CN107043442B - High-thin arch dam, high water reduction, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent - Google Patents
High-thin arch dam, high water reduction, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
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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
- 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 discloses a kind of high-thin arch dam, high water reduction, the preparation methods of anti-stick soil type modified naphthalene series water-reducing agent, include the following steps: naphthalene water reducer is soluble in water, adjust pH value of solution, it heats up and carries out hydrolysis, then calcium hydroxide is added and stirs, supernatant is filtered to take, is neutralized to pH=7 with phosphoric acid to get linear parent N；A certain amount of initiator A is added into the aqueous solution of linear parent N, then the aqueous solution dissolved with a certain amount of monomer B, monomer C and monomer D and the aqueous solution of the monomer B dissolved with chain-transferring agent T, the initiator A of surplus and surplus are respectively dropped into, after being stirred to react 0.5-1h, cool down up to final products.Water-reducing agent product water-reducing rate produced by the present invention is high, slump retaining is good, and stability is good, can further decrease dependence of the current water-reducing agent to ethylene oxide, the clay adaptability of current water-reducing agent is improved, water-reducing agent industry is promoted to develop to the direction of high quality, high level, low energy consumption and low cost.
Description
Technical field
The invention belongs to technical field of concrete additives, and in particular to a kind of high-thin arch dam, high water reduction, anti-stick soil type are modified
The preparation method of naphthalene water reducer.
Background technique
In concrete using additive be it is a kind of it is putative can be improved intensity, improve working performance of concrete,
Save the effective measures of energy consumption.Water-reducing agent is divided into three generations at present, and compare mainstream is polycarboxylic acid super-plasticizer, but polycarboxylic acids is super
Plasticiser has the shortcomings that very sensitive to clay, expensive and various regions substrate adaptability is poor.With current national basis
The progress of Facilities Construction, national sand material quality condition is very bad, and clay content is larger, causes to polycarboxylic acid super-plasticizer
Adsorbance is very big, undoubtedly will increase the preparation cost of its concrete in this way.The super modeling of the polycarboxylic acids of 40% concentration on the market at present
In agent the such polymeric monomer of methyl allyl polyoxyethylene ether accounted for 35% even more than, therefore methacrylic polyoxyethylene
The price decision of the ether price of its polycarboxylic acids, and since its price can not have always been high any more, it is super that this just seriously constrains polycarboxylic acids
The popularization and use of plasticiser.In addition, being prepared when preparing high-grade concrete and high grade prefabricated components using polycarboxylic acids
The viscosity of concrete out is very big, is unfavorable for the normal construction of concrete, and naphthalene water reducer can not only make high grade mixed
The viscosity for coagulating soil is lower, and can also be to well adapting to property of clay, and price is also relatively cheap.But naphthalene water reducer and poly-
Carboxylic acid super plasticizer is compared, and haves the shortcomings that water-reducing rate is relatively low and concrete retention property is bad.But as long as overcoming this disadvantage,
Naphthalene water reducer will have a good application prospect.
Publication No. CN105271887A and CN103804620A individually disclose a kind of naphthalene water reducer, the basic class of the two
Seemingly, the main distinction be adsorption group one position for having used carboxylate radical one to use phosphate radical, but having introduced all be
It on naphthalene nucleus, and is once introduced on naphthalene nucleus and there is space steric effect and charge effect, will existed to polycondensation and negatively affect,
The strong deferred action of phosphate radical can seriously affect entringite crystal form simultaneously.The patent of Publication No. CN101759393A uses naphthalene system
Water-reducing agent is compounded with oxidation-etherification starch, the patent of Publication No. CN105236789A on the basis of naphthalene water reducer,
Phenol ring is introduced, due to its adsorption group or sulfonate radical, naphthalene system rigid structure is not changed, therefore the naphthalene system prepared
The water-reducing rate and function of slump protection of water-reducing agent will not be very superior.The patent of Publication No. CN105807186A uses phenol to be modified
The main structure of naphthalene water reducer, is then compounded with black liquid, and the main component of black liquid is sulfomethylated lignin
Hydrochlorate substance and carbohydrate, main function are slow settings, if concrete is made to keep effect good simply by deferred action
Words, it is possible that the setting time of concrete is also less than, but slump without the case where occur, here it is with
Retarder is come the drawbacks of adjusting concrete retention property.
