CN105732911B - The preparation method and application of viscosity reduction type polycarboxylate water-reducer - Google Patents
The preparation method and application of viscosity reduction type polycarboxylate water-reducer Download PDFInfo
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- CN105732911B CN105732911B CN201610027918.4A CN201610027918A CN105732911B CN 105732911 B CN105732911 B CN 105732911B CN 201610027918 A CN201610027918 A CN 201610027918A CN 105732911 B CN105732911 B CN 105732911B
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- 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
Abstract
The invention provides a kind of preparation method and applications of viscosity reduction type polycarboxylate water-reducer, the viscosity reduction type polycarboxylate water-reducer is on the premise of high diminishing, high-thin arch dam is ensured, the viscosity of concrete can also be greatly reduced, and the preparation method has the advantages that technique is simple, cost is low, pollution is small.The preparation method is that N dialkylamines are in molar ratio (2.5~6.5) by specific unsaturated acid monomer, specific unsaturated polyether polymeric monomer and N (4 vinyl benzyl) N:1:(0.05~0.2) carry out free radicals copolymerization reaction and obtain viscosity reduction type polycarboxylate water-reducer.
Description
Technical field
The present invention relates to a kind of preparation method and application of viscosity reduction type polycarboxylate water-reducer, category concrete admixture technology neck
Domain.
Background technology
At present, concrete is still the material that architectural engineering is main, most large.Sent out with the high speed of China's infrastructure
Exhibition, architectural engineering to maximization, high stratification, complicate development, to the performance requirements of required concrete material also increasingly
It is high.Practice have shown that chemical admixture is added in concrete can be substantially improved its service behaviour, in fact, additive has turned into
The 5th kind of important constituent in modern concrete in addition to cement, sand, stone, water.Water reducer (also referred to as " cement point
Powder ") it is a kind of concrete admixture studied and be most widely used at present, in the case where concrete workability is constant,
Mixing water reducer can be with effectively save cement consumption, reduction water consumption, raising concrete strength.Polycarboxylic acids is as latest generation
High performance concrete water reducer, there is volume is low, slump retaining is good, molecular structure Modulatory character is strong, production technology is green etc.
Outstanding advantages.Polycarboxylate water-reducer is a kind of comb polymer molecule polymer, and it is by main chain and polyether lateral chain rich in hydroxy-acid group
Composition, hydroxy-acid group on main chain can be with oriented attachments on the cement of positively charged or the surface of cement-hydrate, and polyethers side
Chain stretches to form hydrated sheath to provide steric repulsion to prevent water walk from gathering in the solution, therefore this structure imparts cement
Particle dispersiveness good in water.
High-strength concrete generally uses very low water-cement ratio to ensure higher intensity to apply in high building project,
But the reduction of water consumption can cause concrete viscosity to increase, flowing velocity is slack-off, and then influence being smoothed out for construction.Therefore,
A kind of water reducer of viscosity reduction type of market active demand, this water reducer will not only ensure water-reducing rate and slump retaining, also have obvious
Viscosity reduction function, to reduce the viscosity of high-strength concrete, improve service behaviour.Introduced in polycarboxylic acids building-up process and remove unsaturated acids
Third monomer beyond monomer and unsaturated polyether polymeric monomer can improve some service behaviours of water reducer by many works
Work is proved, such as the B of Chinese patent literature CN 102153711 disclose a kind of preparation side of the polycarboxylate water-reducer of retardation setting type
Method, i.e., maleic anhydride grafted cyclodextrin polymeric monomer is introduced into allyl sulphonic acid salt-acrylic compounds-metering system acid polyethylene glycol
In the polycarboxylate water-reducer molecule structure that monomethyl ether ester is formed, the new water reducer so obtained has well latent
Energy, micro- bleed performance and more preferable mobility, and properties of product are stable, cement adaptability is strong, compatibility is good；Chinese patent text
Offer the B of CN 102503226 and disclose a kind of preparation method of high collapse protection type polycarboxylate water-reducer, by acrylamide monomers and
(methyl) acrylic ester monomer is introduced into the main chain of polycarboxylic acids molecule as the auxiliary agent that collapses is protected, and gained water reducer has excellent guarantor
Collapse performance, it is ensured that concrete slump in 3 hours is not lost substantially, has wide applicability.At present, in the market is drawn
The polycarboxylate water-reducer product category for entering Third monomer has a lot, but principally falls into guarantor and collapse product, the viscosity reduction type polycarboxylic acids of urgent need
Water reducer product is but very rare, only a small amount of patent report this kind of product, for example, Chinese patent literature CN 104262550
A discloses a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, i.e., first by unsaturated acid anhydride and unsaturated primary amine in a constant temperature
The unsaturated primary amine class minor comonomer of the lower synthesis of degree, itself and the organic molecule containing epoxide group and halogen group then reacted to obtain
Quaternary ammonium salt unsaturated monomer, finally it is introduced into polycarboxylic acids molecular structure, obtains using this unsaturated quaternary ammonium salt class as Third monomer
The product arrived has reduction concrete viscosity, improves the good function such as slump-retaining, but this method has complex steps, original
Expect the shortcomings of cost is high, production process pollution is big；Chinese patent literature CN 100402457C disclose a kind of polycarboxylic acid concrete
Additive, by (methyl) alkyl acrylate monomer, specific PAG unsaturation polymeric monomer and unsaturated acid monomer
Prepared by free radicals copolymerization reaction, this method introduces the Third monomer alkyl acrylate with hydrophobic effect, gained production
Product have excellent cement dispersiveness, can reduce concrete yield stress and viscosity, but this method has production cost height, protected
The shortcomings of collapsing property is poor, viscosity reducing effect is small.
