CN105271900A - Polycarboxylate superplasticizer with super high early strength and preparation method of polycarboxylate superplasticizer - Google Patents
Polycarboxylate superplasticizer with super high early strength and preparation method of polycarboxylate superplasticizer Download PDFInfo
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- CN105271900A CN105271900A CN201510666206.2A CN201510666206A CN105271900A CN 105271900 A CN105271900 A CN 105271900A CN 201510666206 A CN201510666206 A CN 201510666206A CN 105271900 A CN105271900 A CN 105271900A
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Abstract
The invention provides a polycarboxylate superplasticizer with super high early strength. The polycarboxylate superplasticizer with super high early strength is a compound shown in the formula (I) and is synthesized with an active macromonomer as the raw material, cations are introduced into molecules while the steric hindrance effect of the superplasticizer is further improved, the cations have good soil resistance, so that the water-reducing rate of the superplasticizer is increased, and the soil resistance and the cement adaptability of the superplasticizer are improved. The polycarboxylate superplasticizer has better tolerance for soil and does not have an intercalation reaction with the soil. The cations of the polycarboxylate superplasticizer with super high early strength can inhibit soil expansion, so that admixture adsorption by the soil is reduced. The polycarboxylate superplasticizer with super high early strength can accelerate hydration of cement and has the super high early strength function. The polycarboxylate superplasticizer with super high early strength has super high early strength and soil resistance functions when applied to common concrete.
Description
Technical field
The present invention relates to a kind of water reducer, be specifically related 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.
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.
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 pendant reactive 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 surface-active macromonomer, and the performance of surface-active macromonomer directly determines and affect the performance of the finished product polycarboxylate water-reducer.
Current China market mainly contains for the production of the active polymeric monomer 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.
Summary of the invention
The object of the invention is to overcome weak point that prior art exists and provide a kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof, this water reducer has cationic charge in the molecular structure, due to both sexes structure and the space steric effect of its uniqueness, it is made to have unique dispersive ability, water-reducing rate is high, slump-retaining good, resistance to earth is good.
For achieving the above object, the technical scheme taked: a kind of ultra high early strength poly-carboxylic water reducer, described ultra high early strength poly-carboxylic water reducer is the compound shown in formula I, and the structural formula of the compound shown in described formula I 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 C respectively
1-3alkyl; X
-for 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.
The invention provides the preparation method of ultra high early strength poly-carboxylic water reducer described above, 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, one in acrylamide and 2-acrylamide-2-methyl propane sulfonic, water and molecular weight regulator mixing, be warming up to 85 ~ 95 DEG C, drip initiator, time for adding is 1 ~ 10h, dropwise rear insulation, soaking time is 1 ~ 12h, is then 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 II, and the structural formula of the compound shown in described formula II is as follows:
Wherein R
1for
or
r
2, R
3and R
4be alone C respectively
1-3alkyl; X
-for 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.
Preferably, 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 ~ 100.More preferably, 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 ~ 80.
Preferably, described surface-active macromonomer, one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride, a kind of and acrylamide in APEG, HPEG, VPEG and TPEG and a kind of mol ratio in 2-acrylamide-2-methyl propane sulfonic are described surface-active macromonomer: the one in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride: the one in APEG, HPEG, VPEG and TPEG: one=1.0 ~ 3.0:1 ~ 6.0:1:0.2 ~ 6.0 in acrylamide and 2-acrylamide-2-methyl propane sulfonic.
Preferably, 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 a kind of and acrylamide in APEG, HPEG, VPEG and TPEG and a kind of total mole number in 2-acrylamide-2-methyl propane sulfonic.More preferably, described molecular weight regulator is at least one in 3-thiohydracrylic acid, Thiovanic acid, mercaptoethanol, rongalite and Virahol, the consumption of described molecular weight regulator is described surface-active macromonomer, a kind of and 1 ~ 3.5% of a kind of total mole number in APEG, HPEG, VPEG and TPEG in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride.Most preferably, the consumption of described molecular weight regulator is described surface-active macromonomer, a kind of and 1.2 ~ 2.5% of a kind of total mole number in APEG, HPEG, VPEG and TPEG in methacrylic acid, vinylformic acid, methylene-succinic acid and maleic anhydride.
Preferably, the time for adding of described initiator is 2 ~ 3h; Described soaking time is 2 ~ 4h.