Therefore naphthalene water reducer and the additive of polycarboxylic acid super-plasticizer advantage are had both in preparation becomes this field urgent need to resolve
A technical problem.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series
The preparation method of water-reducing agent, this method are adjusted from the structure of additive, and repetition stability is good, and production cost is low, are made
Modified naphthalene series water-reducing agent product water-reducing rate it is high, slump retaining is good, and stability is good, can further decrease current water-reducing agent to epoxy second
The dependence of alkane, improves the clay adaptability of current water-reducing agent, promotes water-reducing agent industry to high quality, high level, low energy consumption and low
The direction of cost is developed.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of high-thin arch dam, high water reduction, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent, which is characterized in that including such as
Lower synthesis step:
Naphthalene water reducer (NSF) is soluble in water, pH value of solution is adjusted to 3-5 with sour S, then heats to 130-150 DEG C
3-5h is hydrolyzed, calcium hydroxide is added, stirs 5~15min, filters to take supernatant, being neutralized to pH with phosphoric acid is 7, i.e.,
Obtain the aqueous solution of linear parent N；At 65-80 DEG C, initiator A is added into the aqueous solution of linear parent N, the amount of addition is to draw
The 20-40% of agent A total amount is sent out, is stirred 20-40 minutes；Instill the first aqueous solution and the second aqueous solution simultaneously in 1-2h, then
After being stirred for reaction 0.5-1h, cooling is the high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent；
Wherein, first aqueous solution is the aqueous solution dissolved with monomer B, monomer C and monomer D, wherein the additional amount of monomer B
For the 10-20% of monomer B total amount；Second aqueous solution is dissolved with chain-transferring agent T, the initiator A of surplus and surplus
The aqueous solution of monomer B；
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10-15；
The general structure of the threadiness parent N are as follows:
Wherein, n=10-15；
The general structure of the monomer B are as follows:
R in formula1For H or-CH3, R2For-CH2O- or-CH2CH2O-, a=5-10, b=0-3；
The general structure of the monomer C are as follows:
R in formula1For H or-CH3；
The general structure of the monomer D are as follows:
R in formula3For-OCH3、-OCH2CH2OH、-OCH2CH(CH3) OH ,-OCO-CH=CH2Or
Embodiment as a further preference, the molecular weight of the modified naphthalene series water-reducing agent are 20000-35000, molecule
Amount breadth coefficient is 1.5-2.0.
Embodiment as a further preference, the general structure of the modified naphthalene series water-reducing agent are as follows:
N:c:d:e is 10:20-40:0-8:0-3 in formula.
Embodiment as a further preference, the acid S are phosphoric acid (85%) or sulfuric acid.
Embodiment as a further preference, the initiator A be benzoyl peroxide, ammonium persulfate, potassium peroxydisulfate,
One or both of sodium peroxydisulfate.
Embodiment as a further preference, the mole of the initiator A and linear parent N, monomer B, monomer C and
The ratio of monomer D integral molar quantity is 1:8-25；The addition mole and described monomer B, C and D addition mole of the threadiness parent N
The ratio of amount is 1:1-3:20-40:1-8.
Embodiment as a further preference, the chain-transferring agent T are methylpropene sodium sulfonate, thioacetic acid, sulfydryl
One or both of propionic acid and sodium hypophosphite.
Embodiment as a further preference, the mole of the chain-transferring agent T and linear parent N, monomer B, monomer C
Ratio with monomer D integral molar quantity is 1:6-15.
The positive effect of the present invention: the modified naphthalene series water-reducing agent prepared using this method, not only with naphthalene water reducer
Advantage (has extraordinary adaptability, the high grade coagulation prepared very good to the resistivity of clay to concrete substrate
The cohesiveness of soil is preferable), while viscosity is more much lower than the concrete that polycarboxylic acid super-plasticizer prepares, excellent working performance,
And price is lower than polycarboxylic acid super-plasticizer, can further weaken such polymeric monomer such as methyl allyl polyoxyethylene ether and epoxy second
Influence of the alkane to water-reducing agent price；The advantages that being also equipped with the high water reducing rate and high-collapse-retentivity energy of polycarboxylic acid super-plasticizer simultaneously.
Specific embodiment
Below to a preferred embodiment of the present invention will be described in detail.