The content of the invention
Goal of the invention
It is an object of the present invention to provide a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, the poly- carboxylic of viscosity reduction type
Sour water reducer is on the premise of high diminishing, high-thin arch dam is ensured, moreover it is possible to the viscosity of concrete is greatly reduced, and this method has work
The advantages that skill is simple, cost is low, pollution is small.
It is a further object to provide application of the viscosity reduction type polycarboxylate water-reducer as cement dispersants.
Summary of the invention
Researcher of the present invention has found that water film thickness is straight caused by polycarboxylic acids Molecular Adsorption to cement particle surface through experiment
Connecing influences the viscosity of concrete, and the absorption conformation of polycarboxylic acids determines water film thickness, and the introducing of rigid radical can make conformation
More stretch, can improve water film thickness, therefore the present invention, by N- (4- vinyl benzyls)-N, N- dialkylamines are as Third monomer
It is introduced into the molecular structure of polycarboxylic acids, synthesizes a kind of viscosity reduction type polycarboxylate water-reducer.
In the first aspect of the present invention, there is provided a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, by unsaturated acids
Monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkylamines are in molar ratio (2.5~6.5):1:
(0.05~0.2) carry out free radicals copolymerization reaction and obtain, wherein：
Unsaturated acid monomer structural formula is such as shown in (I)：
Wherein, R1For-H or-COOH, R2For-H ,-CH3Or-CH2COOH；
Unsaturated polyether polymeric monomer structural formula is such as shown in (II)：
Wherein, R3For-H or-CH3, R4For-CH2- or-CH2CH2-, n=20~90；
N- (4- vinyl benzyls)-N, N- dialkylamines structural formula is such as shown in (III)：
Wherein, R5For C1~C6 alkyl.
The molecular weight requirement of viscosity reduction type polycarboxylate water-reducer of the present invention subtracts compared with comb shaped structure polycarboxylic acids in technology
The conventional molecular weight ranges of aqua, those skilled in the art can also combine and further determine that preferable molecular weight ranges through experiment.
The weight average molecular weight of viscosity reduction type polycarboxylate water-reducer of the present invention is preferably 10000~60000.
The unsaturated acid monomer works as R1For-COOH when, its can be used to form the alternative form of acid anhydrides with other-COOH.
This acid anhydrides alternative form can change into carboxylic acid during preparation process or use, therefore can be considered equivalent substitute.Preferably,
The unsaturated acid monomer is in acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid (or being substituted with maleic anhydride)
At least one；
Preferably, the unsaturated polyether polymeric monomer is weight average molecular weight MwThe poly- second of pi-allyl between 1000~4000
Glycol (R3=-H, R4=-CH2-), methacrylic polyethylene glycol (R3=-CH3, R4=-CH2-), isopentene group polyethylene glycol
(R3=-CH3, R4=-CH2CH2At least one of -).
