CN100453493C - Method for preparing modified lignin poly-carboxylic-acid cement dispersant - Google Patents
Method for preparing modified lignin poly-carboxylic-acid cement dispersant Download PDFInfo
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- CN100453493C CN100453493C CNB2007100525122A CN200710052512A CN100453493C CN 100453493 C CN100453493 C CN 100453493C CN B2007100525122 A CNB2007100525122 A CN B2007100525122A CN 200710052512 A CN200710052512 A CN 200710052512A CN 100453493 C CN100453493 C CN 100453493C
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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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
- C04B24/2641—Polyacrylates; Polymethacrylates
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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
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0082—Segregation-preventing agents; Sedimentation-preventing agents
- C04B2103/0083—Bleeding-preventing agents
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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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- 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
- C04B2103/308—Slump-loss preventing agents
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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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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- Organic Chemistry (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
This invention relates to preparation method of modified lignin poly carboxylic acid cement dispersant, belongs to concrete admixture. The process: whip amd heating-up lignin sulfonate to 50 to 80 deg, in turns add sodium dichromate 5 to 9 shares, polyvinyl alcohol 10 to 20 shares, acroleic acid 5 to 18 shares, initiator 0.1 to 3 shares, at temperature 80 to 100 deg, take reaction for 3 to 5 hours, gain modified lignin sulphonate water solution. The product brings the cement good consistency, not bleed air, without bleeding, good degree of fluidity and good flexibility.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of cement dispersants, be to use the preparation method of the synthetic a kind of modified lignin poly-carboxylic-acid cement dispersant of macromolecule organic material specifically.
Background technology
Cement dispersants also claims cement water reducing agent, and the water yield that is added in the time of can obviously reducing the mix concrete after using improves Yi Hexing, can significantly improve concrete flowing property and intensity simultaneously, thereby improves the quality of engineering.Concrete is the material of construction of world's consumption maximum, and cement dispersants has become requisite additive in the concrete production.At present, developed country and area, the cement dispersants consumption accounts for more than 80% in the concrete.
Cement dispersants mainly contains following several: the modified lignin mahogany sulfonate water reducer; The naphthalene sulfonic acidformaldehyde condensation product water reducer; Melamine water reducing agent; Sulfamate water reducer; Aliphatic water reducing agent; Carboxylic acid graft multipolymer water reducer.
Sulfonated lignin are the byproducts with paper mill waste liquid gained after operations such as sulfonation, spraying drying are handled, and the branch of calcium lignin sulphonate and sodium lignosulfonate is arranged, and what generally obtain is calcium lignin sulphonate, is referred to as sulfonated lignin.Volume is bigger during as cement water reducing agent, and water-reducing rate is lower.Because calcium lignin sulphonate is cheap, people are many extensively to use it as ordinary water-reducing agent, at present domestic occurred by with its modification to improve water-reducing rate, make it reach the high efficiency water reducing agent standard techniques, but because the limitation of conditions such as technical recipe, the domestic ability that does not still possess scale operation at present.Chinese patent publication number: CN1609041, open day: on April 27th, 2005, denomination of invention: " properties-correcting agent of lignin sulfonate as concrete water reducing agent " has proposed the lignin sulfonate as concrete water reducing agent properties-correcting agent of being made up of trolamine 50-95, sodium lauryl sulfate 4-50, defoamer 0.05-2 that can partly replace high efficiency water reducing agent consumption in the concrete pump-feed agent.Can equivalent replace high efficiency water reducing agent 15%, its water-reducing rate can be brought up to 12-15%, and cost is lower, and volume reduces, but still is difficult to satisfy the technical requirements of national regulation high efficiency water reducing agent.
