CN105732911A - Preparation method and application of viscosity-reducing polycarboxylate superplasticizer - Google Patents
Preparation method and application of viscosity-reducing polycarboxylate superplasticizer Download PDFInfo
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- CN105732911A CN105732911A CN201610027918.4A CN201610027918A CN105732911A CN 105732911 A CN105732911 A CN 105732911A CN 201610027918 A CN201610027918 A CN 201610027918A CN 105732911 A CN105732911 A CN 105732911A
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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
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Abstract
The invention provides a preparation method of a viscosity-reducing polycarboxylate superplasticizer and an application thereof. The viscosity-reducing polycarboxylate superplasticizer can remarkably reduce the viscosity of concrete on the premise of guaranteeing high water reduction and high slump loss resistance; and the preparation method has the advantages of simple technology, low cost, little pollution and the like. In the preparation method, a specific unsaturated acid monomer, a specific unsaturated polyether macromonomer and N-(4-vinyl benzyl)-N, N-dialkylamine in a molar ratio of (2.5-6.5):1:(0.05-0.2) are subjected to free radical copolymerization reaction to obtain the viscosity-reducing polycarboxylate superplasticizer.
Description
Technical field
The present invention relates to the preparation method and application of a kind of viscosity reduction type polycarboxylate water-reducer, belong to concrete admixture
Technical field.
Background technology
At present, concrete remains the material that architectural engineering is main, the most large.Along with China's capital construction
High speed development, architectural engineering to maximization, high stratification, complicate development, to required concrete material
Properties requires more and more higher.Practice have shown that, adding chemical admixture in concrete can be substantially improved
Its service behaviour, it is true that additive has become in modern concrete in addition to cement, sand, stone, water
5th kind of important constituent.Water reducer (also referred to as " cement dispersants ") is research at present and applies
For a kind of concrete admixture widely, in the case of concrete workability is constant, mix water reducer permissible
Effectively save cement consumption, minimizing water consumption, raising concrete strength.Polycarboxylic acids is as the height of latest generation
Performance concrete water reducer, has that volume is low, slump retaining good, molecular structure Modulatory character is strong, production technology
The outstanding advantages such as environmental protection.Polycarboxylate water-reducer is a kind of comb polymer molecule polymer, and it is by rich in carboxylic acid
The main chain of group and polyether lateral chain composition, the hydroxy-acid group on main chain can be with oriented adsorption at the cement of positively charged
Or the surface of cement-hydrate, and polyether lateral chain stretches formation hydrated sheath in the solution to provide steric exclusion
Power is to prevent water walk from gathering, and the most this structure imparts the dispersibility that cement granules is good in water.
High-strength concrete the lowest commonly used water-cement ratio ensures that higher intensity is to apply in skyscraper work
Cheng Zhong, but the minimizing of water consumption can cause concrete viscosity to strengthen, flowing velocity is slack-off, and then impact construction
Be smoothed out.Therefore, the water reducer of market urgent needs a kind of viscosity reduction type, this water reducer not only to be protected
Card water-reducing rate and slump retaining, also to have obvious viscosity reduction function, to reduce the viscosity of high-strength concrete, improves work
Make performance.Polycarboxylic acids building-up process introduces in addition to unsaturated acid monomer and unsaturated polyether polymeric monomer
Third monomer can improve some service behaviour of water reducer and worked by many and prove, such as China is specially
Profit document CN 102153711 B discloses the preparation method of the polycarboxylate water-reducer of a kind of retardation setting type, will
Maleic anhydride grafted cyclodextrin polymeric monomer introduces allyl sulphonic acid salt-poly-second of acrylic compounds-methacrylic acid two
In the polycarboxylate water-reducer molecular structure that alcohol monomethyl ether ester is constituted, the novel water reducer so obtained has good
Good retarding performance, micro-bleed performance and more preferable mobility, and properties of product are stable, cement adaptability
By force, the compatibility is good；Chinese patent literature CN 102503226 B discloses a kind of high collapse protection type polycarboxylic acids and subtracts
The preparation method of water preparation, collapses acrylamide monomers and (methyl) acrylic ester monomer auxiliary agent as guarantor
Introducing in polycarboxylic acids molecular backbone, gained water reducer has the function of slump protection of excellence, it is ensured that concrete