Specifically, N- (4- the vinyl benzyls)-N, N- dialkylamines can be N- (4- vinyl benzyls)-N, N- bis-
Methylamine, N- (4- vinyl benzyls)-N, TMSDEA N diethylamine, N- (4- vinyl benzyls)-N, N- di-n-propylamines, N- (4- vinyl benzyls
Base)-N, N- dibutyl amine, N- (4- vinyl benzyls)-N, N- diamylamines, N- (4- vinyl benzyls)-N, N- dihexylamines are at least
It is a kind of.
At least one, you can be one of which, or the mixture of two or more arbitrary proportions.
Those skilled in the art can select according to monomer reactivity and the molecular weight of target product with reference to prior art
Specific free radicals copolymerization reaction condition.It is for instance possible to use water-based free radical copolymerization common in polycarboxylate water-reducer synthesis
Reaction.Further, water-based free radical copolyreaction of the present invention is preferably turned using oxidation-reduction initiator and water-soluble chain
Agent is moved, Oxidizing and Reducing Agents dosage is respectively that unsaturated acid monomer, unsaturated polyether are big in the oxidation-reduction initiator
Monomer and N- (4- vinyl benzyls)-N, the 1%~4% of N- dialkylamines integral molar quantity (hereinafter referred to as " monomer integral molar quantity ")
With 0.5%~2.0%；The dosage of water-soluble chain transfer agent is the 1%~5.5% of monomer integral molar quantity.It is furthermore preferred that the oxygen
Change-reduction initiator is hydrogen peroxide-ascorbic acid, hydrogen peroxide-ferrous sulfate, ammonium persulfate-ascorbic acid, ammonium persulfate-Asia
One kind in sodium sulphate, ammonium persulfate-sodium bisulfite or potassium peroxydisulfate-sodium sulfite combination, the chain-transferring agent is sulfydryl
Ethanol, TGA, mercaprol, mercaptopropionic acid or n- dodecyl mereaptan；The preparation method of the viscosity reduction type polycarboxylate water-reducer
Comprise the following steps：
1) it is unsaturated polyether polymeric monomer, N- (4- vinyl benzyls)-N, N- dialkylamine, oxidant and water is fully mixed
Close, under protective atmosphere, be warming up to reaction temperature；
2) it is made up of to mixed solution and dripping obtained by step 1) unsaturated acid monomer, reducing agent, chain-transferring agent and water
Dropwise addition solution, 2~4h of time for adding, after completion of dropwise addition, insulation reaction.
In order to form monomer polymer chain architecture arranged in a uniform (it has been generally acknowledged that such properties of product are more excellent) as far as possible,
Above-mentioned reactant addition manner is proposed with very much, i.e.,：The relatively low monomer of polymerization activity is disposable before starting with reaction to be added instead
Answer in container, the higher monomer of polymerization activity is slowly added dropwise at the reaction temperatures, and this is the usual means of this area.
Protective atmosphere can be N2Or inert protective gas, preferably N2, there is the advantages of economic, to be readily available.
Specific reaction temperature and insulation reaction time are selected according to monomer reactivity and initiator, such as upper
In the presence of stating preferable oxidation-reduction initiator, reaction temperature is preferably set as 30~60 DEG C, 1~3h of insulation reaction, is polymerize dense
Degree 40%~50%.The polymerization concentration refers to the mass percent concentration sum of all monomers in reaction mixture.
Gained viscosity reduction type polycarboxylate water-reducer has following structure formula：
Wherein, x, y, z represents the number of repeat unit of each repeat unit of random arrangement.
After copolyreaction terminates, the principal component that reaction product can be directly used as cement dispersants uses, and is more preferably into one
Step uses after being neutralized with alkaline matter, to strengthen the storage stability of product.This is techniques known.Basic species are of fine quality
Elect sodium hydroxide solution, ammoniacal liquor or ethylenediamine solution as (concentration can be determined according to the requirement of final product concentration).Alkalescence
The dosage of material is advisable using the pH value for adjusting reaction product as 6~8.After neutralization, contained carboxyl can part in said structure formula
Or it is completely converted into carboxylate.Due to neutralizing the molecular weight effects very little to the viscosity reduction type polycarboxylate water-reducer, the present invention is right
Ignored.
In another aspect of this invention, the viscosity reduction type polycarboxylate water-reducer answering as cement dispersants is additionally provided
With.
Its application process of viscosity reduction type polycarboxylate water-reducer of the present invention is identical with known cement dispersants, this area
Technical staff generally knows its application process.
Its volume of new polycarboxylic acid water reducer of the present invention is the 0.05%~0.3% of total binder materials, described to mix
It is mass percent to measure as pure solid volume, the percentage.Volume is too low to deteriorate its performance, volume is too high can cause through
Waste and performance in Ji can not improve.
