CN105199060A - Super-early-strength PCE (polycarboxylate ether) superplasticizer and preparation method thereof - Google Patents

Super-early-strength PCE (polycarboxylate ether) superplasticizer and preparation method thereof Download PDF

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CN105199060A
CN105199060A CN201510666030.0A CN201510666030A CN105199060A CN 105199060 A CN105199060 A CN 105199060A CN 201510666030 A CN201510666030 A CN 201510666030A CN 105199060 A CN105199060 A CN 105199060A
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acid
methoxyl group
integer
preparation
active
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CN105199060B (en
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张小富
赵利华
白淑英
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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Abstract

The invention discloses a super-early-strength PCE (polycarboxylate ether) superplasticizer and a preparation method thereof. The super-early-strength PCE superplasticizer has cationic charges in the molecular structure, promotes the cement hydration reaction, accelerates the strength development of hardened concrete and has the super-early-strength function; the PCE superplasticizer has unique cement particle dispersion capacity, high superplasticizing rate and good concrete resistance due to the unique amphipathic structure and steric hindrance effect of the superplasticizer.

Description

A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof
Technical field
The invention belongs to polycarboxylate water-reducer field, particularly relate to a kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof.
Background technology
In recent years, the R & D and manufacture of concrete admixture has tended to towards high-performance, pollution-free future development, and cement water reducing agent is that in concrete admixture, application surface is the widest, the one that usage quantity is maximum.Water reducer mixes in fresh concrete, can destroy the flucculation structure of cement granules, plays the effect of disperse cement particles and hydrated cementitious particle, thus discharges the free water in flucculation structure, increases the mobility of concrete mix.PCEs water reducer belongs to aniorfic surfactant, mixes in cement slurry, is adsorbed on cationic cement particle surface, and is dissociated into hydrophilic and organic anionic groups that is oleophilic function.
Water reducer molecular skeleton is made up of main chain and more side chain.Containing more active group on main chain, and polarity is stronger, rely on these active groups, main chain can " anchoring " on cement particle surface, and side chain has wetting ability, can stretch in the liquid phase, thus form larger three-dimensional adsorption structure at cement particle surface, produce space steric effect, thus cement granules is disperseed and stablizes.Carboxylic acid ion makes the negative charge on cement granules band produce electrostatic repulsion between cement granules, and cement granules is disperseed, and increases the contact of cement granules and water, makes the abundant aquation of cement.In the process of disperse cement particles, discharge the free water that aggregate comprises, improve workability, decrease and mix the water yield.
The polycarboxylate water-reducer (PCEs) with combed molecular structure is made up of to the main chain of negatively charged ion polyethoxye (PEO) side chain graft usually, PEO side chain produces space steric effect between the cement granules being suspended in aqueous phase, by adjusting the molecular structure of PCEs, different objects can be reached, as slump retaining is good, water-reducing rate is high, cohesiveness is good, resistance to mud is good, in addition low cost, the advantage such as pollution-free, the research of polycarboxylate water-reducer has become the focus of domestic and international concrete admixture research and development.
The main raw material of poly carboxylic acid series water reducer has unsaturated acid, as maleic anhydride, toxilic acid and the polymerisable carboxylic acid such as vinylformic acid, methacrylic acid, the thiazolinyl materials such as polyalkenyl hydrocarbon, ether, alcohol, poly styrene sulfonate or ester and acrylate, ester, dihydroxy-benzene, acrylamide etc., synthetic method has the direct copolymerization of polymerisable monomer, polymerization Post functionalization method, in-situ polymerization and grafting etc. substantially.
The direct copolymerization of polymerisable monomer: this synthetic method is generally first prepare the side chain polymeric monomer (being generally methoxy polyethylene glycol methacrylate-styrene polymer) with polymerization activity, then the monomer of certain proportioning is mixed, directly adopt solution polymerization and obtain finished product.This polymerization process, technique is simple, but prerequisite wants composite reactive polymerizable polymeric monomer, and the performance of polymeric monomer directly determines and affect the performance of the finished product polycarboxylate water-reducer.
