CN106749959A - A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof - Google Patents
A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The present invention relates to a kind of Early-strength polycarboxylate superplasticizer and preparation method thereof; acylation reaction is carried out using maleic anhydride and organic amine and obtains maleic acid mono amide monomer; again by the monomer and APEO polymeric monomer, unitary unsaturated carboxylic acid and its derivative, under initiator, chain-transferring agent effect carrying out copolyreaction obtains.The polycarboxylate water-reducer can effectively improve the early strength of concrete, and the common commercially available high early strength poly-carboxylic water reducer of 12h and 24h glue sand compressive strength rate is respectively increased 18% and more than 12%.
Description
Technical field
The present invention relates to a kind of concrete admixture, and in particular to a kind of Early-strength polycarboxylate superplasticizer and its preparation side
Method.
Background technology
Early-strength water reducer can promote the development of early age strength of concrete, shorten the concrete steam-cured time and even exempt steam-cured
Link, and then production efficiency, saving energy consumption are greatly improved, with significant economic and social benefit.
To improve polycarboxylate water-reducer morning epistasis energy, mainly change by polycarboxylate water-reducer molecule structure at present
Property, the polymeric monomer of overlength side chain is such as prepared, unsaturated acyl amine monomer is introduced in main chain or is compounded other organic or inorganic components.
Though the above method can to a certain extent improve the early epistasis energy of polycarboxylate water-reducer, certain deficiency is there is also.Research table
Bright, polycarboxylate water-reducer side chain is more long, and it is to tricalcium aluminate (C3) and tricalcium silicate (C A3S aquation inhibitory action) is smaller, more
Be conducive to the raising of early age strength of concrete.But the polyether lateral chain being made up of polyoxyethylene ether (EO), if largely existed
Excessive bubble can be introduced in concrete, concrete 's air-containing can be macroscopically improved, strength development is influenceed.Meanwhile, with polyethers
The increase of molecular weight, its polymerization activity reduction, causes reaction conversion ratio to decline；And in polycarboxylate water-reducer building-up process
Introducing the unsaturated acyl amine monomers such as acrylamide, AMPS has certain early stage enhancing effect, but primarily focuses on raising 1d, 3d
The strength character of age, it is impossible to which meet some early strong demands (within 24h) higher applies needs.
It is conventional preparation Early-strength polycarboxylate superplasticizer using polycarboxylate water-reducer and inorganic salts or organic alcohol amine compounding
Method.Although common inorganic salts such as villaumite, nitrate or sulfate can to a certain extent improve early age strength of concrete,
But can there is potential negative effect to concrete durability.And the organic early strength agent consumption of alcamines is few, effect is obvious, but to mixing
Amount is sensitive, and volume is too high will not only to improve early strength, and reverse effect is had on the contrary.
The content of the invention
The technical problems to be solved by the invention are directed to the deficiency of above-mentioned prior art presence and provide a kind of early-strength
Polycarboxylate water-reducer and preparation method thereof, effectively improves the 12h and the concrete strength of age earlier of concrete, without appointing
What inorganic salts influential on concrete durability, safety is easy-to-use.
The present invention is to solve the problems, such as that used technical scheme set forth above is：
A kind of Early-strength polycarboxylate superplasticizer, as shown in formula 1~4, wherein a is between 53~112 to its molecular structural formula
Integer, b, d, e are the integer more than 0, and c is the integer more than or equal to 0, R1It is H or CH3, R2It is H or CH3, R3For H or K,
Na, Ca, Mg, R4It is the alkyl of n-hexyl, cyclohexyl, isobutyl group, phenyl, benzyl equimolecular quantity below 1000.Preferably, a
It is the integer between 53~112, b is the integer between 11~33, d is that integer between 27~208, e are between 2~190
Integer, c is the integer less than 9.
By such scheme, the molecular weight of Early-strength polycarboxylate superplasticizer of the present invention is in 40000~100000.