New polycarboxylic acid water reducer of the present invention can with commercially available other water reducers, such as lignosulfonic acid salt diminishing
Agent, naphthalene sulfonic salt water reducer, polycarboxylate water-reducer etc. are used in mixed way, and can also add air entraining agent, retarder, early strength agent, swollen
Used after swollen dose, tackifier, economization agent and defoamer.
The present invention has advantages below compared with prior art：
(1) viscosity reduction type polycarboxylate water-reducer of the invention not only has the advantages that volume is low, water-reducing rate is high, slump retaining is strong,
High-strength concrete viscosity can be also effectively reduced, makes work progress simpler, laborsaving.
(2) simple production process of viscosity reduction type polycarboxylate water-reducer of the invention, pollution is small, cost is low.
Embodiment
The detailed preparation method of viscosity reduction type polycarboxylate water-reducer of the present invention given below, it is familiar its object is to allow
Person skilled in art can understand present disclosure and implement according to this, but these embodiments are in no way intended to limit the model of the present invention
Enclose, any equivalent change or modification in accordance with the spirit of the invention, should all be included within the scope of the present invention.
Starting monomer N- (4- vinyl benzyls)-N used in the present invention, N- dialkylamines are introduced by synthesis example first
Preparation method, its purity is by being equipped with the LC600 of Waters Xbridge C18 chromatographic columns (water generation Science and Technology Ltd.)
High performance liquid chromatograph (HPLC, LabTech Instrument Ltd.) is measured, mobile phase：4:1 methanol/water mixing is molten
Liquid, flow velocity：0.8mL/min, sample solution concentration：0.8%.Then viscosity reduction type polycarboxylic acids of the present invention is introduced by embodiment to subtract
The synthetic method of aqua, polymer molecular weight is using outfit TSK-GELSW (Dong Cao bio tech ltd) chromatographic column
MiniDAWN Tristar aqueous gels permeation chromatograph (GPC, Wyatt Technology) is measured, mobile phase：0.1M
The NaNO3 aqueous solution, flow velocity：1.0mL/min, sample solution concentration：0.5%.
Raw material p-chloromethyl styrene used in the present invention (>95%) Beijing Yi Nuokai companies, unsaturated polyether are purchased from
Polymeric monomer (double bond retention>90%) aqueous solution (concentration 60%) produces for Nanjing Bote Building Materials Co., Ltd., other raw materials
It is commercially available general analysis pure chemistry reagent.
N- (4- vinyl benzyls)-N, N- dialkylamine synthesis example：
Synthetic method reference literature Dan M, Su Y, Xiao X, et al.Macromolecules, 2013,46 (8):
3137-3146, p-chloromethyl styrene (1.0mol, 152.6g), dialkylamine are added into the 1L flasks equipped with agitator
(1.5mol, one kind in dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, diamylamine, dihexylamine), potassium carbonate 120g and solvent three
Chloromethanes 200mL, it is stirred liquid and is warming up to 50 DEG C, react 12h at this temperature.After reaction terminates, potassium carbonate is filtered to remove,
Revolving recovery chloroform and dialkylamine, obtain yellowish crude product, are finally evaporated under reduced pressure and obtain N- (the 4- ethene of colorless liquid
Base benzyl)-N, N- dialkylamines, yield is 82%~88%, and monomer purity is measured more than 97% by HPLC.
Embodiment 1：
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkyl group
The mol ratio of amine is 5.5:1:0.12, the dosage of oxidant, reducing agent and chain-transferring agent is respectively in oxidation-reduction initiator
1.0%, 0.5%, the 5.5% of monomer integral molar quantity.
60% allyl polyglycol (M is added into the 2L flasks equipped with agitatorw=1200, n=26) aqueous solution
480g, N- (4- vinyl benzyls)-N, TMSDEA N diethylamine 5.44g, 30% hydrogen peroxide 1.80g and water 100g, is passed through N2To remove
Oxygen in solution, be subsequently agitated for being warming up to 30 DEG C, at this temperature, be added dropwise by acrylic acid 95.04g, mercaptoethanol 6.82g,
The dropwise addition solution of ferrous sulfate 2.21g and water 220g compositions, time for adding 2h, is incubated 1h, finally with 35% after being added dropwise
Sodium hydroxide solution neutralization reaction liquid to pH value is 6~8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%, molecular weight
MwFor 10900.