The naphthalene sulfonic acidformaldehyde condensation product water reducer is present domestic production amount maximum, uses the widest high efficiency water reducing agent, its technology comparative maturity, and each factory's product quality level is more or less the same.The advantage of naphthalene water reducer is: water-reducing rate is higher, not bleed, and cement adaptability is good, and is good with various admixture composite performances.Can be used for preparing high-strength, high performance concrete.The subject matter that its exists be the slump through the time loss big, concrete is clamminess, and expensive raw material price.The naphthalene water reducer of existing market has 2 kinds on coventional type and highly enriched type.Coventional type generally contains the Na of 18%-22%
2SO
1, generally need composite use, to improve its water-reducing rate, reduce slump-loss; High dense type is with the Na in the coventional type naphthalene water reducer with chemical process
2SO
1Content reduces, and help improving water-reducing rate, reduce slump-loss, preventing to produce precipitation because of temperature is low, but its technology complexity.
Melamine resin water reducer full name is a sulfonated melamine compound resin, also claims melmac, is a kind of water-soluble polymeric resin, and the domestic later stage seventies succeeds in developing, and belongs to efficient non-gas tracting subtractive agent.Its performance and naphthalene are close, and resistance to elevated temperatures is better than naphthalene system, can be used for heat-resisting, refractory concrete.But because of its liquid product concentration is low, storage period is short, the slump through the time loss also big, concrete is clamminess, price is higher relatively, use face is not as good as naphthalene system.Domestic once the experiment replaces the part trimeric cyanamide with urea and comes modification reducing cost, but further promoted not as good as the pure melamine product fine because of its product performance eventually.
Sulfamate water reducer is a kind of non-bleed soluble resin water reducer.Advantage is: volume is little, water-reducing rate is high, the slump is little through time loss, is particularly useful for the less high performance concrete of water cement ratio, and its water-reducing rate can reach 30%.Shortcoming is: the molecular weight of sulfamate water reducer hour causes the cement slurry bleeding very much easily, and concrete slump loss is very fast; When molecule was too big, the diminishing dispersiveness was affected; Cause concrete bleeding when volume is high easily, emanate and harden; And its cost is higher.Sulfamate water reducer is to be formed by the condensation under certain condition of Sulphanilic Acid, phenol, formaldehyde.Also available aniline after sulfonation again with phenol, formaldehyde condensation.Also have at present with the condensation of urea instead of part sulfamate, but the purer thionamic acid salt error of effect is a little.
The aliphatic sulfonate water reducer is based on carbonyl compound, form the aliphatics macromolecular chain of certain molecular weight size under certain condition with formaldehyde condensation, and open carbonyl by sulfonation reaction, introduce the wetting ability sulfonic acid group, it is a kind of polymeric surface active agent that contains hydrophilic radicals such as sulfonic group, hydroxyl, carboxyl, molecular-weight average is at 3300-3500, and main raw material is acetone, formaldehyde, and S-WAT.It is as the reinforcing oil well admixture the earliest, and good high-temperature stability and water-reducing effect are arranged, and can improve and keep the rheological of cement.Afterwards by a large amount of experiments, it is successfully applied to commerical ready-mixed concrete, kept it to compare institute with naphthalene sulfonic salt water reducer and had high-temperature stability as cement dispersants, and synthesis technique is simple, because of not containing the vitriol of separating out under the low temperature, avoided waiting in the winter time the sulphate crystal under the low temperature condition.Its shortcoming is under the situation of identical addition, and water-reducing rate is lower than naphthalene system and poly carboxylic acid, and slump-loss is bigger, also exists the problem of using back cement variable color.