Above-mentioned Early-strength polycarboxylate superplasticizer, its raw material mainly includes following components：APEO, unitary unsaturation carboxylic
Acid and its derivative, maleic acid mono amide, and initiator, chain-transferring agent.
Further, each raw material components consumption is by mass percentage 70~80wt% of APEO, unitary
5~15wt% of unsaturated carboxylic acid and its derivative, 5~25wt% of maleic acid mono amide, three's mass percent sum is
100%；Initiator account for APEO, unitary unsaturated carboxylic acid and its derivative, maleic acid mono amide gross mass 0.1~
5wt%, chain-transferring agent accounts for APEO, unitary unsaturated carboxylic acid and its derivative, the 0.05 of maleic acid mono amide gross mass
~2wt%.
The preparation method of above-mentioned Early-strength polycarboxylate superplasticizer is：By APEO, unitary unsaturated carboxylic acid and its spread out
Biological, maleic acid mono amide, under initiator, chain-transferring agent effect, in 20~90 DEG C of the aqueous solution copolyreaction 1~
3.5h, then adds alkali to be neutralized to pH 7~8, prepares Early-strength polycarboxylate superplasticizer.
Further, the preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, specifically the step of be：In inert atmosphere
Under, by water, monomer APEO, monomer unitary unsaturated carboxylic acid and its derivative Hybrid Heating and stirring；Treat monomer polyoxy
After the dissolving of vinethene, monomer unitary unsaturated carboxylic acid and its derivative, when being warmed up to 20~90 DEG C, maleic acid is added dropwise simultaneously respectively
The aqueous solution of the aqueous solution, initiator and chain-transferring agent of monoamides, after the aqueous solution completion of dropping of maleic acid mono amide, will be surplus
Remaining initiator and the aqueous solution of the chain-transferring agent completion of dropping in 0.5~2h, 1~3h of insulated and stirred after completion of dropping；Then
Cooling plus alkali are neutralized to pH between 7~8, obtain Early-strength polycarboxylate superplasticizer.
In such scheme, the solid content standard according to required Early-strength polycarboxylate superplasticizer, it is determined that in early-strength polycarboxylic acids
Amount of water in water reducer preparation method.Preferably, the solid content of described Early-strength polycarboxylate superplasticizer is 30~60wt%.
In such scheme, the chain-transferring agent is methylpropene sodium sulfonate, ALS, TGA, sulfydryl second
In alcohol, 2- sulfydryl propanethiols, 3- mercaprols, 3- mercaptopropionic acids, 2- dimercaptosuccinic acids etc. one or more in any proportion
Mixture.
In such scheme, described initiator may be selected from ammonium persulfate, potassium peroxydisulfate, sodium formaldehyde sulfoxylate, ascorbic acid, sulfurous acid
One or more mixture in any proportion in hydrogen sodium, sodium sulfite, hydrogen peroxide etc..
In such scheme, the polyoxyethylene ether is 4- hydroxy butyl vinyl ethers APEO (VPEG), iso-amylene
One kind in alcohol APEO (TPEG), isobutene alcohol APEO (HPEG), allyl alcohol polyethenoxy ether (APEG) etc.
Or several mixtures in any proportion.Wherein, VPEG, TPEG, HPEG, APEG molecular weight are preferably between 2400~5000.
In such scheme, described unitary unsaturated carboxylic acid and its derivative be acrylic acid, methacrylic acid and they
One or several mixtures in any proportion in monovalence alkali metal salt, divalence alkali metal salt, ammonium salt etc..
In such scheme, described maleic acid mono amide molecular structural formula is as shown in Equation 5, wherein R4It is alkyl, including just
The mix-configuration of one or several structures in hexyl, cyclohexyl, isobutyl group, phenyl, benzyl etc..