Current China market mainly contains for the production of the surface-active macromonomer of PCEs water reducer:
MPEG: poly glycol monomethyl ether
VPEG:4-hydroxy butyl vinyl ether Soxylat A 25-7
APEG: allyl alcohol polyethenoxy ether
HPEG: isobutene alcohol Soxylat A 25-7
TPEG: isopentenol polyoxyethylene ether
APEG is bar-shaped rigid structure, high to cement adsorptive capacity, and TPEG microtexture is star-shape polymer, has soft segment microtexture, few to cement adsorptive capacity.
APEG is the main raw material of synthesizing polycarboxylic acid high-performance water reducing agent, the advantages such as PCEs water reducer has good dispersity, volume is low, and water-reducing rate is high, adaptability is good of synthesis; Shortcoming is inferior suitability, and Slump Time losing of Large is large.HPEG and TPEG is the water reducer of raw material production, and water-reducing rate is more or less the same, but summer uses, and slump retaining gap is comparatively large, and cement adaptability is slightly poor.Use the polycarboxylate water-reducer that TPEG is main material production, water-reducing rate is high, and slump retaining is good, strong to cement adaptability, and production process equipment is simple, and by polycarboxylate water-reducer, manufacturers is favored.But due to complicacy and the diversity of China's concrete raw material, especially when the earth content of sandstone is large, concrete slump-loss is large, the polycarboxylate water-reducer produced by TPEG, because PEG side chain and earth occur to connect intercalation, make its resistance to mud poor, can not meet the requirement of concrete construction performance.
RCOO -with Ca 2+ionization forms complex compound, reduces the Ca in solution 2+concentration, delays Ca (OH) 2form crystallization, reduce the formation of C-H-S gel, delayed the aquation of cement.
Summary of the invention
The invention provides a kind of ultra high early strength poly-carboxylic water reducer, this water reducer has cationic charge in the molecular structure, the water of cement can be promoted and change reaction, accelerate the strength development of maturing, there is super hardening effect, and due to the both sexes structure of its uniqueness and space steric effect, make it have unique cement granules dispersive ability, water-reducing rate is high, and resistance to earth is good.
The technical solution used in the present invention is: a kind of ultra high early strength poly-carboxylic water reducer, and the structural formula of described ultra high early strength poly-carboxylic water reducer is such as formula shown in (1):
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
N is r 2, R 3and R 4be alone C respectively 1-3alkyl; 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.
As the further improvement to technique scheme, described m is the integer of 10 ~ 180, and described n is the integer of 0 ~ 40, and described z is the integer of 1 ~ 120, and described X is Cl.
As the further improvement to technique scheme, described m is the integer of 12 ~ 100, and described n is the integer of 0 ~ 30, and described z is the integer of 1 ~ 100.
Present invention also offers the preparation method of described ultra high early strength poly-carboxylic water reducer, said method comprising the steps of:
By surface-active macromonomer, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, one in APEG, HPEG, VPEG and TPEG, sodium allyl sulfonate, water and molecular weight regulator mix, and are warming up to 85 ~ 95 DEG C, drip initiator, dropwise rear insulation, then be cooled to 45 ~ 50 DEG C, add sodium hydroxide solution and regulate pH to 7.0-8.0, obtain ultra high early strength poly-carboxylic water reducer;
Described surface-active macromonomer is the compound shown in formula (2), and the structural formula of the compound shown in described formula (2) is as follows:
it is the integer of 5 ~ 200; N is the integer of 0 ~ 50; Z is the integer of 1 ~ 150.M is the integer of 5 ~ 200, and n is the integer of 0 ~ 50, and z is the integer of 1 ~ 150.
As the further improvement to technique scheme, described m is the integer of 10 ~ 180, and described n is the integer of 0 ~ 40, and described z is the integer of 1 ~ 120, and described X is Cl.
As the further improvement to technique scheme, described m is the integer of 12 ~ 100, and described n is the integer of 0 ~ 30, and described z is the integer of 1 ~ 100.