Embodiment 2：
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkyl group
The mol ratio of amine is 4.5:1:0.09, the dosage of oxidant, reducing agent and chain-transferring agent is respectively in oxidation-reduction initiator
2.0%, 0.5%, the 2.85% of monomer integral molar quantity.
60% methacrylic polyethylene glycol (M is added into the 2L flasks equipped with agitatorw=1800, n=39) water
Solution 480g, N- (4- vinyl benzyls)-N, N- di-n-propylamines 3.12g, 30% hydrogen peroxide solution 2.03g and water 100g, is passed through N2
To remove the oxygen in solution, it is subsequently agitated for being warming up to 43 DEG C, at this temperature, is added dropwise by acrylic acid 46.08g and metering system
The dropwise addition solution that sour 6.88g, mercaptopropionic acid 2.70g, L-AA 0.79g and water 190g are formed, time for adding 3h, is dripped
1h is incubated after finishing, is finally 6~8 with the pH of 35% sodium hydroxide solution neutralization reaction liquid, obtains the viscosity reduction of solid content 40%
Type polycarboxylate water-reducer, molecular weight MwFor 24800.
Embodiment 3：
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkyl group
The mol ratio of amine is 2.5:1:0.05, the dosage of oxidant, reducing agent and chain-transferring agent is respectively in oxidation-reduction initiator
3.0%, 1.0%, the 2.5% of monomer integral molar quantity.
60% isopentene group polyethylene glycol (M is added into the 2L flasks equipped with agitatorw=2400, n=53) it is water-soluble
Liquid 480g, N- (4- vinyl benzyls)-N, N- dihexylamine 1.81g, ammonium persulfate 2.91g and water 100g, is passed through N2It is molten to remove
Oxygen in liquid, it is subsequently agitated for being warming up to 50 DEG C, at this temperature, is added dropwise by methacrylic acid 15.48g and maleic anhydride
The dropwise addition solution that 11.76g, TGA 0.98g, L-AA 0.75g and water 160g are formed, time for adding 3.5h, it is added dropwise
After be incubated 1h, finally with 35% sodium hydroxide solution neutralization reaction liquid pH be 6~8, obtain the drop of solid content 40%
Viscous type polycarboxylate water-reducer, molecular weight MwFor 30600.
Embodiment 4：
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkyl group
The mol ratio of amine is 4.75:1:0.18, the dosage difference of oxidant, reducing agent and chain-transferring agent in oxidation-reduction initiator
For the 3.5% of monomer integral molar quantity, 1.25%, 2.0%.
60% allyl polyglycol (M is added into the 2L flasks equipped with agitatorw=2400, n=53) aqueous solution
480g, N- (4- vinyl benzyls)-N, TMSDEA N diethylamine 4.08g, potassium peroxydisulfate 6.72g and water 100g, is passed through N2To remove solution
In oxygen, be subsequently agitated for being warming up to 55 DEG C, at this temperature, be added dropwise by acrylic acid 38.88g and itaconic acid 3.90g, sulfydryl third
Sour 1.51g, sodium sulfite 1.12g and water 170g compositions dropwise addition solution, time for adding 3h, are incubated 2h, finally after being added dropwise
PH with 35% ammoniacal liquor neutralization reaction liquid is 6~8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%, molecular weight Mw
For 37100.
Embodiment 5：
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkyl group
The mol ratio of amine is (6:1:0.14), the dosage of oxidant, reducing agent and chain-transferring agent is respectively in oxidation-reduction initiator
3.5%, 1.5%, the 1.35% of monomer integral molar quantity.
60% isopentene group polyethylene glycol (M is added into the 2L flasks equipped with agitatorw=3300, n=73) it is water-soluble
Liquid 480g, N- (4- vinyl benzyls)-N, N- dibutyl amine 2.99g, ammonium persulfate 4.97g and water 100g, is passed through N2It is molten to remove
Oxygen in liquid, it is subsequently agitated for being warming up to 60 DEG C, at this temperature, is added dropwise by acrylic acid 31.42g and fumaric acid 10.12g, mercapto
Base propyl alcohol 0.77g, sodium hydrogensulfite 0.97g and water 190g compositions dropwise addition solution, time for adding 4h, are incubated after being added dropwise
3h, it is finally 6~8 with the pH of 35% ethylenediamine solution neutralization reaction liquid, the viscosity reduction type polycarboxylic acids for obtaining solid content 40% subtracts
Aqua, molecular weight MwFor 49100.