Illustrate: the number content of each component refers to molfraction in following embodiment.Calcium hydroxide in each embodiment
Additional amount is usually excessive, until mixed solution system shows alkaline (pH is preferably 9 or so).
Embodiment 1
The preferred embodiment of the present invention 1 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 with the phosphoric acid that volumetric concentration is 85%, is then heated to
3h is hydrolyzed at 130 DEG C, calcium hydroxide is then added, stirs 10min, filters to take supernatant, be neutralized to pH with phosphoric acid
=7 to get linear parent N；At 65 DEG C, 0.184 part of benzoyl peroxide is added into the aqueous solution of 1 part of linear parent N, stirs
Mix 20 minutes, it then will be dissolved with the aqueous solution of 0.1 part of monomer B, 20 parts of monomer C and 1 part of monomer D and dissolved with 1.54 parts of methyl-props
The aqueous solution of alkene sodium sulfonate, 0.736 part of benzoyl peroxide and 0.9 part of monomer B, while instilling and wherein (being dripped in 1h
Finish), after being then stirred for reaction 0.5h, cooling is the high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, and molecular weight is
20010, molecular weight distribution index 1.8, number LYNP-1.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 2
The preferred embodiment of the present invention 2 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats to and carries out water at 135 DEG C
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 75 DEG C, 1.3 parts of ammonium persulfates are added into the aqueous solution of 1 part of linear parent N, stir 40 minutes, it then will be dissolved with
The aqueous solution of 0.6 part of monomer B, 40 parts of monomer C and 8 parts of monomer D and dissolved with 8.67 parts of thioacetic acid, 5.2 parts of ammonium persulfates and 2.4
The aqueous solution of part monomer B, instills in 2h wherein respectively, and after being then stirred for reaction 1h, the cooling as high-thin arch dam, height subtract
Water type modified naphthalene series water-reducing agent, molecular weight 34850, molecular weight distribution index 2.0, number LYNP-2.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 3
The preferred embodiment of the present invention 3 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with phosphoric acid (85%), then heat at 140 DEG C into
Row hydrolysis 5h, is then added calcium hydroxide, stirs 10min, filter to take supernatant, be neutralized to pH=7 with phosphoric acid to get line
Shape parent N；At 80 DEG C, 0.368 part of potassium peroxydisulfate of addition into the aqueous solution of 1 part of linear parent N, stirring 30 minutes, then
It will be dissolved with the aqueous solution of 0.3 part of monomer B, 40 parts of monomer C and 8 parts of monomer D and dissolved with 3 parts of mercaptopropionic acids, 0.552 part of persulfuric acid
The aqueous solution of potassium and 2.7 parts of monomer B instills in 1.5h wherein respectively, and after being then stirred for reaction 1h, cooling is the height
Guarantor collapses, high water reduction type modified naphthalene series water-reducing agent, molecular weight 30025, molecular weight distribution index 1.5, number LYNP-3.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 4
The preferred embodiment of the present invention 4 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats to and carries out water at 150 DEG C
3h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 65 DEG C, 2.6 parts of sodium peroxydisulfates are added into the aqueous solution of 1 part of linear parent N, stir 40 minutes, it then will be dissolved with
The aqueous solution of 0.2 part of monomer B, 20 parts of monomer C and 1 part of monomer D and dissolved with 5 parts of sodium hypophosphites, 3.6 parts of sodium peroxydisulfates and
The aqueous solution of 0.8 part of monomer B instills in 1h wherein respectively, and after being then stirred for reaction 1h, cooling is the high guarantor
It collapses, high water reduction type modified naphthalene series water-reducing agent, molecular weight 33250, molecular weight distribution index 2.0, number LYNP-4.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 5
The preferred embodiment of the present invention 5 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with phosphoric acid (85%), then heat at 130 DEG C into
Row hydrolysis 5h, is then added calcium hydroxide, stirs 10min, filter to take supernatant, be neutralized to pH=7 with phosphoric acid to get line
Shape parent N；At 75 DEG C, 1 part of benzoyl peroxide and 0.5 part of ammonium persulfate is added into the aqueous solution of 1 part of linear parent N,
Stirring 30 minutes, then will be dissolved with the aqueous solution of 0.5 part of monomer B, 20 parts of monomer C and 5 parts of monomer D and dissolved with 1 part of methyl-prop