In 3 hours, the slump is not lost, and has wide applicability.At present, market introduces the 3rd single
The polycarboxylate water-reducer product category of body has a lot, but principally falls into guarantor and collapse product, the poly-carboxylic of viscosity reduction type of urgent need
Acid water reducer product is the rarest, this series products of the most a small amount of patent report, such as, and Chinese patent literary composition
Offer CN 104262550 A and disclose the preparation method of a kind of viscosity reduction type polycarboxylate water-reducer, the most first by insatiable hunger
Unsaturated primary amine class minor comonomer is synthesized at a certain temperature, subsequently by it and containing ring with anhydride and unsaturated primary amine
The organic molecule reaction of oxygen groups and halogen group obtains quaternary ammonium salt unsaturated monomer, finally by this insatiable hunger
Introducing in polycarboxylic acids molecular structure as Third monomer with quaternary ammonium salt, the product obtained has reduction concrete
Viscosity, the good function such as slump-retaining that improve, but the method have complex steps, cost of material high,
Production process pollutes the shortcomings such as big；Chinese patent literature CN 100402457C discloses a kind of polycarboxylic acid mixed
Solidifying soil additive, by (methyl) alkyl acrylate monomer, the unsaturated big list of specific poly alkylene glycol
Body and unsaturated acid monomer are prepared by free radicals copolymerization reaction, and the method introduces has the of hydrophobic interaction
Three monomer alkyl acrylate, products obtained therefrom has the cement dispersibility of excellence, it is possible to reduce concrete surrender
Stress and viscosity, but the method has the shortcomings such as production cost is high, slump retaining is poor, viscosity reducing effect is little.
Summary of the invention
Goal of the invention
It is an object of the present invention to provide the preparation method of a kind of viscosity reduction type polycarboxylate water-reducer, described viscosity reduction
Type polycarboxylate water-reducer is on the premise of ensureing high diminishing, high-thin arch dam, moreover it is possible to the viscosity of concrete is greatly reduced,
And the advantages such as the method has, and technique is simple, low cost, pollution are little.
It is a further object to provide described viscosity reduction type polycarboxylate water-reducer answering as cement dispersants
With.
Summary of the invention
Researcher of the present invention finds through experiment, the water film that polycarboxylic acids Molecular Adsorption to cement particle surface produces
Thickness directly affects the viscosity of concrete, and the absorption conformation of polycarboxylic acids determines water film thickness, and rigidity base
The introducing of group can make conformation more stretch, and can improve water film thickness, therefore the present invention is by N-(4-vinyl benzyl
Base)-N, N-dialkylamine introduces in the molecular structure of polycarboxylic acids as Third monomer, synthesizes a kind of viscosity reduction type and gather
Carboxylic acid water reducer.
In a first aspect of the present invention, it is provided that the preparation method of a kind of viscosity reduction type polycarboxylate water-reducer, by insatiable hunger
With acid monomers, unsaturated polyether polymeric monomer with N-(4-vinyl benzyl)-N, N-dialkylamine 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 as shown in (I):
Wherein, R1For-H or-COOH, R2For-H ,-CH3Or-CH2COOH；
Unsaturated polyether polymeric monomer structural formula is as shown in (II):
Wherein, R3For-H or-CH3, R4For-CH2-or-CH2CH2-, n=20～90；
N-(4-vinyl benzyl)-N, N-dialkylamine structural formula is as shown in (III):
Wherein, R5Alkyl for C1～C6.
The molecular weight requirement of viscosity reduction type polycarboxylate water-reducer of the present invention is compared with the poly-carboxylic of comb shaped structure in technology
The conventional molecular weight ranges of acid water reducer, those skilled in the art also can further determine that preferably in conjunction with through test
Molecular weight ranges.The weight average molecular weight of viscosity reduction type polycarboxylate water-reducer of the present invention is preferably
10000～60000.
Described unsaturated acid monomer works as R1During for-COOH, it can be used to form anhydride with other-COOH
Alternative form.This anhydride alternative form can change into carboxylic acid, the most visually during preparation process or use
Substitute for equivalent.Preferably, described unsaturated acid monomer is acrylic acid, methacrylic acid, itaconic acid, rich horse
At least one in acid, maleic acid (or substituting with maleic anhydride)；
Preferably, described unsaturated polyether polymeric monomer is weight average molecular weight MwAllyl between 1000～4000
Base Polyethylene Glycol (R3=-H, R4=-CH2-), methacrylic Polyethylene Glycol (R3=-CH3, R4=-CH2-), different
Pentenyl Polyethylene Glycol (R3=-CH3, R4=-CH2CH2-) at least one.