Polycarboxylate graft copolymer water reducer is present novel high-performance water reducing agent, and it has the following advantages: the water-reducing rate height, slump-loss is little, the later strength height: the 28d gain in strength is more than 40%.Volume is less, generally below 1%.Though it is littler than naphthalene system or trimeric cyanamide to mix the Zeta potential value of cement slurry, its cement particle surface of this type of water reducer, the slump was not lost substantially at 1-2 hour.Its reason be carboxylic acid ion can with Ca in the cement slurry
2+In conjunction with, the hydration rate that slowed down is because the less and unlikely relatively very fast reduction water reducer concentration of hydrate.Relevant with polycarboxylate in addition at the suction type of cement surface; it is three-dimensional spination absorption at cement surface its master chain molecular architecture decision; therefore the horizontal suction type that is different from naphthalene system has more three-dimensional current potential provide protection, and can the long period keep the stably dispersing state.This type of water reducer is suitable for high performance concrete.Its shortcoming is: consistency is poor, to concrete predictable poor, as: when poly carboxylic acid series water reducer and other admixture used jointly, its concrete slump loss was too fast and be prone to phenomenons such as fast hard, has cement and chemical admixture compatibility problem; In the concrete that uses high-performance water reducing agent, when unit water yield minimizing, when the slump increases, following problem usually takes place: the water reducer consumption is excessive, concrete viscosity is too big, segregation excreting water phenomenon, pumping difficulty occur.And poly carboxylic acid series water reducer synthesis technique complexity, raw material ratio is expensive.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of modified lignin poly-carboxylic-acid cement dispersant is provided.It is grafting polycarboxylate compound on modified lignin mahogany sulfonate, and makes the technical feature of its cement dispersants satisfy the requirement of national regulation high-efficiency cement dispersion agent, and production method is simple, and cost is lower.
Technical solution of the present invention is: comprise following composition by weight and step:
A. get solid content and be 30～60 parts of the lignosulfonic acid salt brine solutions of 20-40%, drop into reactor, stirring is warmed up to 50～80 ℃, drop into 5～9 parts of sodium dichromate 99s more successively, 10～20 parts of polyvinyl alcohol, 5～18 parts in vinylformic acid, 0.1～3 part of initiator, under 80～100 ℃ of temperature, reacted 3-5 hour, obtain the modified lignin mahogany sulfonate aqueous solution.
B. with maleic anhydride 10-35 part, vinylformic acid hydroxyl ester 20-60 part, vinylbenzene 10-25 part and superoxide 1-5 part are dropped in the reactor, stir and heat up, and 80 ℃-160 ℃ reactions 2-6 hour down, obtain poly carboxylic acid modified dose;
C. with water 200-400 part; ammonium persulphate 10-40 part; sulphite 10-18 part adds in the reactor successively, is warming up to 40-60 ℃, charges into rare gas element; under protection of inert gas, add modified lignin mahogany sulfonate aqueous solution 10-40 part; keep 70-90 ℃ of temperature, reacted 3-5 hour, add poly carboxylic acid modified dose of 5-30 part again; reacted 1-2 hour, and promptly obtained modified lignin poly-carboxylic-acid cement dispersant.
Initiator of the present invention is a persulphate, and described superoxide is hydrogen peroxide or perborate or percarbonate, and rare gas element is nitrogen or neon.
The present invention can also get 40 parts of the lignosulfonic acid salt brine solutions of 20-40%, drop into reactor, stirring is warmed up to 60 ℃, drop into 6 parts of dichromates more successively, 15 parts of polyvinyl alcohol, 10 parts in vinylformic acid, 0.2 part of initiator, under 90 ℃ of temperature, reacted 4 hours, obtain the modified lignin mahogany sulfonate aqueous solution.
The present invention can also be with 20 parts of maleic anhydrides, 40 parts of vinylformic acid hydroxyl esters, and 3 parts of 15 parts of vinylbenzene and superoxide drop in the reactor, stir and heat up, and react 4 hours down at 80 ℃, obtain poly carboxylic acid modified dose.
The present invention can also be with 300 parts in water; 15 parts of ammonium persulphates; S-WAT adds in the reactor for 20 parts successively, is warming up to 50 ℃, charges into rare gas element; under the protection of inert gas condition, add 20 parts of the modified lignin mahogany sulfonate aqueous solution; keep 80 ℃ of temperature, reacted 4 hours, add poly carboxylic acid modified dose 20 parts again; reacted 1.5 hours, and promptly obtained modified lignin poly-carboxylic-acid cement dispersant.