As the further improvement to technique scheme, one in described methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, one in APEG, HPEG, VPEG and TPEG, the mol ratio of surface-active macromonomer and sodium allyl sulfonate is the one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride: the one in APEG, HPEG, VPEG and TPEG: surface-active macromonomer: sodium allyl sulfonate=1 ~ 6.0:1.0:1.0 ~ 3.0:0.2 ~ 6.0.
As the further improvement to technique scheme, described molecular weight regulator 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 the total mole number of a kind of and sodium allyl sulfonate in APEG, VPEG, HPEG and TPEG.
As the further improvement to technique scheme, described sulfhydryl compound is 3-thiohydracrylic acid, Thiovanic acid, mercaptoethanol or rongalite.
As the further improvement to technique scheme, the time for adding of described initiator is 1 ~ 10h, and described soaking time is 1 ~ 12h.
As the further improvement to technique scheme, described initiator 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, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, 0.05% ~ 5% of a kind of and acrylamide in APEG, VPEG, HPEG and TPEG and a kind of total mole number in 2-acrylamide-2-methyl propane sulfonic.
As the further improvement to technique scheme, described surface-active macromonomer is prepared by following steps:
1) 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; The reaction equation of this step is:
2) synthesis of methoxyl group PEG active intermediate
Step 1 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; The reaction equation of this step is:
3) synthesis of surface-active macromonomer
Quaternization reactant and stopper is added in reactor, be warming up to 10-80 DEG C, slow dropping step 2) 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;
Described quaternization reactant is N (R 2r 3r 4), wherein R 2, R 3and R 4be alone C respectively 1-3alkyl; The reaction equation of this step is:
Wherein, R 1for r 2, R 3and R 4be alone C respectively 1-3alkyl; X is Cl, Br or I; M is the integer of 5 ~ 200; N is the integer of 0 ~ 50; Z is the integer of 1 ~ 150.
As the further improvement to technique scheme, described quaternization reactant is Trimethylamine 99, triethylamine, tripropyl amine, N, N-dimethyl amine, N, N-diethyl methyl amine, N, N-dimethyl propylamine, N, N-diisopropyl methylamine or DIPEA.
As the further improvement to technique scheme, described step 1) in, the mixture of methyl alcohol, oxyethane or oxyethane and propylene oxide, the mol ratio of epoxyhalopropane are methyl alcohol: the mixture of oxyethane or oxyethane and propylene oxide: epoxyhalopropane=1:5 ~ 200:1 ~ 150.
As the further improvement to technique scheme, described step 2) in, the mol ratio of methoxyl group hydroxyl PEG intermediate and olefin(e) acid is 1:1.0 ~ 8.0.
As the further improvement to technique scheme, described step 3) in, the mol ratio of quaternization reactant and described methoxyl group PEG active intermediate is 0.2 ~ 2:1.
As the further improvement to technique scheme, described step 1) in catalyzer be sodium hydride or sodium; Described step 2) in catalyzer be at least one in methylsulfonic acid and p-methyl benzenesulfonic acid; Described stopper is Resorcinol and at least one in methyl ether phenol; The consumption of described stopper is 0.002% ~ 0.010% of described methoxyl group PEG active intermediate mole number.
Present invention also offers the described application of ultra high early strength poly-carboxylic water reducer in concrete.
Ultra high early strength poly-carboxylic water reducer of the present invention can accelerate the water of cement and turn use into, has super hardening effect.Ultra high early strength poly-carboxylic water reducer of the present invention, in normal concrete, has resistance to mud, protects the effect of collapsing, be used in pipe pile body concrete, have super hardening effect, can realize singly exempting from and twoly exempting from technique of pile tube, and not need to add any active mineral admixture.
Relative to prior art, beneficial effect of the present invention is:
Ultra high early strength poly-carboxylic water reducer of the present invention take surface-active macromonomer as Material synthesis, while the space steric effect improving water reducer further, introduce positively charged ion in the molecule, accelerate cement water and change reaction, there is super hardening effect, positively charged ion has good anti-mud simultaneously, thus improves water-reducing rate, resistance to mud and the adaptability to cement of water reducer.To earth, there is better tolerance, do not occur to connect intercalation with earth.