Concrete, described N-(4-vinyl benzyl)-N, N-dialkylamine can be N-(4-vinyl benzyl)-N, N-
Dimethylamine, N-(4-vinyl benzyl)-N, N dimethylamine, N-(4-vinyl benzyl)-N, N-di-n-propylamine, N-(4-
Vinyl benzyl)-N, N-dibutyl amine, N-(4-vinyl benzyl)-N, N-diamylamine, N-(4-vinyl benzyl)-N, N-
At least one of dihexylamine.
Described at least one, can be i.e. one of which, or the mixture of two or more arbitrary proportion.
Those skilled in the art can be according to monomer reactivity and the molecular weight of target product, in conjunction with prior art
Select concrete free radicals copolymerization reaction condition.It is for instance possible to use water common in polycarboxylate water-reducer synthesis
Free love base copolyreaction.Further, water-based free radical copolyreaction of the present invention preferably employ oxidation-
Reduction initiator and water-soluble chain transfer agent, in described oxidation-reduction initiator, Oxidizing and Reducing Agents consumption divides
Wei unsaturated acid monomer, unsaturated polyether polymeric monomer and total mole of N-(4-vinyl benzyl)-N, N-dialkylamine
The 1%～4% and 0.5%～2.0% of amount (hereinafter referred to as " monomer integral molar quantity ")；The use of water-soluble chain transfer agent
Amount is the 1%～5.5% of monomer integral molar quantity.It is furthermore preferred that described oxidation-reduction initiator is hydrogen peroxide-anti-bad
Hematic acid, hydrogen peroxide-ferrous sulfate, Ammonium persulfate .-ascorbic acid, Ammonium persulfate .-sodium sulfite, Ammonium persulfate .-
One in sodium sulfite or potassium peroxydisulfate-sodium sulfite combination, described chain-transferring agent is mercaptoethanol, sulfydryl
Acetic acid, mercaprol, mercaptopropionic acid or n-dodecyl mereaptan；The preparation method of described viscosity reduction type polycarboxylate water-reducer
Comprise the following steps:
1) unsaturated polyether polymeric monomer, N-(4-vinyl benzyl)-N, N-dialkylamine, oxidant and water are filled
Divide mixing, under protective atmosphere, be warming up to reaction temperature；
2) to step 1) gained mixed solution and dripping is by unsaturated acid monomer, reducing agent, chain-transferring agent and water
The dropping solution of composition, time for adding 2～4h, after completion of dropwise addition, insulation reaction.
(it has been generally acknowledged that such properties of product more to form monomer polymer chain architecture arranged in a uniform as far as possible
Excellent), it is proposed with very much above-mentioned reactant addition manner, it may be assumed that the relatively low monomer of polymerization activity starts with reaction
In front disposable addition reaction vessel, the monomer that polymerization activity is higher is slowly added dropwise at the reaction temperatures, and this is this
The usual means in field.
Protective atmosphere can be N2Or inert protective gas, preferably N2, have economy, be readily available excellent
Point.
Concrete reaction temperature and insulation reaction time select according to monomer reactivity and initiator, such as
In the presence of above-mentioned preferred oxidation-reduction initiator, preferably set reaction temperature as 30～60 DEG C, insulation reaction
1～3h, polymerization concentration 40%～50%.Described polymerization concentration refers to the quality of all monomers in reaction mixture
Percent concentration sum.
Gained viscosity reduction type polycarboxylate water-reducer has a following structure formula:
Wherein, x, y, z represents the number of repeat unit of each repetitive of random arrangement.
After copolyreaction terminates, product can be directly used as the main constituent of cement dispersants and use, more preferably
Use in alkaline matter further and rear use, to strengthen the storage stability of product.This is the known skill of this area
Art.Alkaline matter is preferably sodium hydroxide solution, ammonia or ethylenediamine solution, and (concentration can be dense according to end product
The requirement of degree is determined).The consumption of alkaline matter is 6～8 to be advisable with the pH value of regulation product.Neutralize
After, in said structure formula, contained carboxyl can partly or entirely be converted into carboxylate.Owing to neutralizing described viscosity reduction
The molecular weight effects of type polycarboxylate water-reducer is the least, and it is ignored by the present invention.