Preferably, the mass concentration of described sodium hydroxide solution is 30%; Described initiator is the one in Potassium Persulphate, ammonium persulphate, hydrogen peroxide 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, HPEG, VPEG and TPEG and a kind of total mole number in 2-acrylamide-2-methyl propane sulfonic.
Preferably, described cation quaternary ammonium salt PEO surface-active macromonomer is prepared from by following methods:
(1) by the one in vinyl carbinol, isobutene alcohol, 4-hydroxy butyl vinyl ether and prenol, one in the mixture of oxyethane and oxyethane and propylene oxide, mix with epoxyhalopropane, add catalyzer, react 2 ~ 10 hours under temperature is 80 ~ 150 DEG C of conditions, obtain active intermediate; Its reaction equation is as follows:
(2) quarternary ammonium salt compound is mixed with stopper, slowly add the active intermediate that step (1) synthesizes and react 1 ~ 10h under temperature is 10 ~ 80 DEG C of conditions, obtain described surface-active macromonomer; Its reaction equation is as follows:
Described quarternary ammonium salt compound is N (R
2r
3r
4), wherein R
2, R
3and R
4be alone C respectively
1-3alkyl.
Preferably, one in step (1) described in described step (1) in vinyl carbinol, isobutene alcohol, 4-hydroxy butyl vinyl ether and prenol, one in the mixture of oxyethane and oxyethane and propylene oxide is the one in vinyl carbinol, isobutene alcohol, 4-hydroxy butyl vinyl ether and prenol with the mol ratio of epoxyhalopropane: the one in the mixture of oxyethane and oxyethane and propylene oxide: epoxyhalopropane=1:5 ~ 250:1 ~ 150.
Preferably, in described step (2), the mol ratio of quarternary ammonium salt compound and active intermediate is 0.2:1 ~ 2:1.
Preferably, in described step (1), catalyzer is sodium hydride or sodium; Stopper is Resorcinol or to methyl ether phenol, the consumption of described stopper is 0.02% ~ 0.08% of described active intermediate mole number in described step (2).
Beneficial effect of the present invention is: the invention provides a kind of ultra high early strength poly-carboxylic water reducer, and relative to prior art, its advantage is:
Ultra high early strength poly-carboxylic water reducer of the present invention with cation quaternary ammonium salt PEO surface-active macromonomer for Material synthesis, while the space steric effect improving water reducer further, introduce positively charged ion in the molecule, and positively charged ion has good anti-mud, thus improve 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.
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 ultra high early strength poly-carboxylic water reducer 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 effect, is 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.
Embodiment 1
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention:
1), the synthesis of active intermediate
5mol prenol is injected, 5g sodium hydride, 25mol oxyethane in the autoclave closed, and 5mol epoxy chloropropane, stir, 80 DEG C of reaction 10h, obtain reaction product active intermediate.
2) synthesis of surface-active macromonomer
1mol triethylamine and 0.001mol Resorcinol are added in flask, is warming up to 10 DEG C, slowly drip the triethylamine solution of the active intermediate synthesized containing 5mol step (1), after dropwising, under 10 DEG C of conditions, continue insulation reaction 10h, obtain surface-active macromonomer.
Embodiment 2
A kind of embodiment of the preparation method of cation quaternary ammonium salt PEO surface-active macromonomer of the present invention:
1), the synthesis of active intermediate
5mol isobutene alcohol is injected, 20g sodium hydride, 500mol oxyethane, 250mol propylene oxide in the autoclave closed, and 750mol epoxy bromopropane, stir, 150 DEG C of reaction 2h, obtain reaction product active intermediate.
2) synthesis of surface-active macromonomer
3mol Trimethylamine 99 and 0.004mol Resorcinol are added in flask, is warming up to 30 DEG C, slowly drip the trimethylamine solution of the active intermediate synthesized containing 5mol step (1), after dropwising, under 30 DEG C of conditions, continue insulation reaction 10h, obtain surface-active macromonomer.
Embodiment 3
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention:
1), the synthesis of active intermediate
5mol vinyl carbinol is injected, 10g sodium hydride, 1000mol oxyethane in the autoclave closed, and 400mol Epiiodohydrin, stir, 100 DEG C of reaction 6h, obtain reaction product active intermediate.
2) synthesis of surface-active macromonomer
5mol tripropyl amine and 0.0015mol Resorcinol are added in flask, is warming up to 50 DEG C, slowly drip the tripropyl amine solution of the active intermediate synthesized containing 5mol step (1), after dropwising, under 50 DEG C of conditions, continue insulation reaction 8h, obtain surface-active macromonomer.