In such scheme, the preparation method of the maleic acid mono amide is：Under an inert atmosphere：By maleic anhydride and organic
Amine (H2N-R4) monomer is according to 1:The amount ratio of 1 material, is dissolved in inert organic solvents, adds catalyst, 30~60 DEG C of stirrings
After 1~5h of backflow, vacuum distillation removes organic solvent, obtains maleic acid mono amide.Its reaction equation is as follows：
In above-mentioned maleic acid mono amide building-up process, described organic amine (H2N-R4) it is n-hexylamine, cyclohexylamine, isobutyl group
The unary primary amine of amine, aniline, benzylamine equimolecular quantity below 1000.
In above-mentioned maleic acid mono amide building-up process, the catalyst is boric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, chlorination
The mixture of one or more in hydrogen, diamino-pyridine (DMAP) etc..Preferably, catalyst amount account for maleic anhydride with it is organic
0.01~0.1wt% of amine gross mass.
In above-mentioned maleic acid mono amide building-up process, the organic solvent is DMF (DMF), toluene, four
In chlorination carbon, n-hexane, dimethyl sulfoxide (DMSO) (DMSO), ethyl acetate, dichloromethane, tetrahydrofuran etc. one or more by appoint
The mixture of meaning ratio.
In above-mentioned maleic acid mono amide building-up process, maleic anhydride and organic amine shared mass percent in organic solvent
Concentration is preferably 30~70wt%.
The maleic acid mono amide monomer that the present invention is used, it is with polyoxyethylene ether monomer and unitary unsaturated carboxylic acid and its spreads out
Biomonomer is polymerized, and obtains the polycarboxylate superplasticizer mother liquor with early epistasis energy.Wherein, maleic anhydride is used as carrier, first by it
Acylation reaction is carried out with organic amine, the maleic acid mono amide with early epistasis energy is obtained, existing maleic anhydride compatibility is good
Characteristic has the function of promoting hydrated cementitious again.
Compared with prior art, beneficial effects of the present invention：
1st, tradition early-strength water reducer lays particular emphasis on the intensity for improving concrete 1d, 3d age, the early-strength that the present invention is provided
Polycarboxylate water-reducer, it is possible to increase the concrete strength of 12h and earlier age, 12h and 24h glue sand compressive strength rates are commonly commercially available
High early strength poly-carboxylic water reducer is respectively increased 18% and more than 12%
2nd, the polycarboxylate water-reducer of preparation provided by the present invention is without any nothing influential on concrete durability
Machine salt, safety is easy-to-use.
3rd, it is early strong monomer that conventional method uses the polyethers of overlength side chain, and polymerization activity is relatively low, easily causes concrete and draws
Gas, and the maleic acid mono amide monomer that the present invention is used, with reactivity higher, do not result in concrete bleed.
Specific embodiment
In order to production method of the present invention is better described, the present invention is further described below by instantiation,
But the present invention includes and non-is only limitted to following examples.
In following embodiments, molecular weight detection equipment is：Gel permeation chromatography (GPC)；The molecular weight distribution determination of sample
Using Waters2414 chromatographic systems, wherein chromatographic column is that the U.S. matches point (Sepax) company Nanofilm SEC-150, using poly-
Acrylic acid is standard specimen, 30 DEG C of column temperature, and detector is UV-detector, and using PBS as mobile phase, sample size is
50 μ L, flow velocity is 1mL/min.
Embodiment 1
A kind of Early-strength polycarboxylate superplasticizer, as shown in Equation 7, wherein a is that 53~55, b is 14~16 to its molecular structural formula,
D is that 94~96, e is that 21~23, c is 2~4, and a, b, c, d are integer；R1It is CH3, R2It is H, R3It is H, R4It is n-hexyl.GPC
Test mean molecule quantity is 45000 or so.
The preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, specific step is：
(1) preparation method of maleic acid mono amide is：Under an inert atmosphere, n-hexylamine and maleic anhydride are put into reactor
In, solvent DMF and catalyst benzene sulfonic acid are added, n-hexylamine is 40wt% with the mass concentration of maleic anhydride total amount, in stirring
During be slowly warmed up to 40 DEG C, be stirred at reflux 2h, vacuum distillation removes solvent DMF and obtains maleic acid mono amide (N- n-hexyls
Maleic acid mono amide).Wherein, maleic anhydride and the amount ratio of n-hexylamine material are 1:1, catalyst benzene sulfonic acid consumption is maleic anhydride
With the 0.01% of n-hexylamine gross mass.Preparation process key reaction equation is as follows：
Be (2) 75wt% according to monomer APEO TPEG, monomeric acrylic, maleic acid mono amide mass ratio,
15wt%, 10wt% get the raw materials ready；The amount of getting the raw materials ready of potassium peroxydisulfate (initiator) by mass for monomer TPEG, monomeric acrylic, N- just
The 0.5wt% of hexyl maleic acid mono amide gross mass；The amount of getting the raw materials ready of methylpropene sodium sulfonate (chain-transferring agent) is list by mass
Body TPEG, monomeric acrylic, maleic acid mono amide gross mass are 1wt%；
The aqueous solution of related raw material is prepared, the mass concentration of the maleic acid mono amide aqueous solution is 40wt%, potassium peroxydisulfate water
Concentration of polymer solution is 10wt%, and TGA aqueous solution mass concentration is 10wt%, and above dissolving water used is deionization
Water；
(3) under an inert atmosphere, deionized water, monomer APEO, monomeric acrylic are put into successively to reactor simultaneously
Heating stirring, it is to be dissolved uniform and well mixed after when being warming up to 50 DEG C, respectively while the maleic acid mono amide c1 aqueous solution, over cure
Sour aqueous solutions of potassium and the TGA aqueous solution；After after maleic acid mono amide c1 aqueous solution completion of dropping, by remaining potassium peroxydisulfate
With the TGA aqueous solution in 2h completion of dropping, drip rear keeping temperature stirring 2h；Then plus alkali be neutralized to pH7~8 it
Between, obtain Early-strength polycarboxylate superplasticizer, quality solid content 40wt%, marked as A1.Reaction equation is as follows：
Note：The amount of the getting the raw materials ready m of deionized water is monomer APEO, monomeric acrylic, maleic acid mono amide, TGA
1.5 times of the gross mass M of (chain-transferring agent), potassium peroxydisulfate (initiator) and alkali, i.e., prepared high performance water reducing agent of polyocarboxy acid
Solid content is M/ (m+M), i.e., the solid content of the Early-strength polycarboxylate superplasticizer aqueous solution is 40wt% in the present embodiment.
Embodiment 2
Early-strength polycarboxylate superplasticizer of the present invention, as shown in Equation 10, wherein a is its molecular structural formula for 73~76, b
11~13, d be 123~125, e for 45~47, c be 0, a, b, d are integer；R2It is H, R3It is H, R4It is cyclohexyl.GPC is tested
Mean molecule quantity is 60000 or so.
The preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, specific step is：
(1) preparation method of maleic acid mono amide is：Under an inert atmosphere, cyclohexylamine and maleic anhydride are put into reactor
In, solvent DMF and catalyst p-methyl benzenesulfonic acid are added, cyclohexylamine is 50wt% with the mass concentration of maleic anhydride total amount,
25 DEG C are slowly warmed up in whipping process, 3.5h is stirred at reflux, vacuum distillation removes solvent DMF and obtains maleic acid mono amide
(N- cyclohexyl maleic acid mono amide).Wherein, maleic anhydride and the amount ratio of cyclohexylamine material are 1:1, catalyst is to methylbenzene sulphur
Sour consumption is the 0.012% of maleic anhydride and cyclohexylamine gross mass.Preparation process key reaction equation is as follows：
Be (2) 70wt% according to monomer APEO APEG, monomeric acrylic, maleic acid mono amide mass ratio,
15wt%, 15wt% get the raw materials ready；The amount of getting the raw materials ready of potassium peroxydisulfate (initiator) is monomer APEO APEG, monomer third by mass
The 1wt% of olefin(e) acid, maleic acid mono amide gross mass；The amount of getting the raw materials ready of TGA (chain-transferring agent) is monomer polyoxy second by mass
Alkene ether APEG, monomeric acrylic, maleic acid mono amide gross mass are 0.3wt%, and reaction equation is as follows：
The aqueous solution of related raw material is prepared, the mass concentration of maleic acid mono amide solution is 40wt%, potassium persulfate solution
Mass concentration is 10wt%, and mercaptoacetic acid solution mass concentration is 10wt%, and above dissolving water used is deionized water；
(3) under an inert atmosphere, deionized water, monomer APEO, monomeric acrylic are put into successively to reactor simultaneously
Heating stirring, it is to be dissolved uniform and well mixed after when being warming up to 50 DEG C, respectively while maleic acid mono amide solution, potassium peroxydisulfate
Solution and mercaptoacetic acid solution；It is after after maleic acid mono amide solution completion of dropping, remaining potassium peroxydisulfate and TGA is molten
Liquid completion of dropping in 2h, drips rear keeping temperature stirring 3h；Finally plus alkali is neutralized between pH 7~8, early-strength is obtained
Polycarboxylate water-reducer, quality solid content 45wt%, marked as A2.Reaction equation is as follows：
Embodiment 3
Early-strength polycarboxylate superplasticizer of the present invention, as shown in Equation 13, wherein a is 110~112, b to its molecular structural formula
For 12~14, d be 50~52, e for 89~91, c be 0, a, b, d are integer；R2It is CH3, R3It is H, R4It is phenyl.GPC is tested
Mean molecule quantity is 86000 or so.
The preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, specific step is：
(1) preparation method of maleic acid mono amide is：Under an inert atmosphere, aniline and maleic anhydride are put into reactor
In, solvent toluene and catalyst DMAP are added, aniline is 60wt% with the mass concentration of maleic anhydride total amount, in whipping process
In be slowly warmed up to 60 DEG C, be stirred at reflux 5h, vacuum distillation removes solvent toluene and obtains maleic acid mono amide (N- phenyl maleic acids
Monoamides).Wherein, maleic anhydride and the amount ratio of aniline material are 1:1, catalyst DMAP consumption are maleic anhydride and the total matter of aniline
The 0.05% of amount.Reaction equation is as follows：
Be (2) 75wt% according to monomer APEO VPEG, monomer methacrylic acid, maleic acid mono amide mass ratio,
5wt%, 20wt% get the raw materials ready；The amount of getting the raw materials ready of ammonium persulfate (initiator) is monomer APEO VPEG, monomer first by mass
The 0.5wt% of base acrylic acid, maleic acid mono amide gross mass；The amount of getting the raw materials ready of mercaptoethanol (chain-transferring agent) is monomer by mass
APEO VPEG, monomer methacrylic acid, maleic acid mono amide c3 gross masses are 0.2wt%；
The aqueous solution of related raw material is prepared, the mass concentration of maleic acid mono amide solution is 50wt%, potassium persulfate solution
Mass concentration is 10wt%, and mercaptoacetic acid solution mass concentration is 10wt%, and above dissolving water used is deionized water；
(3) under an inert atmosphere, deionized water, monomer APEO, monomer metering system are put into successively to reactor
Acid and heating stirring, it is to be dissolved uniform and well mixed after when being warming up to 50 DEG C, respectively simultaneously dropwise addition maleic acid mono amide solution,
Potassium persulfate solution and mercaptoacetic acid solution；After after maleic acid mono amide solution completion of dropping, by remaining potassium peroxydisulfate and mercapto
Guanidine-acetic acid solution completion of dropping in 2h, drips rear keeping temperature stirring 5h；Finally plus alkali is neutralized between pH 7~8, obtain
To Early-strength polycarboxylate superplasticizer, quality solid content 40wt%, marked as A3.Reaction equation is as follows：
Embodiment 4
Early-strength polycarboxylate superplasticizer of the present invention, as shown in Equation 16, wherein a is its molecular structural formula for 53~55, b
16~18, d is that 33~35, e is that 70~72, c is 0, and a, b, d are integer；R2It is CH3, R3It is H, R4It is benzyl.GPC tests are flat
Average molecular weight is 58000 or so.
The preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, specific step is：
(1) preparation method of maleic acid mono amide is：Under an inert atmosphere, benzylamine and maleic anhydride are put into reactor
In, solvent toluene and catalyst boric acid are added, benzylamine is 50wt% with the mass concentration of maleic anhydride total amount, in whipping process
In be slowly warmed up to 60 DEG C, be stirred at reflux 5h, vacuum distillation removes solvent toluene and obtains maleic acid mono amide (N- benzyls Malaysia
Sour monoamides).Wherein, maleic anhydride and the amount ratio of benzylamine material are 1:1, catalyst boric acid consumption is that maleic anhydride is total with benzylamine
The 0.1% of quality.Reaction equation is as follows：
Be (2) 70wt% according to monomer APEO HPEG, monomer methacrylic acid, maleic acid mono amide mass ratio,
5wt%, 25wt% get the raw materials ready；The amount of getting the raw materials ready of ammonium persulfate (initiator) is monomer APEO HPEG, monomer first by mass
The 0.3wt% of base acrylic acid, maleic acid mono amide gross mass；The amount of getting the raw materials ready of mercaptoethanol (chain-transferring agent) is monomer by mass
APEO HPEG, monomer methacrylic acid, maleic acid mono amide gross mass are 0.4wt%；
The aqueous solution of related raw material is prepared, the mass concentration of maleic acid mono amide solution is 50wt%, potassium persulfate solution
Mass concentration is 10wt%, and mercaptoacetic acid solution mass concentration is 10wt%, and above dissolving water used is deionized water.
(3) under an inert atmosphere, deionized water, monomer APEO, monomer metering system are put into successively to reactor
Acid and heating stirring, it is to be dissolved uniform and well mixed after when being warming up to 50 DEG C, respectively while maleic acid mono amide solution, over cure
Sour potassium solution and mercaptoacetic acid solution；After after maleic acid mono amide solution completion of dropping, by remaining potassium peroxydisulfate and sulfydryl second
Acid solution completion of dropping in 2h, drips rear keeping temperature stirring 5h；Finally plus alkali is neutralized between pH 7~8, morning is obtained
Strong type polycarboxylate water-reducer, quality solid content 50wt%, marked as A4.Reaction equation is as follows：
Cement mortar contrast test
Early-strength polycarboxylate superplasticizer (i.e. A1, A2, A3, A4) prepared by embodiment 1-4 is (with reference to national standard
GB17671-1999 strength of cement mortar detection) is carried out respectively.During detection：Testing cement consumption be 450g, normal sand 1350g,
The effective solid masses for adding water reducer is 0.9g, and water-cement ratio is 0.35.To mix water reducer glue sand mixture stir after,
Divide two-layer to load 40mm × 40mm × 160mm prism die trials, curing box is put into after vibration compacting, in temperature (20 ± 1) DEG C, humidity
Maintenance is to test age under >=90% environment, then glue sand test block after the demoulding is carried out into intensity survey by GB GB17671-1999 requirements
Examination.And choose the commercially available common Early-strength polycarboxylate superplasticizer of different solid contents as control, numbering be respectively B1, B2, B3,
B4.Cement mortar early strength testing result is as shown in table 1.