Embodiment 6：
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkyl group
The mol ratio of amine is 6.5:1:0.2, the dosage of oxidant, reducing agent and chain-transferring agent is respectively in oxidation-reduction initiator
4.0%, 2.0%, the 1.0% of monomer integral molar quantity.
60% methacrylic polyethylene glycol (M is added into the 2L flasks equipped with agitatorw=4000, n=89) water
Solution 480g, N- (4- vinyl benzyls)-N, TMSDMA N dimethylamine 2.32g, 30% hydrogen peroxide solution 2.51g and water 100g, is passed through N2
To remove the oxygen in solution, it is subsequently agitated for being warming up to 50 DEG C, at this temperature, is added dropwise by acrylic acid 33.7g, mercaptopropionic acid
0.51g, L-AA 1.95g and water 180g compositions dropwise addition solution, time for adding 4h, are incubated 3h, finally after being added dropwise
PH with 35% sodium hydroxide solution neutralization reaction liquid is 6~8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%,
Molecular weight MwFor 59200.
Comparative example 1：
60% methacrylic polyethylene glycol (M is added into the 2L flasks equipped with agitatorw=1800, n=39) water
Solution 480g, 30% hydrogen peroxide solution 1.99g and water 100g, are passed through N2To remove the oxygen in solution, it is subsequently agitated for being warming up to
43 DEG C, at this temperature, it is added dropwise by acrylic acid 46.08g and methacrylic acid 6.88g, mercaptopropionic acid 2.66g, L-AA
0.77g and water 190g composition dropwise addition solution, time for adding 3h, 1h is incubated after being added dropwise, finally with 35% sodium hydroxide
The pH of solution neutralization reaction liquid is 6~8, obtains the polycarboxylate water-reducer of solid content 40%, molecular weight MwFor 27500.
Comparative example 2：
60% allyl polyglycol (M is added into the 2L flasks equipped with agitatorw=2400, n=53) aqueous solution
480g, potassium peroxydisulfate 6.52g and water 100g, are passed through N2To remove the oxygen in solution, it is subsequently agitated for being warming up to 55 DEG C, it is warm herein
Under degree, it is added dropwise what is be made up of acrylic acid 38.88g and itaconic acid 3.9g, mercaptopropionic acid 1.46g, sodium sulfite 1.09g and water 170g
Solution is added dropwise, time for adding 3h, 2h is incubated after being added dropwise, is finally 6~8 with the pH of 35% ammoniacal liquor neutralization reaction liquid, obtains
To the polycarboxylate water-reducer of solid content 40%, molecular weight MwFor 40100.
Application Example：
In Application Example, used cement is small wild field P II 52.5, and sand is modulus of fineness M=2.6 middle sand, stone
Son is the rubble of particle diameter 5~20mm continuous gradings.
Application Example 1
The polycarboxylate water-reducer of the present invention is according to GB/T8077-2000《Concrete admixture homogeneity test method》To net
Slurry fluidity is measured, and the fixed ratio of mud is 0.29, adjusts water reducer volume, makes initial flow degree between 200-250mm,
As a result such as table 1.
The flowing degree of net paste of cement test result of table 1
Note：" -- " indicates no fluidity
From the flowing degree of net paste of cement test result of table 1, embodiment is in the case where volume is below comparative example, just
Beginning fluidity and slump retaining will be better than comparative example.For example, embodiment 4 is far below the (0.10%vs of comparative example 2 in volume
0.14%) in the case of, initial flow degree is higher 34mm than comparative example, and comparative example has lost fluidity after 120min, and implements
Example 4 remains to keep 196mm fluidity；Embodiment 3 has similar initial flow degree with comparative example 1, but embodiment 3 has
Excellent slump retaining, fluidity can be kept to be lost after 120min less than 10%, and comparative example now lost flowability,
This proves that the polycarboxylate water-reducer of the present invention has the excellent properties of high diminishing, high-thin arch dam.
