fuel cost is saved 5.0 yuan/meter (rule of thumb data, Ge Jia factory is slightly different).

Total cost also reduces 1.42 yuan/meter, and produces simple, without the handling cost of boiler and autoclave.

Finally to should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although be explained in detail the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.

Claims

1. the preparation method of a pile tube, it is characterized in that: comprise the following steps: concrete material mix and blend is formed pile concrete, the pile concrete be stirred is loaded in mould, carry out prestressed stretch-draw, pile concrete after prestressed stretch-draw is carried out centrifugal, until pile tube is shaping, carry out demoulding natural curing subsequently, obtain described PHC piles; Described concrete material comprises ultra high early strength poly-carboxylic water reducer, and described ultra high early strength poly-carboxylic water reducer is the compound shown in formula (1) or formula (2);

A is r is H or CH3;

B is

C is

M is r ₂, R ₃and R ₄be alone C1-3 alkyl respectively; X is Cl, Br or I; M is the integer of 5 ~ 200, and n is the integer of 0 ~ 50, and z is the integer of 1 ~ 150.

2. the preparation method of pile tube as claimed in claim 1, is characterized in that: described concrete material comprises: cement, sand, rubble, ultra high early strength poly-carboxylic water reducer and water.

3. the preparation method of pile tube as claimed in claim 2, is characterized in that: the solid volume of folding of described ultra high early strength poly-carboxylic water reducer is 0.1% ~ 0.3% of cement weight.

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

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

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

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

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

9. the pile tube that the preparation method of the pile tube according to claim arbitrary in claim 1 ~ 8 obtains.