Embodiment 4
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention:
1), the synthesis of active intermediate
In the autoclave closed, inject 5mol4-hydroxy butyl vinyl ether, 10g sodium hydride, 50mol oxyethane, 5mol propylene oxide and 500mol Epiiodohydrin, stir, 120 DEG C of reaction 5h, obtain reaction product active intermediate.
2) synthesis of surface-active macromonomer
By 7molN, N-dimethyl amine and 0.0005mol add in flask to methyl ether phenol, be warming up to 70 DEG C, slow dropping contains the N of the active intermediate that 5mol step (1) is synthesized, N-dimethyl amine solution, after dropwising, under 70 DEG C of conditions, continue insulation reaction 4h, obtain surface-active macromonomer.
Embodiment 5
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention:
1), the synthesis of active intermediate
5mol vinyl carbinol is injected, 10g sodium, 900mol oxyethane, 150mol propylene oxide in the autoclave closed, and 150mol Epiiodohydrin, stir, 120 DEG C of reaction 5h, obtain reaction product active intermediate.
2) synthesis of surface-active macromonomer
By 10molN, N-diethyl methyl amine and 0.002mol add in flask to methyl ether phenol, be warming up to 80 DEG C, slow dropping contains the N of the active intermediate that 5mol step (1) is synthesized, N-diethyl methyl amine solution, after dropwising, under 80 DEG C of conditions, continue insulation reaction 1h, obtain surface-active macromonomer.
Embodiment 6
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 1mol embodiment 1, 1mol methacrylic acid, 1.0molAPEG, 0.2mol 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, 0.005% of acrylamide and APEG total mole number, be warming up to 85 DEG C, drip the aqueous solution of initiator, described initiator is Potassium Persulphate, the consumption of described initiator is described surface-active macromonomer, methacrylic acid, 0.05% of acrylamide 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 7
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 2mol embodiment 2, 2.5mol vinylformic acid, 1molHPEG, 1mol2-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 is 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 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 8
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 3mol embodiment 3, 6mol vinylformic acid, 1molTPEG, 6mol 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 is matter benzoyl peroxide, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 0.1% of acrylamide and TPEG total mole number, time for adding is 5h, after dropwising, insulation reaction 6h, 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 9
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 2mol embodiment 4, 1.2mol methacrylic acid, 1.0molVPEG, 0.6mol2-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, 3.5% 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 is 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
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 2mol embodiment 5, 2.5mol vinylformic acid, 1molHPEG, 2mol acrylamide and 600ml deionized water, described molecular weight regulator is rongalite, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 1.2% of acrylamide and HPEG total mole number, be warming up to 95 DEG C, drip the aqueous solution of initiator, described initiator is ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 2% of acrylamide 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 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 1mol embodiment 1, 4mol vinylformic acid, 1molTPEG, 4mol2-acrylamide-2-methyl propane sulfonic and 500ml deionized water, described molecular weight regulator is mercaptoethanol, the consumption of described molecular weight regulator is described surface-active macromonomer, vinylformic acid, 2.5% of 2-acrylamide-2-methyl propane sulfonic and TPEG total mole number, be warming up to 90 DEG C, drip the aqueous solution of initiator, described initiator is benzoyl peroxide, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 1% of 2-acrylamide-2-methyl propane sulfonic and TPEG total mole number, time for adding is 7h, after dropwising, insulation reaction 8h, 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
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 1mol embodiment 2, 1mol methacrylic acid, 1.0molAPEG, 1mol 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 is 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 9h, after dropwising, insulation reaction 10h, 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 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 3mol embodiment 3, 3mol vinylformic acid, 1molHPEG, 3mol2-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, 0.1% 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 is ammonium persulphate, the consumption of described initiator is described surface-active macromonomer, vinylformic 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 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 1mol embodiment 4, 6mol vinylformic acid, 1molTPEG, 6mol 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, 0.01% of acrylamide and TPEG total mole number, be warming up to 90 DEG C, drip the aqueous solution of initiator, described initiator is benzoyl peroxide, the consumption of described initiator is described surface-active macromonomer, vinylformic acid, 4% of acrylamide and TPEG total mole number, time for adding is 1h, 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 15: the practical application technique effect of ultra high early strength poly-carboxylic water reducer of the present invention in concrete
Adopt the ultra high early strength poly-carboxylic water reducer of synthesis in the embodiment of the present invention 6 ~ 14 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 6 ~ 14, then prepare concrete by following proportioning, measure the performance such as concrete time of coagulation and 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 6 ~ 14 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 6 ~ 14 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, simultaneously because the positively charged ion of side chain is adsorbed with restraining effect to clay, thus this product has good resistance to mud effect; There is super hardening effect simultaneously, can promote that cement hydrationization is reacted, the strength development of maturing is played a driving role.