In another aspect of this invention, described viscosity reduction type polycarboxylate water-reducer is additionally provided as cement dispersants
Application.
Viscosity reduction its application process of type polycarboxylate water-reducer of the present invention is identical with known cement dispersants, this
Skilled person 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
Volume is pure solid volume, and described percentage ratio is mass percent.The too low meeting of volume makes its performance deteriorate, volume
Too high meeting causes waste economically and performance not to improve.
New polycarboxylic acid water reducer of the present invention can be with other commercially available water reducer, as lignosulfonic acid salt subtracts
Water preparation, naphthalene sulfonic salt water reducer, polycarboxylate water-reducer etc. are used in mixed way, and also can add air entraining agent, slow setting
Use after agent, early strength agent, extender, viscosifier, economization agent and defoamer.
The present invention compared with prior art has the advantage that
(1) the viscosity reduction type polycarboxylate water-reducer of the present invention not only has that volume is low, water-reducing rate is high, slump retaining is strong
Etc. advantage, also can effectively reduce high-strength concrete viscosity, make work progress simpler, laborsaving.
(2) production technology of the viscosity reduction type polycarboxylate water-reducer of the present invention is simple, pollute little, low cost.
Detailed description of the invention
The detailed preparation method of viscosity reduction type polycarboxylate water-reducer of the present invention given below, its object is to allow
One skilled in the art will appreciate that present disclosure and implements according to this, but these embodiments never limit
The scope of the present invention processed, all equivalence changes made according to spirit of the invention or modification, all should contain at this
Within the protection domain of invention.
First pass through synthesis example and introduce starting monomer N-(4-vinyl benzyl)-N, N-dioxane used in the present invention
The preparation method of base amine, (water generation science and technology is limited by being equipped with Waters Xbridge C18 chromatographic column for its purity
Company) LC600 high performance liquid chromatograph (HPLC, LabTech Instrument Ltd.) be measured,
The methanol/water mixed solution of flowing phase: 4:1, flow velocity: 0.8mL/min, sample solution concentration: 0.8%.Lead to subsequently
Crossing embodiment and introduce the synthetic method of viscosity reduction type polycarboxylate water-reducer of the present invention, polymer molecular weight uses
It is equipped with the miniDAWN Tristar aqueous gel of TSK-GELSW (Dong Cao bio tech ltd) chromatographic column
Permeation chromatograph (GPC, Wyatt Technology) is measured, and flow phase: 0.1M NaNO3 aqueous solution,
Flow velocity: 1.0mL/min, sample solution concentration: 0.5%.
Raw material p-chloromethyl styrene (> 95% used in the present invention) it is purchased from Beijing Yi Nuokai company, insatiable hunger
It is that Nanjing Bo Te new material is limited with polyether macromonomer (double bond retention > 90%) aqueous solution (concentration 60%)
Company produces, and other raw material is commercially available general analysis pure chemistry reagent.
N-(4-vinyl benzyl)-N, N-dialkylamine synthesis example:
Synthetic method reference literature Dan M, Su Y, Xiao X, et al.Macromolecules, 2013,
46 (8): 3137-3146, to equipped with in the 1L flask of agitator add p-chloromethyl styrene (1.0mol,
152.6g), dialkylamine (1.5mol, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine, diamylamine, two
One in hexylamine), potassium carbonate 120g and solvent chloroform 200mL, stirring mixed liquor is warming up to 50 DEG C,
React 12h at this temperature.After reaction terminates, being filtered to remove potassium carbonate, rotation is steamed and is reclaimed chloroform and dioxane
Base amine, obtains yellowish crude product, and finally decompression distillation obtains N-(4-the vinyl benzyl)-N, N-of colorless liquid
Dialkylamine, yield is 82%～88%, records monomer purity all more than 97% by HPLC.
Embodiment 1:
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-vinyl benzyl)-N, N-
The mol ratio of dialkylamine is 5.5:1:0.12, oxidant, reducing agent and chain tra nsfer in oxidation-reduction initiator
The consumption of agent is respectively the 1.0% of monomer integral molar quantity, 0.5%, 5.5%.