Compared with common polycarboxylate water-reducer, identical volume, the water-reducing rate of ultra high early strength poly-carboxylic water reducer of the present invention improves 10-20%.
To the concrete (silt content 5%) of high silt content, compared with common polycarboxylate water-reducer, identical volume, the water-reducing rate of ultra high early strength poly-carboxylic water reducer of the present invention improves 20-35%.
The positively charged ion of ultra high early strength poly-carboxylic water reducer of the present invention can suppress the expansion of earth, thus reduces earth to the absorption of admixture.When product of the present invention joins in cement slurry, the anionic charge of main chain is adsorbed on positively charged cement particle surface, and the positive charge of side chain end group is then adsorbed on electronegative cement particle surface, disperse cement particles.Because poly-hydroxy becomes hydrogen bond with water, add the viscosity of cement slurry, improve mobility and the cohesiveness of concrete mix.
Ultra high early strength poly-carboxylic water reducer of the present invention can accelerate the water of cement and turn use into, has super hardening effect.Ultra high early strength poly-carboxylic water reducer of the present invention, in normal concrete, has resistance to mud, protects the effect of collapsing, be used in pipe pile body concrete, have super hardening effect, can realize singly exempting from and twoly exempting from technique of pile tube, and not need to add any active mineral admixture.
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.
Embodiment 1
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject 1.0mol methyl alcohol, 80mol oxyethane, 20mol epoxy chloropropane and 3g sodium hydride respectively, stir, react 8h at 80 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, 7.2mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 15h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 1.0mol Trimethylamine 99 and 0.01g Resorcinol is added, be warming up to 75 DEG C, slow dropping contains 0.5mol step 2) trimethylamine solution of described methoxyl group active intermediate is (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 5%), after dropwising, under 75 DEG C of conditions, continue insulation reaction 1.5h, obtain described surface-active macromonomer.
Embodiment 2
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject 1mol methyl alcohol, 5mol oxyethane, 1mol epoxy chloropropane and 2g sodium hydride respectively, stir, react 2h 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 0.8mol methoxyl group hydroxy intermediate, 0.85mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 3h at 70 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 0.1mol triethylamine and 0.01g Resorcinol is added, be warming up to 80 DEG C, slow dropping contains 0.5mol step 2) triethylamine solution of described methoxyl group PEG active intermediate is (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 12%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 1h, obtain described surface-active macromonomer.
Embodiment 3
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject 1mol methyl alcohol, 200mol oxyethane, 150mol epoxy chloropropane and 2g sodium respectively, stir, react 10h at 150 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 maleic anhydride, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 10h at 170 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 1.5mol 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 described methoxyl group PEG active intermediate is (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 10%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 6h, obtain described surface-active macromonomer.
Embodiment 4
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject 1mol methyl alcohol, 175mol oxyethane, 75mol epoxy chloropropane and 2g sodium 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 0.7mol methoxyl group hydroxy intermediate, 4.2mol methacrylic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 15h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 0.5molN is added, N-dimethyl amine and 0.01g Resorcinol, be warming up to 50 DEG C, slow dropping is containing 0.5mol step 2) N of described methoxyl group PEG active intermediate, N-dimethyl amine solution (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 50 DEG C of conditions, continue insulation reaction 10h, obtain described surface-active macromonomer.
Embodiment 5
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject 1mol methyl alcohol, 100mol oxyethane, 80mol epoxy chloropropane and 2g sodium hydride respectively, stir, react 8h at 120 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 0.8mol methoxyl group hydroxy intermediate, 4.0mol methacrylic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 9h at 100 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 0.2molN is added, N-dimethyl propylamine and 0.01g Resorcinol, be warming up to 30 DEG C, slow dropping is containing 0.7mol step 2) N of described methoxyl group PEG active intermediate, N-dimethyl propylene amine aqueous solution (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 15%), after dropwising, under 30 DEG C of conditions, continue insulation reaction 10h, obtain described surface-active macromonomer.