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, described ultra high early strength poly-carboxylic water reducer is the compound shown in formula I, and the structural formula of the compound shown in described formula I 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 C respectively
1-3alkyl; X
-for 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, one in acrylamide and 2-acrylamide-2-methyl propane sulfonic, water and molecular weight regulator mixing, be warming up to 85 ~ 95 DEG C, drip initiator, time for adding is 1 ~ 10h, dropwise rear insulation, soaking time is 1 ~ 12h, is then 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 II, and the structural formula of the compound shown in described formula II is as follows:
Wherein R
1for H
2c=CH-O-CH
2cH
2cH
2cH
2-, H
2c=CHCH
2-,
or
r
2, R
3and R
4be alone C respectively
1-3alkyl; X
-for 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.
3. preparation method according to claim 2, it is characterized in that, described surface-active macromonomer, methacrylic acid, vinylformic acid, one in methylene-succinic acid and maleic anhydride, APEG, HPEG, a kind of and acrylamide in VPEG and TPEG and a kind of mol ratio in 2-acrylamide-2-methyl propane sulfonic are described surface-active macromonomer: methacrylic acid, vinylformic acid, one in methylene-succinic acid and maleic anhydride: APEG, HPEG, one in VPEG and TPEG: one=1.0 ~ 3.0:1 ~ 6.0:1:0.2 ~ 6.0 in acrylamide and 2-acrylamide-2-methyl propane sulfonic.
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 a kind of and acrylamide in APEG, HPEG, VPEG and TPEG and a kind of total mole number in 2-acrylamide-2-methyl propane sulfonic.
5. preparation method according to claim 2, is characterized in that, the time for adding of described initiator is 2 ~ 3h; Described soaking time is 2 ~ 4h.
6. preparation method according to claim 2, is characterized in that, the mass concentration of described sodium hydroxide solution is 30%; Described initiator is the one in Potassium Persulphate, ammonium persulphate, hydrogen peroxide 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, HPEG, VPEG and TPEG and a kind of total mole number in 2-acrylamide-2-methyl propane sulfonic.
7. preparation method according to claim 2, is characterized in that, described cation quaternary ammonium salt PEO surface-active macromonomer is prepared from by following methods:
(1) by the one in vinyl carbinol, isobutene alcohol, 4-hydroxy butyl vinyl ether and prenol, one in the mixture of oxyethane and oxyethane and propylene oxide, mix with epoxyhalopropane, add catalyzer, react 2 ~ 10 hours under temperature is 80 ~ 150 DEG C of conditions, obtain active intermediate;
(2) quarternary ammonium salt compound is mixed with stopper, slowly add the active intermediate that step (1) synthesizes and react 1 ~ 10h under temperature is 10 ~ 80 DEG C of conditions, obtain described surface-active macromonomer;
Described quarternary ammonium salt compound is N (R
2r
3r
4), wherein R
2, R
3and R
4be alone C respectively
1-3alkyl.
8. preparation method according to claim 7, it is characterized in that, one in step (1) described in described step (1) in vinyl carbinol, isobutene alcohol, 4-hydroxy butyl vinyl ether and prenol, one in the mixture of oxyethane and oxyethane and propylene oxide is the one in vinyl carbinol, isobutene alcohol, 4-hydroxy butyl vinyl ether and prenol with the mol ratio of epoxyhalopropane: the one in the mixture of oxyethane and oxyethane and propylene oxide: epoxyhalopropane=1:5 ~ 250:1 ~ 150.
9. preparation method according to claim 7, is characterized in that, in described step (2), the mol ratio of quarternary ammonium salt compound and active intermediate is 0.2:1 ~ 2:1.
10. preparation method according to claim 7, is characterized in that, in described step (1), catalyzer is sodium hydride or sodium; Stopper is Resorcinol or to methyl ether phenol, the consumption of described stopper is 0.02% ~ 0.08% of described active intermediate mole number in described step (2).
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