The Early-strength polycarboxylate superplasticizer of table 1 and commercially available prod performance comparison
As can be seen from Table 1, Early-strength polycarboxylate superplasticizer product of the present invention is than common commercially available early-strength polycarboxylic acids diminishing
The 12h glue sand compression strength of agent product is at least high by more than 18%, and (A3 groups are than B1 group 12h intensity 18%) high；24h glue sand pressure resistances
Degree is at least high by more than 12%, and (A1 groups are than B4 group 24h intensity 12%) high；72h cement mortar strengths are at least high by more than 5%, and (A1 groups are than B1 group
Intensity is high 5.7%).
Above experimental data explanation；By the use of maleic anhydride as carrier, by itself and monoamine amine molecule reaction generation acyl
Amine, then be polymerized with polyethers and acrylic monomer, can obtain Early-strength polycarboxylate superplasticizer.The poly- carboxylic that the method synthesis is obtained
Sour water reducer can make glue sand 12h and 24h compression strength be respectively increased 18% He compared with common commercially available high early strength poly-carboxylic water reducer
More than 12%.Its principle is as follows：Organic amine molecule can photocatalytic cements aquation, quickening hyrate throughput rate；Acrylic amide
Organic amine is used to synthesis Early-strength polycarboxylate superplasticizer by wide coverage.But many morning epistasis can preferable small point of organic amine
Son, due to poor compatibility or the reason such as molecular structure is special, it is impossible to be copolymerized instead with polyether monomer and acrylic monomer
Should.The present invention can make some script dissolubilities difference or the organic amide monomer without double bond structure by the use of maleic anhydride as carrier,
Be converted into compatibility good and be easy to the structure of copolymerization, with this further reaction can obtain early epistasis can preferable polycarboxylic acids diminishing
Agent.
The above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art
Say, without departing from the concept of the premise of the invention, can also make some modifications and variations, these belong to of the invention
Protection domain.
Claims (10)
1. a kind of Early-strength polycarboxylate superplasticizer, it is characterised in that its molecular structural formula as shown in formula 1~4, wherein a is 53~
Integer between 112, b, d, e are the integer more than 0, and c is the integer more than or equal to 0, R1It is H or CH3, R2It is H or CH3,
R3It is H or K, Na, Ca, Mg, R4It is the alkyl of n-hexyl, cyclohexyl, isobutyl group, phenyl, benzyl equimolecular quantity below 1000.
2. a kind of preparation method of Early-strength polycarboxylate superplasticizer, it is characterised in that APEO, unitary unsaturated carboxylic acid and
Its derivative and maleic acid mono amide, under initiator, chain-transferring agent effect, the copolyreaction 1 in 20~90 DEG C of the aqueous solution
~3.5h, then adds alkali to be neutralized to pH 7~8, prepares Early-strength polycarboxylate superplasticizer.
3. a kind of preparation method of Early-strength polycarboxylate superplasticizer according to claim 2, it is characterised in that each raw material group
Point consumption is by mass percentage 70~80wt% of APEO, 5~15wt% of unitary unsaturated carboxylic acid and its derivative,
5~25wt% of maleic acid mono amide, three's mass percent sum is 100%；It is unsaturated that initiator accounts for APEO, unitary
Carboxylic acid and its derivative, 0.1~5wt% of maleic acid mono amide gross mass, it is unsaturated that chain-transferring agent accounts for APEO, unitary
Carboxylic acid and its derivative, 0.05~2wt% of maleic acid mono amide gross mass.