To equipped with the allyl polyglycol (M adding 60% in the 2L flask of agitatorw=1200, n=26)
Aqueous solution 480g, N-(4-vinyl benzyl)-N, N dimethylamine 5.44g, the hydrogen peroxide 1.80g of 30% and water
100g, is passed through N2To remove the oxygen in solution, it is subsequently agitated for being warming up to 30 DEG C, at this temperature, dropping
The dropping solution being made up of acrylic acid 95.04g, mercaptoethanol 6.82g, ferrous sulfate 2.21g and water 220g,
Time for adding 2h, is incubated 1h after dropping, finally with in the sodium hydroxide solution of 35% with reactant liquor to pH
Value is 6～8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%, molecular weight MwIt is 10900.
Embodiment 2:
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-vinyl benzyl)-N, N-
The mol ratio of dialkylamine is 4.5:1:0.09, oxidant, reducing agent and chain tra nsfer in oxidation-reduction initiator
The consumption of agent is respectively the 2.0% of monomer integral molar quantity, 0.5%, 2.85%.
To equipped with the methacrylic Polyethylene Glycol (M adding 60% in the 2L flask of agitatorw=1800, n
=39) aqueous solution 480g, N-(4-vinyl benzyl)-N, N-di-n-propylamine 3.12g, 30% hydrogen peroxide solution 2.03g
With water 100g, it is passed through N2To remove the oxygen in solution, it is subsequently agitated for being warming up to 43 DEG C, at this temperature,
Dropping is by acrylic acid 46.08g and methacrylic acid 6.88g, mercaptopropionic acid 2.70g, L-AA 0.79g
With the dropping solution of water 190g composition, time for adding 3h, it is incubated 1h after dropping, finally with 35%
In sodium hydroxide solution, the pH with reactant liquor is 6～8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%,
Molecular weight MwIt is 24800.
Embodiment 3:
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-vinyl benzyl)-N, N-
The mol ratio of dialkylamine is 2.5:1:0.05, oxidant, reducing agent and chain tra nsfer in oxidation-reduction initiator
The consumption of agent is respectively the 3.0% of monomer integral molar quantity, 1.0%, 2.5%.
To equipped with the isopentene group Polyethylene Glycol (M adding 60% in the 2L flask of agitatorw=2400, n=
53) aqueous solution 480g, N-(4-vinyl benzyl)-N, N-dihexylamine 1.81g, Ammonium persulfate. 2.91g and water
100g, is passed through N2To remove the oxygen in solution, it is subsequently agitated for being warming up to 50 DEG C, at this temperature, dropping
By methacrylic acid 15.48g and maleic anhydride 11.76g, TGA 0.98g, L-AA 0.75g and
Water 160g composition dropping solution, time for adding 3.5h, after dropping be incubated 1h, finally with 35% hydrogen
In sodium hydroxide solution, the pH with reactant liquor is 6～8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%,
Molecular weight MwIt is 30600.
Embodiment 4:
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-vinyl benzyl)-N, N-
The mol ratio of dialkylamine is 4.75:1:0.18, and in oxidation-reduction initiator, oxidant, reducing agent and chain turn
The consumption moving agent is respectively the 3.5% of monomer integral molar quantity, 1.25%, 2.0%.
To equipped with the allyl polyglycol (M adding 60% in the 2L flask of agitatorw=2400, n=53)
Aqueous solution 480g, N-(4-vinyl benzyl)-N, N dimethylamine 4.08g, potassium peroxydisulfate 6.72g and water 100g,
It is passed through N2To remove the oxygen in solution, being subsequently agitated for being warming up to 55 DEG C, at this temperature, dropping is by propylene
Acid 38.88g and itaconic acid 3.90g, mercaptopropionic acid 1.51g, sodium sulfite 1.12g and water 170g composition
Dropping solution, time for adding 3h, be incubated 2h after dropping, finally with in the ammonia of 35% with reactant liquor
PH is 6～8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%, molecular weight MwIt is 37100.
Embodiment 5:
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-vinyl benzyl)-N, N-
The mol ratio of dialkylamine is (6:1:0.14), and in oxidation-reduction initiator, oxidant, reducing agent and chain turn
The consumption moving agent is respectively the 3.5% of monomer integral molar quantity, 1.5%, 1.35%.
To equipped with the isopentene group Polyethylene Glycol (M adding 60% in the 2L flask of agitatorw=3300, n=
73) aqueous solution 480g, N-(4-vinyl benzyl)-N, N-dibutyl amine 2.99g, Ammonium persulfate. 4.97g and water
100g, is passed through N2To remove the oxygen in solution, it is subsequently agitated for being warming up to 60 DEG C, at this temperature, dropping
By acrylic acid 31.42g and fumaric acid 10.12g, mercaprol 0.77g, sodium sulfite 0.97g and water 190g
Composition dropping solution, time for adding 4h, after dropping be incubated 3h, finally with 35% ethylenediamine solution
The pH neutralizing reactant liquor is 6～8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%, molecular weight Mw
It is 49100.