Embodiment 6
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject the mixture of 1.0mol methyl alcohol, 100mol oxyethane and 50mol propylene oxide, 100mol epoxy chloropropane and 4g sodium hydride respectively, stir, react 9h at 120 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, 3.5mol vinylformic acid, 1g methylsulfonic acid and the 0.01g Resorcinol synthesized, stir, react 12h at 120 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 0.35mol Trimethylamine 99 and 0.01g Resorcinol is added, be warming up to 50 DEG C, slow dropping contains 0.6mol step 2) trimethylamine solution of described methoxyl group PEG active intermediate is (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 5%), after dropwising, under 50 DEG C of conditions, continue insulation reaction 5h, obtain described surface-active macromonomer.
Embodiment 7
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject the mixture of 1.0mol methyl alcohol, 90mol oxyethane and 20mol propylene oxide, 75mol Epiiodohydrin and 2.5g sodium hydride respectively, stir, react 7h 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) in the 0.8mol methoxyl group hydroxyl PEG intermediate of synthesis, 2.4mol methylene-succinic acid, 1.5g methylsulfonic acid and 0.01g be to methyl ether phenol, stir, react 15h at 120 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 6.0mol triethylamine and 0.01g Resorcinol is added, be warming up to 80 DEG C, slow dropping is containing 0.65mol step 2) triethylamine solution of described methoxyl group PEG active intermediate is (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 12%), after dropwising, under 80 DEG C of conditions, continue insulation reaction 1h, obtain described surface-active macromonomer.
Embodiment 8
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
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 10h at 90 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 15h at 90 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 1.0mol tripropyl amine and 0.01g Resorcinol is added, be warming up to 10 DEG C, slow dropping is containing 0.5mol step 2) the tripropyl amine solution of described methoxyl group PEG active intermediate is (wherein, the Mole percent specific concentration of methoxyl group PEG active intermediate is 10%), after dropwising, under 10 DEG C of conditions, continue insulation reaction 10h, obtain described surface-active macromonomer.
Embodiment 9
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject the mixture of 0.5mol methyl alcohol, 60mol oxyethane and 20mol propylene oxide, 2mol epoxy bromopropane and 2g sodium hydride respectively, stir, react 9h at 90 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, 2.4mol maleic anhydride, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 3h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 0.12molN is added, N-dimethyl amine and 0.01g Resorcinol, be warming up to 80 DEG C, slow dropping is containing 0.6mol step 2) N of described methoxyl group PEG active intermediate, 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.
Embodiment 10
An embodiment of the preparation method of surface-active macromonomer of the present invention, comprises the following steps:
1) in the autoclave closed, inject the mixture of 1mol methyl alcohol, 165mol oxyethane and 35mol propylene oxide, 120mol epoxy bromopropane and 3g sodium hydride respectively, stir, react 10h at 130 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, 1.3mol vinylformic acid, 3g p-methyl benzenesulfonic acid and the 0.01g Resorcinol synthesized, stir, react 20h at 110 DEG C, obtain reaction product methoxyl group PEG active intermediate;
3) in glass flask, 0.75molN is added, N-dimethyl propylamine and 0.01g Resorcinol, be warming up to 50 DEG C, slow dropping is containing 0.72mol step 2) N of described methoxyl group PEG active intermediate, N-dimethyl propylene amine aqueous solution (wherein, the Mole percent specific 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.