Alkene sodium sulfonate, 2 parts of thioacetic acid, 2 parts of benzoyl peroxides, 1.5 parts of ammonium persulfates and 2.5 parts of monomer B aqueous solution, respectively
It is instilled in 1h wherein, after being then stirred for reaction 0.5h, cooling is the high-thin arch dam, high water reduction type modified naphthalene series diminishing
Agent, molecular weight 20078, molecular weight distribution index 1.9, number LYNP-5.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 6
The preferred embodiment of the present invention 6 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 with the concentrated sulfuric acid, then heats to and carries out water at 150 DEG C
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 80 DEG C, 1.3 parts of benzoyl peroxides and 0.65 part of potassium peroxydisulfate is added into the aqueous solution of 1 part of linear parent N, stirs
Mix 30 minutes, it then will be dissolved with the aqueous solution of 0.6 part of monomer B, 30 parts of monomer C and 8 parts of monomer D and dissolved with 2 parts of metering system sulphurs
Sour sodium, 2 parts of mercaptopropionic acids, 4 parts of benzoyl peroxides, 0.55 part of potassium peroxydisulfate and 2.4 parts of monomer B aqueous solution, respectively in 1h
Wherein, after being then stirred for reaction 1h, cool down the as high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent for interior instillation, point
Son amount is 22520, molecular weight distribution index 1.6, number LYNP-6.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 7
The preferred embodiment of the present invention 7 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with phosphoric acid (85%), then heat at 140 DEG C into
Row hydrolysis 4h, is then added calcium hydroxide, stirs 10min, filter to take supernatant, be neutralized to pH=7 with phosphoric acid to get line
Shape parent N；At 80 DEG C, 0.5 part of benzoyl peroxide and 0.4 part of persulfuric acid is added into the aqueous solution of 1 part of linear parent N
Sodium stirs 40 minutes, then will be dissolved with the aqueous solution of 0.6 part of monomer B, 20 parts of monomer C and 5 parts of monomer D and dissolved with 3 parts of methyl-props
Alkene sodium sulfonate, 2 parts of sodium hypophosphites, 1.5 parts of benzoyl peroxides, 0.6 part of sodium peroxydisulfate and 2.4 parts of monomer B aqueous solution, point
It is not instilled in 2h wherein, after being then stirred for reaction 1h, cooling is the high-thin arch dam, high water reduction type modified naphthalene series diminishing
Agent, molecular weight 29985, molecular weight distribution index 1.6, number LYNP-7.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 8
The preferred embodiment of the present invention 8 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with phosphoric acid (85%), then heat at 140 DEG C into
Row hydrolysis 3h, is then added calcium hydroxide, stirs 10min, filter to take supernatant, be neutralized to pH=7 with phosphoric acid to get line
Shape parent N；At 65 DEG C, 1 part of ammonium persulfate and 0.6 part of potassium peroxydisulfate, stirring is added into the aqueous solution of 1 part of linear parent N
It 30 minutes, then will be dissolved with the aqueous solution of 0.3 part of monomer B, 30 parts of monomer C and 8 parts of monomer D and dissolved with 2 parts of thioacetic acid, 2 parts
Mercaptopropionic acid, 0.4 part of ammonium persulfate, 2 parts of potassium peroxydisulfates and 2.7 parts of monomer B aqueous solution, instilled in 1.5h respectively wherein,
Then after being stirred for reaction 1h, the cooling as high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, molecular weight 33254,
Molecular weight distribution index is 1.5, number LYNP-8.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 9
The preferred embodiment of the present invention 9 provides the preparation side of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats to and carries out water at 150 DEG C
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 70 DEG C, 0.6 part of ammonium persulfate and 0.6 part of sodium peroxydisulfate, stirring 30 is added into the aqueous solution of 1 part of linear parent N
Minute, it then will be dissolved with the aqueous solution of 0.3 part of monomer B, 40 parts of monomer C and 5 parts of monomer D and dissolved with 3 parts of mercaptopropionic acids, 2 parts times
Sodium phosphite, 1 part of ammonium persulfate, 0.8 part of sodium peroxydisulfate and 0.7 part of monomer B aqueous solution, instilled in 2h respectively wherein, so
After be stirred for reaction 1h after, cooling be the high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, molecular weight 26658, divide
Son amount breadth coefficient is 1.8, number LYNP-9.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 10