Embodiment 6:
In the present embodiment, unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-vinyl benzyl)-N, N-
The mol ratio of dialkylamine is 6.5:1:0.2, oxidant, reducing agent and chain tra nsfer in oxidation-reduction initiator
The consumption of agent is respectively the 4.0% of monomer integral molar quantity, 2.0%, 1.0%.
To equipped with the methacrylic Polyethylene Glycol (M adding 60% in the 2L flask of agitatorw=4000, n
=89) aqueous solution 480g, N-(4-vinyl benzyl)-N, N dimethylamine 2.32g, 30% hydrogen peroxide solution 2.51g
With water 100g, it is passed through N2To remove the oxygen in solution, it is subsequently agitated for being warming up to 50 DEG C, at this temperature,
The dropping that dropping is made up of acrylic acid 33.7g, mercaptopropionic acid 0.51g, L-AA 1.95g and water 180g
Solution, time for adding 4h, after dropping be incubated 3h, finally with in the sodium hydroxide solution of 35% and react
The pH of liquid is 6～8, obtains the viscosity reduction type polycarboxylate water-reducer of solid content 40%, molecular weight MwIt is 59200.
Comparative example 1:
To equipped with the methacrylic Polyethylene Glycol (M adding 60% in the 2L flask of agitatorw=1800, n
=39) aqueous solution 480g, 30% hydrogen peroxide solution 1.99g and water 100g, be passed through N2To remove in solution
Oxygen, is subsequently agitated for being warming up to 43 DEG C, and at this temperature, dropping is by acrylic acid 46.08g and methacrylic acid
6.88g, mercaptopropionic acid 2.66g, L-AA 0.77g and the dropping solution of water 190g composition, during dropping
Between 3h, be incubated 1h after dropping, finally with the sodium hydroxide solution of 35% is 6～8 with the pH of reactant liquor,
Obtain the polycarboxylate water-reducer of solid content 40%, molecular weight MwIt is 27500.
Comparative example 2:
To equipped with the allyl polyglycol (M adding 60% in the 2L flask of agitatorw=2400, n=53)
Aqueous solution 480g, potassium peroxydisulfate 6.52g and water 100g, be passed through N2To remove the oxygen in solution, stir subsequently
Mixing and be warming up to 55 DEG C, at this temperature, dropping is by acrylic acid 38.88g and itaconic acid 3.9g, mercaptopropionic acid
1.46g, sodium sulfite 1.09g and the dropping solution of water 170g composition, time for adding 3h, protect after dropping
Temperature 2h, finally with being 6～8 with the pH of reactant liquor in the ammonia of 35%, the polycarboxylic acids obtaining solid content 40% subtracts
Water preparation, molecular weight MwIt is 40100.
Application Example:
In Application Example, the cement used is little wild field P II 52.5, and sand is modulus of fineness M=2.6's
Medium sand, stone is the rubble of particle diameter 5～20mm continuous grading.
Application Example 1
The polycarboxylate water-reducer of the present invention is according to GB/T8077-2000 " concrete admixture homogeneity test side
Method " paste flowing degree is measured, the fixing ratio of mud is 0.29, adjusts water reducer volume, makes initial flow
Spend between 200-250mm, result such as table 1.
Table 1 flowing degree of net paste of cement test result
Note: "--" indicates without fluidity
From the flowing degree of net paste of cement test result of table 1, embodiment is below the situation of comparative example at volume
Under, initial flow degree and slump retaining will be better than comparative example.Such as, embodiment 4 is far below comparative example at volume
In the case of 2 (0.10%vs 0.14%), initial flow degree 34mm higher than comparative example is right after 120min
Ratio has lost fluidity, and embodiment 4 remains to keep the fluidity of 196mm；Embodiment 3 and contrast
Example 1 has close initial flow degree, but embodiment 3 has the slump retaining of excellence, can keep fluidity
After 120min, loss is less than 10%, and comparative example the most lost flowability, this proves that the present invention's is poly-
Carboxylic acid water reducer has the excellent properties of high diminishing, high-thin arch dam.