Embodiment 11
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.7mol embodiment 1, 0.7mol vinylformic acid, 0.7molTPEG, 1.4molmol sodium allyl sulfonate and 500ml 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 TPEG 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 TPEG 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 12
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.5mol embodiment 2, 1.5mol methylene-succinic acid, 0.5molHPEG, 3.0mol 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, methylene-succinic 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, methylene-succinic 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 13
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.5mol embodiment 3, 1.0mol methacrylic acid, 0.17molTPEG, 1.0mol sodium allyl sulfonate and 500ml deionized water, described molecular weight regulator is mercaptoethanol, the consumption of described molecular weight regulator is described surface-active macromonomer, methacrylic acid, 0.005% of sodium allyl sulfonate 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, methacrylic acid, 0.05% of sodium allyl sulfonate and TPEG total mole number, time for adding is 10h, after dropwising, insulation reaction 12h, 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 14
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.5mol embodiment 4, 0.75mol methacrylic acid, 0.25molVPEG, 1.0mol sodium allyl sulfonate and 400ml deionized water, described molecular weight regulator is Virahol, the consumption of described molecular weight regulator is described surface-active macromonomer, methacrylic acid, 5% of sodium allyl sulfonate 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, 5% of sodium allyl sulfonate 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 15
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.5mol embodiment 5, 0.66mol maleic anhydride, 0.33molTPEG, 0.99mol sodium allyl sulfonate and 600ml deionized water, described molecular weight regulator is rongalite, the consumption of described molecular weight regulator is described surface-active macromonomer, maleic anhydride, 1.2% of sodium allyl sulfonate and TPEG 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, maleic anhydride, 2% of sodium allyl sulfonate and TPEG 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
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.5mol embodiment 6, 1.2mol vinylformic acid, 0.5molAPEG, 1.5mol sodium allyl sulfonate and 500ml deionized water, described molecular weight regulator is mercaptoethanol, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 0.25% of sodium allyl sulfonate and APEG 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, 0.1% of sodium allyl sulfonate and APEG total mole number, time for adding is 6h, after dropwising, insulation reaction 5h, 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 17
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.7mol embodiment 7, 0.7mol maleic anhydride, 0.35molAPEG, 0.7mol 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, maleic anhydride, 2% 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, maleic anhydride, 1.5% 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 18
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.5mol embodiment 8, 0.68mol vinylformic acid, 0.17molHPEG, 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, 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, vinylformic acid, 0.5% of sodium allyl sulfonate and HPEG total mole number, time for adding is 7h, 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 19
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.6mol embodiment 9, 1.8mol vinylformic acid, 0.6molTPEG, 2.4mol sodium allyl sulfonate and 500ml deionized water, described molecular weight regulator is mercaptoethanol, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 1.8% of sodium allyl sulfonate 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, 4% of sodium allyl sulfonate 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 20
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water reducer of the present invention:
Agitator is being housed, in the 1000ml four-hole boiling flask of thermometer and reflux condensing tube, add molecular weight regulator, surface-active macromonomer described in 0.7mol embodiment 10, 1.75mol vinylformic acid, 0.35molHPEG, 1.2mol 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, 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, vinylformic acid, 5% of sodium allyl sulfonate and HPEG total mole number, time for adding is 1h, after dropwising, insulation reaction 1h, 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.
Application examples 1
the feasibility Experiment that super hardening carboxylic acid water reducer is applied in concrete
Adopt the ultra high early strength poly-carboxylic water reducer of synthesis in the embodiment of the present invention 11 ~ 20 to prepare concrete, with common polycarboxylate water-reducer as a comparison, common polycarboxylate water-reducer is the polycarboxylate water-reducer of not cation quaternary ammonium salt.First measure the ultra high early strength poly-carboxylic water reducer of synthesis and the water-reducing rate of common polycarboxylate water-reducer in the embodiment of the present invention 11 ~ 20, then prepare concrete by following proportioning, measure the performance such as concrete time of coagulation, maturing strength development.
The proportioning of normal concrete is as follows:
Cement: flyash: breeze: river sand: rubble: water: common polycarboxylate water-reducer=200:90:60:800:1080:165:8.5;
The mix proportion that the embodiment of the present invention 11 ~ 20 ultra high early strength poly-carboxylic water reducer obtains is as follows:
Cement: flyash: breeze: river sand: rubble: water: polycarboxylate water-reducer=200:9:60:800:1080:165:7.0 of the present invention.
The concrete effectiveness comparison prepared by the embodiment of the present invention 11 ~ 20 ultra high early strength poly-carboxylic water reducer and common polycarboxylate water-reducer is as follows:
As can be seen here, ultra high early strength poly-carboxylic water reducer of the present invention is used in concrete, compared with common polycarboxylate water-reducer, better dispersiveness is had to cement slurry, water-reducing rate improves, and simultaneously because the positively charged ion of side chain is adsorbed with restraining effect to clay, resistance to mud well has super hardening effect simultaneously, can promote that cement hydrationization is reacted, the strength development of maturing is played a driving role.