The invention has the beneficial effects as follows:
1. employing oxidation--polycondensation principle is carried out modification to sulfonated lignin, reduces the delayed coagulation of sulfonated lignin, reduces relative volume, improves water-reducing rate.By modification, appropriateness is introduced different surfaces tensile active group, has a plurality of active groups on the dispersant molecule main chain that makes, and also has the active group of different hydrophilic on the side chain.In the building-up process, molecular structure distributes, the molecular weight size can be regulated control arbitrarily, the molecular chain of hydrophobic group is shorter, quantity is few, selected comonomer difference when synthetic, molecular composition is also different, because the existence of various hydrophilic radicals, so certain liquid-gas interface active function is arranged, therefore has certain bleed and slow setting.Make its consistency good, not bleed, no excreting water phenomenon, flowing degree of net paste of cement height.
2. pass through lignin sulfonate modified follow-up continued access branch co-poly carboxylic acid, obtain modified polycarboxylic acid cement dispersants based on xylogen, it is little to obtain the volume that the polycarboxylic acid cement dispersants had, the water-reducing rate height, slump-loss is little, excellent characteristic such as late strength of concrete height, and it is good simultaneously to have kept cement adaptability and consistency that lignosulfonic acid salt cement dispersants self has again, not bleed, the advantage of no excreting water phenomenon and cement paste good fluidity.Significantly improved the technical feature of lignosulfonic acid salt cement dispersants, make its every technical indicator all meet or exceed the standard of national regulation high-efficiency cement dispersion agent, turnout maximum in can subrogate country, use the widest naphthalene series high-efficiency water-reducing agent and polycarboxylic acid cement dispersants, cost performance height.
3. the xylogen poly-carboxylic-acid cement dispersant volume of its making is little, the water-reducing rate height, and cement adaptability is good, can significantly improve concrete intensity.At volume is that 1.0% o'clock water-reducing rate can reach 25%, and increase volume then water-reducing rate obviously improves, and is that 1.5% o'clock water-reducing rate can reach 35% at volume, concrete 3d, 7d, 28d, 90d ultimate compression strength improves 85%, 70%, 50% respectively, more than 35%, concrete surface does not have bleeding, no air pocket, alkali content is low, chloride ion-containing not, the cement products, the dispersing agent performance that adapt to plurality of specifications, model are stable, and long storage does not have layering, does not have precipitation, do not have crystallization winter.Under lower volume, just can obtain the high slump, and have good slump hold facility.
4. production method is simple, and starting material are easy to get, and production cost is lower, is easy to suitability for industrialized production.
Embodiment
Below the present invention is described in further detail by embodiment:
The preparation method of modified lignin poly-carboxylic-acid cement dispersant is characterized in that comprising following composition by weight and step:
A. get solid content and be 30～60 parts of the lignosulfonic acid salt brine solutions of 20-40%, drop into reactor, stirring is warmed up to 50～80 ℃, drop into 5～9 parts of sodium dichromate 99s more successively, 10～20 parts of polyvinyl alcohol, 5～18 parts in vinylformic acid, 0.1～3 part of initiator, under 80～100 ℃ of temperature, reacted 3-5 hour, obtain the modified lignin mahogany sulfonate aqueous solution.
B. with maleic anhydride 10-35 part, vinylformic acid hydroxyl ester 20-60 part, vinylbenzene 10-25 part and superoxide 1-5 part are dropped in the reactor, stir and heat up, and 80 ℃-160 ℃ reactions 2-6 hour down, obtain poly carboxylic acid modified dose;
C. with water 200-400 part; ammonium persulphate 10-40 part; sulphite 10-18 part adds in the reactor successively, is warming up to 40-60 ℃, charges into rare gas element; under the protection of inert gas condition, add modified lignin mahogany sulfonate aqueous solution 10-40 part; keep 70-90 ℃ of temperature, reacted 3-5 hour, add poly carboxylic acid modified dose of 5-30 part again; reacted 1-2 hour, and promptly obtained modified lignin poly-carboxylic-acid cement dispersant.
Initiator of the present invention is a persulphate; Superoxide is hydrogen peroxide or perborate or percarbonate; Rare gas element is nitrogen or neon.