The preferred embodiment of the present invention 10 provides the preparation of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with the concentrated sulfuric acid, then heats to and carries out water at 145 DEG C
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 80 DEG C, 2 parts of potassium peroxydisulfates and 0.2 part of sodium peroxydisulfate is added into the aqueous solution of 1 part of linear parent N, stirs 40 points
Clock, then by dissolved with the aqueous solution of 0.2 part of monomer B, 40 parts of monomer C and 5 parts of monomer D and dissolved with 3 parts of thioacetic acid, 5 parts times it is sub-
Sodium phosphate, 2.2 parts of potassium peroxydisulfates, 1.1 parts of sodium peroxydisulfates and 0.8 part of monomer B aqueous solution, instilled in 2h respectively wherein, so
After be stirred for reaction 0.5h after, cooling be the high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, molecular weight 34522,
Molecular weight distribution index is 1.9, number LYNP-10.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 11
The preferred embodiment of the present invention 11 provides the preparation of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with phosphoric acid (85%), then heat at 130 DEG C into
Row hydrolysis 4h, is then added calcium hydroxide, stirs 10min, filter to take supernatant, be neutralized to pH=7 with phosphoric acid to get line
Shape parent N；At 80 DEG C, 0.5 part of benzoyl peroxide and 0.7 part of persulfuric acid is added into the aqueous solution of 1 part of linear parent N
Ammonium stirs 30 minutes, then will be dissolved with the aqueous solution of 0.6 part of monomer B, 40 parts of monomer C and 1 part of monomer D and dissolved with 5 parts phosphorous
Sour sodium, 4 parts of benzoyl peroxides, 0.8 part of ammonium persulfate and 2.4 parts of monomer B aqueous solution, instilled in 1h respectively wherein, so
After be stirred for reaction 0.5h after, cooling be the high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, molecular weight 22350,
Molecular weight distribution index is 1.6, number LYNP-11.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 12
The preferred embodiment of the present invention 12 provides the preparation of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with phosphoric acid (85%), then heat at 140 DEG C into
Row hydrolysis 5h, is then added calcium hydroxide, stirs 10min, filter to take supernatant, be neutralized to pH=7 with phosphoric acid to get line
Shape parent N；At 75 DEG C, 1 part of ammonium persulfate and 0.8 part of potassium peroxydisulfate, stirring is added into the aqueous solution of 1 part of linear parent N
It 30 minutes, then will be dissolved with the aqueous solution of 0.5 part of monomer B, 20 parts of monomer C and 1 part of monomer D and dissolved with 7 parts of thioacetic acid, 1 part
The aqueous solution of ammonium persulfate, 0.2 part of potassium peroxydisulfate and 2.5 parts of monomer B, instills wherein in 1h respectively, is then stirred for reacting
After 0.5h, cooling is the high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, molecular weight 32500, molecular weight distribution system
Number is 2.0, number LYNP-12.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 13
The preferred embodiment of the present invention 13 provides the preparation of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 with the concentrated sulfuric acid, then heats to and carries out water at 145 DEG C
3h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 70 DEG C, 1 part of potassium peroxydisulfate and 1 part of sodium peroxydisulfate is added into the aqueous solution of 1 part of linear parent N, stirs 40 minutes,
It then will be dissolved with the aqueous solution of 0.2 part of monomer B, 30 parts of monomer C and 5 parts of monomer D and dissolved with 3 parts of mercaptopropionic acids, 1 part of persulfuric acid
The aqueous solution of potassium, 2 parts of sodium peroxydisulfates and 0.8 part of monomer B, instills in 1.5h wherein respectively, after being then stirred for reaction 1h, drop
The temperature as high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, molecular weight 28570, molecular weight distribution index 1.9,
Number LYNP-13.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 14
The preferred embodiment of the present invention 14 provides the preparation of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 with phosphoric acid (85%), then heat at 130 DEG C into
Row hydrolysis 3h, is then added calcium hydroxide, stirs 10min, filter to take supernatant, be neutralized to pH=7 with phosphoric acid to get line
Shape parent N；At 70 DEG C, 0.2 part of benzoyl peroxide and 0.25 part of persulfuric acid is added into the aqueous solution of 1 part of linear parent N