Application Example 2
The following method specified according to GB8076-2008 is to detect the viscosity reduction type polycarboxylate water-reducer of the present invention
Impact on fresh concrete, the fixing ratio of mud is 0.30, adjusts water reducer volume, makes concrete initially collapse
Spend between 21 ± 2cm, concrete quality match ratio: cement 267, breeze 53, flyash 60, sand 767,
Great Shi 800, gravelstone 260, water 114.Concrete viscosity is surveyed flow time by inverted slump test tube and is quantified,
Method particularly includes: slump cone is inverted, bottom seal cap, fills concrete and floating (typically inversion collapsed
Degree of falling cylinder is fixed on a support, bottom is liftoff 50cm), slip off rapidly bottom, test concrete stream with stopwatch
The empty time.Concrete experiments the results are shown in Table 2.
Table 2 testing concrete performance result
By the concrete test result of table 2 it is recognized that while the volume of embodiment is all far below comparative example, but it mixes
Coagulate the soil slump initially and after 30min and divergence is close with comparative example, show the polycarboxylic acids diminishing of the present invention
Agent has the excellent properties of high diminishing, high-thin arch dam.Additionally, the flow time of embodiment is all within 20 seconds,
The 35-37 second of comparative example to be far smaller than, the workability of embodiment is the most more excellent, stirs and is also very easy to,
Show that the polycarboxylate water-reducer of the present invention can effectively reduce concrete viscosity.
Claims (9)
1. the preparation method of a viscosity reduction type polycarboxylate water-reducer, it is characterised in that by unsaturated acid monomer, no
Saturated polyether macromonomer and N-(4-vinyl benzyl)-N, N-dialkylamine (2.5～6.5) in molar ratio: 1:
(0.05～0.2) carries out free radicals copolymerization reaction and obtains, wherein:
Unsaturated acid monomer structural formula is as shown in (I):
Wherein, R1For-H or-COOH, R2For-H ,-CH3Or-CH2COOH；
Unsaturated polyether polymeric monomer structural formula is as shown in (II):
Wherein, R3For-H or-CH3, R4For-CH2-or-CH2CH2-, n=20～90；
N-(4-vinyl benzyl)-N, N-dialkylamine structural formula is as shown in (III):
Wherein, R5Alkyl for C1～C6.
2. the preparation method of viscosity reduction type polycarboxylate water-reducer as claimed in claim 1, it is characterised in that described
The weight average molecular weight of viscosity reduction type polycarboxylate 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
Described unsaturated acid monomer be in acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid extremely
Few one；
Described unsaturated polyether polymeric monomer is weight average molecular weight MwThe poly-second of pi-allyl two between 1000～4000
At least one in alcohol, methacrylic 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 radicals copolymerization reaction is 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 described
Water-based free radical copolyreaction uses oxidation-reduction initiator and water-soluble chain transfer agent, and described oxidation-reduction is drawn
Send out Oxidizing and Reducing Agents consumption in agent and be respectively unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-second
Thiazolinyl benzyl)-N, N-dialkylamine integral molar quantity 1%～4% and 0.5%～2.0%；Water-soluble chain transfer agent
Consumption is that unsaturated acid monomer, unsaturated polyether polymeric monomer and N-(4-vinyl benzyl)-N, N-dialkylamine always rub
The 1%～5.5% of that amount.
6. the preparation method of the viscosity reduction type polycarboxylate water-reducer as described in claim 4 or 5, it is characterised in that
Described oxidation-reduction 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, described chain-transferring agent
For mercaptoethanol, TGA, mercaprol, mercaptopropionic acid or n-dodecyl mereaptan.
7. the preparation method of the viscosity reduction type polycarboxylate water-reducer as described in claim 4 or 5, it is characterised in that
Comprise the following steps:
1) unsaturated polyether polymeric monomer, N-(4-vinyl benzyl)-N, N-dialkylamine, oxidant and water are filled
Divide mixing, under protective atmosphere, be warming up to reaction temperature；
2) to step 1) gained mixed solution and dripping is by unsaturated acid monomer, reducing agent, chain-transferring agent and water
The dropping solution of composition, time for adding 2～4h, 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 is 30～60 DEG C, insulation reaction 1～3h, polymerization concentration 40%～50%.
9. preparation method gained viscosity reduction type polycarboxylate water-reducer any one of claim 1～8 disperses as cement
The application of agent.
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