Application Example 2
Next the viscosity reduction type polycarboxylate water-reducer of the present invention is detected to newly mixing according to method as defined in GB8076-2008
The influence of concrete, the fixed ratio of mud are 0.30, adjust water reducer volume, make concrete initial slump between 21 ± 2cm,
Concrete quality match ratio：Cement 267, miberal powder 53, flyash 60, sand 767, great Shi 800, gravelstone 260, water 114.Concrete glues
Degree surveys flow time to quantify by inverted slump test tube, and specific method is：Slump cone is inverted, bottom seal cap, filled mixed
Solidifying native and floating (will typically be inverted slump cone to be fixed on a support, bottom is liftoff 50cm), slips off rapidly bottom, uses stopwatch
Test concrete flow time.Concrete experiments the results are shown in Table 2.
The testing concrete performance result of table 2
By the concrete test result of table 2 it is recognized that while the volume of embodiment is far below comparative example, but at the beginning of its concrete
Begin and 30min after the slump and divergence it is close with comparative example, show that polycarboxylate water-reducer of the invention has high diminishing, height
Protect the excellent properties to collapse.In addition, the flow time of embodiment all within 20 seconds, will be far smaller than the 35-37 seconds of comparative example, it is real
It is also more excellent to apply the workability of example, stirs and is also very easy to, coagulation can effectively be reduced by showing the polycarboxylate water-reducer of the present invention
Native viscosity.
Claims (9)
1. a kind of preparation method of viscosity reduction type polycarboxylate water-reducer, it is characterised in that big by unsaturated acid monomer, unsaturated polyether
Monomer and N- (4- vinyl benzyls)-N, N- dialkylamines are in molar ratio (2.5~6.5):1:(0.05~0.2) free radical is carried out
Copolyreaction and obtain, wherein：
Unsaturated acid monomer structural formula is such as shown in (I)：
Wherein, R1For-H or-COOH, R2For-H ,-CH3Or-CH2COOH；
Unsaturated polyether polymeric monomer structural formula is such as shown in (II)：
Wherein, R3For-H or-CH3, R4For-CH2- or-CH2CH2-, n=20~90；
N- (4- vinyl benzyls)-N, N- dialkylamines structural formula is such as shown in (III)：
Wherein, R5For C1~C6 alkyl.
2. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 1, it is characterised in that the poly- carboxylic of viscosity reduction type
The weight average molecular weight of sour water reducer is 10000~60000.
3. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 1, it is characterised in that
The unsaturated acid monomer is at least one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid；
The unsaturated polyether polymeric monomer is weight average molecular weight MwAllyl polyglycol, methyl alkene between 1000~4000
At least one of propyl group polyethylene glycol, isopentene group polyethylene glycol.
4. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 1, it is characterised in that described free-radical polymerized
React for water-based free radical copolyreaction.
5. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 4, it is characterised in that the water-based free radical
Copolyreaction uses oxidation-reduction initiator and water-soluble chain transfer agent, oxidant and also in the oxidation-reduction initiator
Former agent dosage is respectively that unsaturated acid monomer, unsaturated polyether polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkylamines are total
The 1%~4% of mole and 0.5%~2.0%；The dosage of water-soluble chain transfer agent is unsaturated acid monomer, unsaturated polyether
The 1%~5.5% of polymeric monomer and N- (4- vinyl benzyls)-N, N- dialkylamine integral molar quantity.
6. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 5, it is characterised in that the oxidationreduction
Initiator be hydrogen peroxide-ascorbic acid, hydrogen peroxide-ferrous sulfate, ammonium persulfate-ascorbic acid, ammonium persulfate-sodium sulfite,
Ammonium persulfate-sodium bisulfite or potassium peroxydisulfate-sodium sulfite, the chain-transferring agent are mercaptoethanol, TGA, sulfydryl third
Alcohol, mercaptopropionic acid or n- dodecyl mereaptan.
7. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 5, it is characterised in that comprise the following steps：
1) unsaturated polyether polymeric monomer, N- (4- vinyl benzyls)-N, N- dialkylamine, oxidant and water are sufficiently mixed,
Under protective atmosphere, reaction temperature is warming up to；
2) dropwise addition being made up of to mixed solution and dripping obtained by step 1) unsaturated acid monomer, reducing agent, chain-transferring agent and water
Solution, 2~4h of time for adding, after completion of dropwise addition, insulation reaction.
8. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 7, it is characterised in that reaction temperature be 30~
60 DEG C, 1~3h of insulation reaction, polymerization concentration 40%~50%, the polymerization concentration refers to all monomers in reaction mixture
Mass percent concentration sum.
9. application of the viscosity reduction type polycarboxylate water-reducer as cement dispersants obtained by any one of claim 1~8 preparation method.
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