Embodiment 1
Getting solid content is 40 parts of 20-40% lignosulfonic acid salt brine solutions, drops into reactor, stirs and is warmed up to 60 ℃, drops into 6 parts of sodium dichromate 99s more successively, 15 parts of polyvinyl alcohol, 10 parts in vinylformic acid, 0.1 part of persulphate, under 90 ℃ of temperature, reacted 4 hours, obtain the modified lignin mahogany sulfonate aqueous solution.
Embodiment 2
Getting solid content is 30 parts of 20-40% lignosulfonic acid salt brine solutions, drops into reactor, stirs and is warmed up to 60 ℃, drops into 5 parts of sodium dichromate 99s more successively, 10 parts of polyvinyl alcohol, 5 parts in vinylformic acid, 1 part of persulphate, under 90 ℃ of temperature, reacted 5 hours, obtain the modified lignin mahogany sulfonate aqueous solution.
Embodiment 3
Getting solid content is 60 parts of 20-40% lignosulfonic acid salt brine solutions, drops into reactor, stirs and is warmed up to 60 ℃, drops into 9 parts of sodium dichromate 99s more successively, 20 parts of polyvinyl alcohol, 18 parts in vinylformic acid, 3 parts of persulphates, under 100 ℃ of temperature, reacted 4 hours, obtain the modified lignin mahogany sulfonate aqueous solution.
Embodiment 4
With 20 parts of maleic anhydrides, 30 parts of vinylformic acid hydroxyl esters, 3 parts of 15 parts of vinylbenzene and hydrogen peroxide drop in the reactor, stir and heat up, and react 8 hours down at 80 ℃, obtain poly carboxylic acid modified dose.
Embodiment 5
With 10 parts of maleic anhydrides, 20 parts of vinylformic acid hydroxyl esters, 5 parts of 10 parts of vinylbenzene and perborate drop in the reactor, stir and heat up, and react 7 hours down at 90 ℃, obtain poly carboxylic acid modified dose.
Embodiment 6
With 35 parts of maleic anhydrides, 60 parts of vinylformic acid hydroxyl esters, 1 part of 25 parts of vinylbenzene and percarbonate drop in the reactor, stir and heat up, and react 3 hours down at 160 ℃, obtain poly carboxylic acid modified dose.
Embodiment 7
With 300 parts in water, 25 parts of ammonium persulphates, S-WAT adds in the reactor for 30 parts successively, is warming up to 50 ℃, charges into nitrogen, add 20 parts of embodiment 1 prepared modified lignin mahogany sulfonates then, keep 80 ℃ of temperature, reacted 4 hours, add 20 parts of embodiment 4 prepared poly carboxylic acid modified dose of cement dispersants again, reacted 1.5 hours, and promptly obtained modified lignin poly-carboxylic-acid cement dispersant.
Embodiment 8
With 200 parts in water, 10 parts of ammonium persulphates, S-WAT adds in the reactor for 20 parts successively, is warming up to 50 ℃, charges into nitrogen, add 10 parts of embodiment 2 prepared modified lignin mahogany sulfonates then, keep 80 ℃ of temperature, reacted 4 hours, add embodiment 5 prepared poly carboxylic acid modified dose 5 parts again, reacted 1 hour, and promptly obtained modified lignin poly-carboxylic-acid cement dispersant.
Embodiment 9
With 400 parts in water, 40 parts of ammonium persulphates, S-WAT adds in the reactor for 60 parts successively, is warming up to 60 ℃, charges into nitrogen, add 40 parts of embodiment 4 prepared modified lignin mahogany sulfonates then, keep 80 ℃ of temperature, reacted 4 hours, add embodiment 6 prepared poly carboxylic acid modified dose 30 parts again, reacted 2 hours, and promptly obtained modified lignin poly-carboxylic-acid cement dispersant.
Embodiment 10
NP type modified lignin poly-carboxylic-acid cement dispersant volume of the present invention is to the influence of clean slurry degree of mobilization.