Application examples 2
ultra high early strength poly-carboxylic water reducer is in two feasibility Experiment exempting from the application of pile tube production technique
1.1 raw-materially select
(1) cement: select P II 52.5 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 11 ~ 20.
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, silt content 0.2%.
(4) rubble: grouan 5 ~ 25mm, crush values index 8%, silt content 0.1%.
1.2 contents of the test and analysis
Under natural curing condition, require that concrete can form removal in 7-10 hour, concrete strength reaches more than 45-50MPa, when after full 3 ~ 5 days of the age of concrete, intensity can reach more than more than 100% of design strength (80MPa), 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 water reducer, concrete can realize early strong, natural curing 7-10h days intensity reaches more than 43-52MPa, can safe form removal, when the age of concrete is to 3-5 days, intensity reaches more than 100% of design strength (80MPa), 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 7-10 hour, after form removal in husky pond and autoclave timing trickle, to ensure effectively completing of hydrated cementitious process in early stage.1 day laggard enter outdoor stockyard, full can to dispatch from the factory after 3-5 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 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.
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 (10)

1. a ultra high early strength poly-carboxylic water reducer, is characterized in that: the structural formula of described ultra high early strength poly-carboxylic water reducer is such as formula shown in (1):
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
N is
r 2, R 3and R 4be alone C respectively 1-3alkyl; 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. a preparation method for ultra high early strength poly-carboxylic water reducer as claimed in claim 1, is characterized in that, said method comprising the steps of:
By surface-active macromonomer, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, one in APEG, HPEG, VPEG and TPEG, sodium allyl sulfonate, water and molecular weight regulator mix, and are 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 ultra high early strength poly-carboxylic water reducer;
Described surface-active macromonomer is the compound shown in formula (2), and the structural formula of the compound shown in described formula (2) is as follows:
be the integer of 5 ~ 200, n is the integer of 0 ~ 50, and z is the integer of 1 ~ 150.
3. preparation method according to claim 2, it is characterized in that, one in described methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, one in APEG, HPEG, VPEG and TPEG, the mol ratio of surface-active macromonomer and sodium allyl sulfonate is the one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride: the one in APEG, HPEG, VPEG and TPEG: surface-active macromonomer: sodium allyl sulfonate=1 ~ 6.0:1.0:1.0 ~ 3.0:0.2 ~ 6.0.
4. preparation method according to claim 2, it is characterized in that, described molecular weight regulator 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 the total mole number of a kind of and sodium allyl sulfonate in APEG, VPEG, HPEG and TPEG.
5. preparation method according to claim 2, is characterized in that, the time for adding of described initiator is 1 ~ 10h, and described soaking time is 1 ~ 12h.
6. preparation method according to claim 2, is characterized in that, described initiator 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, the one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, 0.05% ~ 5% of the total mole number of a kind of and sodium allyl sulfonate in APEG, VPEG, HPEG and TPEG.
7. preparation method as claimed in claim 2, it is characterized in that, described surface-active macromonomer is prepared by following steps:
1) 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;
2) synthesis of methoxyl group PEG active intermediate
Step 1 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;
3) synthesis of surface-active macromonomer
Quaternization reactant and stopper is added in reactor, be warming up to 10-80 DEG C, slow dropping step 2) 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;
Described quaternization reactant is N (R 2r 3r 4), wherein R 2, R 3and R 4be alone C respectively 1-3alkyl.
8. preparation method as claimed in claim 7, it is characterized in that, described step 1) in, the mixture of methyl alcohol, oxyethane or oxyethane and propylene oxide, the mol ratio of epoxyhalopropane are methyl alcohol: the mixture of oxyethane or oxyethane and propylene oxide: epoxyhalopropane=1:5 ~ 200:1 ~ 150.
9. preparation method as claimed in claim 7, is characterized in that, described step 2) in, the mol ratio of methoxyl group hydroxyl PEG intermediate and olefin(e) acid is 1:1.0 ~ 8.0.
10. preparation method as claimed in claim 7, is characterized in that, described step 3) in, the mol ratio of quaternization reactant and described methoxyl group PEG active intermediate is 0.2 ~ 2:1.
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