Sodium stirs 40 minutes, then will be dissolved with the aqueous solution of 0.6 part of monomer B, 40 parts of monomer C and 8 parts of monomer D and dissolved with 7 parts of methyl-props
Alkene sodium sulfonate, 0.25 part of benzoyl peroxide, 0.8 part of sodium peroxydisulfate and 2.4 parts of monomer B aqueous solution, instilled in 2h respectively
Wherein, after being then stirred for reaction 1h, cooling is the high-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, and molecular weight is
25400, molecular weight distribution index 1.7, number LYNP-14.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 15
The preferred embodiment of the present invention 15 provides the preparation of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats to and carries out water at 140 DEG C
5h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 80 DEG C, 1.2 parts of ammonium persulfates are added into the aqueous solution of 1 part of linear parent N, stir 20 minutes, it then will be dissolved with
The aqueous solution of 0.1 part of monomer B, 20 parts of monomer C and 1 part of monomer D and dissolved with 5.5 parts of sodium hypophosphites, 2.8 parts of ammonium persulfates and
The aqueous solution of 0.9 part of monomer B instills in 1h wherein respectively, and after being then stirred for reaction 0.5h, cooling is the high guarantor
It collapses, high water reduction type modified naphthalene series water-reducing agent, molecular weight 29855, molecular weight distribution index 1.5, number LYNP-15.
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Embodiment 16
The preferred embodiment of the present invention 16 provides the preparation of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent
Method, specifically:
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with the concentrated sulfuric acid, then heats to and carries out water at 150 DEG C
5h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, is neutralized to pH=7 with phosphoric acid to get linear female
Body N；At 65 DEG C, 0.9 part of potassium peroxydisulfate is added into the aqueous solution of 1 part of linear parent N, stirs 40 minutes, it then will be dissolved with
The aqueous solution of 0.5 part of monomer B, 30 parts of monomer C and 5 parts of monomer D and dissolved with 2 parts of thioacetic acid, 2.5 parts of mercaptopropionic acids, 2.1 parts of mistakes
The aqueous solution of potassium sulfate and 2.5 parts of monomer B instills in 2h wherein respectively, and after being then stirred for reaction 1h, cooling is described
High-thin arch dam, high water reduction type modified naphthalene series water-reducing agent, molecular weight 32540, molecular weight distribution index 1.8, number LYNP-
16。
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=15；
The structural formula of the monomer B are as follows:
The structural formula of the monomer C are as follows:
The structural formula of the monomer D are as follows:
Comparative example 1
The crude naphthalene of 1.2mol is heated to 150 DEG C, the sulfonating reaction that 98% concentrated sulfuric acid carries out 3h is added, is then cooled to
120 DEG C, the hydrolysis of 1h occurs, is then cooled to 90 DEG C, the formalin of 1.2mol is added, the condensation reaction at 100 DEG C
5h, end of reaction, is added in sodium hydroxide solution and pH to 7-8 is to get to conventional naphthalene water reducer, number NF-DB.
Comparative example 2
220g methyl allyl polyoxyethylene ether (M=2400) and 150g water are put into four-hole boiling flask, stirring in water bath adds
Heat is to 60 DEG C.3g thioacetic acid is added in 60g water and is configured to solution A, 23g acrylic acid is configured to monomer with 35g water and is mixed
Object solution B.After polymeric monomer is completely dissolved, 2g ammonium persulfate is poured into four-hole bottle, starts while being added dropwise solution A and B, and divide
It Di Jia not 3h, 3.5h.After completion of dropwise addition, isothermal reaction 1h.40 DEG C are cooled to hereinafter, the hydroxide that mass fraction is 30% is added
Sodium solution is until pH=7.Moisturizing obtains the polycarboxylic acid super-plasticizer product that concentration is 40%, number PC-DB.
Experiment effect:
Test is carried out according to GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", W/C=0.29, volume
To roll over solid volume.Test determines each water-reducing agent when reference cement mini-slump extension is 260 ± 5mm, required each water-reducing agent
Solid volume is rolled over, while testing and being 2% in montmorillonite volume, when mini-slump extension is 260 ± 5mm, the folding of required water-reducing agent is solid
Volume.And select naphthalene water reducer NF-DB and polycarboxylic acid super-plasticizer PC-DB as a comparison case, specific test result is shown in Table 1.