Clean slurry test:
Clean slurry degree of mobilization test (GB/T 8077-2000): adopt reference cement, test the clean slurry degree of mobilization that NP type modified lignin poly-carboxylic-acid cement dispersant of the present invention, certain naphthalene series high-efficiency water-reducing agent and commercially available high-efficiency water-reducing agent of poly-carboxylic acid are mixed back cement respectively according to GB8077-87, and carrying out Technological Economy relatively, it the results are shown in Table 1, table 2.
Table 1: the clean slurry slump test of mixing NP type modified lignin poly-carboxylic-acid cement dispersant
Table 2: technical economy relatively
| The cement dispersants kind | Consistency | Fast hard phenomenon | Cementability | Bleeding | Pumping | Price |
| NP type dispersion agent | Good | Do not have | Not bonding | Do not have | Good | Rationally |
| Naphthalene water reducer | Generally | Do not have | Generally | Have | Difference | More expensive |
| Poly-carboxylic water reducer | Difference | Seriously | Seriously | Have | Generally | Expensive |
From table 1, table 2 as can be known, NP type modified lignin poly-carboxylic-acid cement dispersant of the present invention is compared with the high-efficiency water-reducing agent of poly-carboxylic acid that sell in naphthalene series high-efficiency water-reducing agent and market, there are better dispersiveness and dispersion stabilization and NP type modified lignin poly-carboxylic-acid cement dispersant to overcome the shortcoming that high-efficiency water-reducing agent of poly-carboxylic acid can not be compatible with other admixtures and cementability is big, no bleeding, good, the reasonable price of pumping are ideal high-efficiency cement dispersion agents comparatively.
Concrete test:
Gelatinous material adopts ordinary Portland cement, and fine aggregate adopts medium sand (fineness modulus 2.9, silt content 0.2%), and coarse aggregate uses rubble (particle diameter 5-25mm, continuous grade, voidage 43%).Concrete mix sees Table 3.
Table 3: concrete mix
Under above-mentioned condition, use NP type lignin modification poly-carboxylic-acid cement dispersant mix concrete, and measure the concrete slump, air content, slump retention value, and with certain naphthalene series high-efficiency water-reducing agent and commercially available high-efficiency water-reducing agent of poly-carboxylic acid relatively, it the results are shown in Table 4.
Table 4: the concrete test of mixing NP type modified lignin poly-carboxylic-acid cement dispersant
Annotate: slump retention value: leave standstill the slump/initial slump * 100% after 60 minutes
Above-mentioned test shows, adopt the NP type modified lignin poly-carboxylic-acid cement dispersant of the present invention's preparation under lower volume, just can obtain the high slump, and has good slump hold facility, the concrete pumping of preparation is good, intensity is high, adapts to city commerical ready-mixed concrete production especially.
Claims (8)
1. the preparation method of modified lignin poly-carboxylic-acid cement dispersant is characterized in that comprising following composition by weight and step:
A. get solid content and be 30～60 parts of the lignosulfonic acid salt brine solutions of 20-40%, drop into reactor, stirring is warmed up to 50～80 ℃, drop into 5～9 parts of sodium dichromate 99s more successively, 10～20 parts of polyvinyl alcohol, 5～18 parts in vinylformic acid, 0.1～3 part of initiator, under 80～100 ℃ of temperature, reacted 3-5 hour, obtain the modified lignin mahogany sulfonate aqueous solution;
B. with maleic anhydride 10-35 part, vinylformic acid hydroxyl ester 20-60 part, vinylbenzene 10-25 part and superoxide 1-5 part are dropped in the reactor, stir and heat up, and 80 ℃-160 ℃ reactions 2-6 hour down, obtain poly carboxylic acid modified dose;
C. with water 200-400 part; ammonium persulphate 10-40 part; sulphite 10-18 part adds in the reactor successively, is warming up to 40-60 ℃, charges into rare gas element; under protection of inert gas, add modified lignin mahogany sulfonate aqueous solution 10-40 part; keep 70-90 ℃ of temperature, reacted 3-5 hour, add poly carboxylic acid modified dose of 5-30 part again; reacted 1-2 hour, and promptly obtained modified lignin poly-carboxylic-acid cement dispersant.