4. a kind of preparation method of Early-strength polycarboxylate superplasticizer according to claim 2, it is characterised in that specific step
Suddenly it is：Under an inert atmosphere, by water, monomer APEO, monomer unitary unsaturated carboxylic acid and its derivative Hybrid Heating and
Stirring；After after the dissolving of monomer APEO, monomer unitary unsaturated carboxylic acid and its derivative, when being warmed up to 20~90 DEG C, divide
The aqueous solution of the aqueous solution, initiator and chain-transferring agent of maleic acid mono amide is not added dropwise not simultaneously, in the water-soluble of maleic acid mono amide
After liquid completion of dropping, by the aqueous solution of remaining initiator and chain-transferring agent in 0.5~2h completion of dropping, after completion of dropping protect
1~3h of temperature stirring；Then cooling plus alkali are neutralized to pH between 7~8, obtain Early-strength polycarboxylate superplasticizer.
5. a kind of preparation method of the Early-strength polycarboxylate superplasticizer according to Claims 2 or 3 or 4, it is characterised in that institute
Polyoxyethylene ether is stated for 4- hydroxy butyl vinyl ethers APEO, isopentenol polyoxyethylene ether, isobutene alcohol polyoxy second
One or more mixtures in any proportion in alkene ether, allyl alcohol polyethenoxy ether；The polyoxyethylene ether molecular weight
Between 2400~5000.
6. a kind of preparation method of the Early-strength polycarboxylate superplasticizer according to Claims 2 or 3 or 4, it is characterised in that institute
The unitary unsaturated carboxylic acid and its derivative stated are acrylic acid, methacrylic acid and their monovalence alkali metal salt, diatomic base gold
One or several mixtures in any proportion in category salt, ammonium salt etc..
7. a kind of preparation method of the Early-strength polycarboxylate superplasticizer according to Claims 2 or 3 or 4, it is characterised in that institute
The maleic acid mono amide molecular structural formula stated is as shown in Equation 5, wherein R4It is n-hexyl, cyclohexyl, isobutyl group, phenyl, benzyl etc.
In one or several structures mix-configuration.
8. a kind of preparation method of Early-strength polycarboxylate superplasticizer according to claim 7, it is characterised in that the Malaysia
The preparation method of sour monoamides is：Under an inert atmosphere：By maleic anhydride and organic amide monomer according to 1:The amount ratio of 1 material,
It is dissolved in inert organic solvents, adds catalyst, after 30~60 DEG C are stirred at reflux 1~5h, vacuum distillation removes organic solvent,
Obtain maleic acid mono amide.
9. the preparation method of a kind of Early-strength polycarboxylate superplasticizer according to claim 7, it is characterised in that described has
Machine amine is unary primary amine of the molecular weight below 1000；The catalyst be boric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, hydrogen chloride,
The mixture of one or more in diamino-pyridine.
10. a kind of preparation method of Early-strength polycarboxylate superplasticizer according to claim 8, it is characterised in that the Malaysia
Shared mass percent concentration is altogether 30~70wt% in organic solvent for acid anhydrides and organic amine；Catalyst amount accounts for maleic anhydride
With 0.01~0.1wt% of organic amine gross mass.
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| CN107235650A (en) * | 2017-07-03 | 2017-10-10 | 中建西部建设西南有限公司 | Strong additive of a kind of water nano compound morning and preparation method thereof |
| CN107686540A (en) * | 2017-10-23 | 2018-02-13 | 南京建高新材料科技有限公司 | A kind of preparation method of Early-strength polycarboxylate superplasticizer |
| CN108516866A (en) * | 2018-04-20 | 2018-09-11 | 安徽瑞和新材料有限公司 | The preparation method of curing agent in a kind of modified high hydroscopic resin |
| CN108864379A (en) * | 2018-08-01 | 2018-11-23 | 武汉奥克化学有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN112708074A (en) * | 2020-12-29 | 2021-04-27 | 科之杰新材料集团浙江有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
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| CN113637124A (en) * | 2021-09-07 | 2021-11-12 | 科之杰新材料集团浙江有限公司 | Early-strength water reducing agent and preparation method thereof |
| CN118359771A (en) * | 2024-06-20 | 2024-07-19 | 安徽海螺材料科技股份有限公司 | Solid polycarboxylate superplasticizer and preparation method and application thereof |
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