2. the preparation method of modified lignin poly-carboxylic-acid cement dispersant according to claim 1, it is characterized in that: 40 parts of lignosulfonic acid salt brine solutions getting solid content and be 20-40%, drop into reactor, stir and be warmed up to 60 ℃, drop into 6 parts of sodium dichromate 99s more successively, 15 parts of polyvinyl alcohol, 10 parts in vinylformic acid, 0.2 part of initiator is under 90 ℃ of temperature, reacted 4 hours, and obtained the modified lignin mahogany sulfonate aqueous solution.
3. the preparation method of modified lignin poly-carboxylic-acid cement dispersant according to claim 1 and 2, it is characterized in that: initiator is a persulphate.
4. the preparation method of modified lignin poly-carboxylic-acid cement dispersant according to claim 1, it is characterized in that: with 20 parts of maleic anhydrides, 40 parts of vinylformic acid hydroxyl esters, 3 parts of 15 parts of vinylbenzene and superoxide, drop in the reactor, stir and heat up, reacted 4 hours down, obtain poly carboxylic acid modified dose at 80 ℃.
5. according to the preparation method of claim 1 or 4 described modified lignin poly-carboxylic-acid cement dispersants, it is characterized in that: superoxide is hydrogen peroxide or perborate or percarbonate.
6. according to the preparation method of claim 1 or 2 or 4 described modified lignin poly-carboxylic-acid cement dispersants; it is characterized in that: with 300 parts in water, 15 parts of ammonium persulphates, S-WAT adds in the reactor for 20 parts successively; be warming up to 50 ℃; charge into rare gas element, under the protection of inert gas condition, add poly carboxylic acid modified dose 20 parts, keep 80 ℃ of temperature; reacted 4 hours; add 20 parts of the modified lignin mahogany sulfonate aqueous solution again, reacted 1.5 hours, promptly obtain modified lignin poly-carboxylic-acid cement dispersant.
7. the preparation method of modified lignin poly-carboxylic-acid cement dispersant according to claim 1, it is characterized in that: rare gas element is nitrogen or neon.
8. the preparation method of modified lignin poly-carboxylic-acid cement dispersant according to claim 6, it is characterized in that: rare gas element is nitrogen or neon.
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| CN102294199B (en) * | 2011-05-16 | 2013-10-30 | 福州大学 | Lignosulfonate grafted copolymer dispersant, preparation technology thereof, and application thereof |
| CN102504138B (en) * | 2011-11-17 | 2014-04-16 | 郑州轻工业学院 | Lignin grafting functional vinyl macromonomer high efficiency water reducer and preparation method thereof |
| CN105731868A (en) * | 2015-12-31 | 2016-07-06 | 文登蓝岛建筑工程有限公司 | Composite water reducer and preparation method thereof |
| CN109912249A (en) * | 2019-04-04 | 2019-06-21 | 湖北合力久盛混凝土有限公司 | High effective and modified water-reducing agent |
| CN111403681B (en) * | 2020-03-10 | 2021-07-06 | 浙江埃登达新能源材料有限公司 | Negative electrode expanding agent for storage battery |
| CN113321440A (en) * | 2021-07-06 | 2021-08-31 | 四川宇砼建材有限公司 | Modified lignosulfonate water reducing agent and preparation method thereof |
| CN115594435B (en) * | 2022-10-18 | 2023-09-29 | 东南大学 | Modified lignin dispersing agent material and preparation method and application thereof |
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| CN1693342A (en) * | 2005-04-30 | 2005-11-09 | 江苏工业学院 | Process for preparing modified lignocellulose sulfonate graft copolymer |
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| 木质素磺酸盐与丙烯酸类单体的接枝共聚研究. 李建法等.林产化学与工业，第24卷第3期. 2004 |
| 木质素磺酸盐与丙烯酸类单体的接枝共聚研究. 李建法等.林产化学与工业，第24卷第3期. 2004 * |
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