Diminishing, holding and the anti-Property of Clay result of the different water-reducing agent samples of table 1
As can be seen from Table 1, the modified naphthalene series water-reducing agent prepared using method of the present invention, water-reducing rate compare naphthalene
Based water reducer is much higher, and its gradual loss is more much smaller than naphthalene water reducer, subtracts with the polycarboxylic acids using aqua-solution method preparation
Aqua is compared, in the presence of having montmorillonite, it is anti-stick soil ability it is better than polycarboxylate water-reducer, and clay there are the case where
Under, net slurry retention property is superior.Therefore there is high water reduction, high-thin arch dam and highly resistance using the modified naphthalene water reducer of the method
The performance of clay.More excellent than polycarboxylic acids in anti-stick earthwork face performance, performance is than traditional naphthalene system diminishing in terms of diminishing and holding
Agent is excellent.
It is above-described to be merely a preferred embodiment of the present invention, it should be understood that the explanation of above embodiments is only used
In facilitating the understanding of the method and its core concept of the invention, it is not intended to limit the scope of protection of the present invention, it is all of the invention
Any modification for being made within thought and principle, equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. the preparation method of a kind of high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent, which is characterized in that including as follows
Synthesis step:
Naphthalene water reducer (NSF) is soluble in water, pH value of solution is adjusted to 3-5 with sour S, then heats to 130-150 DEG C of progress
3-5h is hydrolyzed, calcium hydroxide is added, 5~15min is stirred, filters to take supernatant, being neutralized to pH with phosphoric acid is 7 to get line
The aqueous solution of shape parent N；At 65-80 DEG C, initiator A is added into the aqueous solution of linear parent N, the amount of addition is initiator
The 20-40% of A total amount is stirred 20-40 minutes；The first aqueous solution and the second aqueous solution are instilled simultaneously and are dripped in 1-2h
Finish, after being then stirred for reaction 0.5-1h, cooling is the high-thin arch dam, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent；
Wherein, first aqueous solution is the aqueous solution dissolved with monomer B, monomer C and monomer D, and wherein the additional amount of monomer B is single
The 10-20% of body B total amount；Second aqueous solution is the monomer B dissolved with chain-transferring agent T, the initiator A of surplus and surplus
Aqueous solution；
The structural formula of the naphthalene water reducer NSF are as follows:
Wherein, n=10-15；
The general structure of the threadiness parent N are as follows:
Wherein, n=10-15；
The general structure of the monomer B are as follows:
R in formula1For H or-CH3, R2For-CH2O- or-CH2CH2O-, a=5-10, b=0-3；
The general structure of the monomer C are as follows:
R in formula1For H or-CH3；
The general structure of the monomer D are as follows:
R in formula3For-OCH3、-OCH2CH2OH、-OCH2CH(CH3) OH ,-OCO-CH=CH2Or
2. the preparation method of a kind of high-thin arch dam according to claim 1, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized by: the molecular weight of the modified naphthalene series water-reducing agent is 20000-35000, molecular weight distribution index 1.5-2.0.
3. the preparation method of a kind of high-thin arch dam according to claim 1, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized by: the general structure of the modified naphthalene series water-reducing agent are as follows:
N:c:d:e is 10:20-40:0-8:0-3 in formula.
4. the preparation method of a kind of high-thin arch dam according to claim 1, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized by: the acid S is sulfuric acid.
5. the preparation method of a kind of high-thin arch dam according to claim 1, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized by: the initiator A is one of benzoyl peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate or two
Kind.
6. the preparation method of a kind of high-thin arch dam according to claim 1, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized by: the mole of the initiator A and the ratio of linear parent N, monomer B, monomer C and monomer D integral molar quantity are
1:8-25；The ratio that mole is added in the addition mole of the threadiness parent N and described monomer B, C and D is 1:1-3:20-
40:1-8。
7. the preparation method of a kind of high-thin arch dam according to claim 1, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized by: the chain-transferring agent T is one in methylpropene sodium sulfonate, thioacetic acid, mercaptopropionic acid and sodium hypophosphite
Kind or two kinds.
8. the preparation method of a kind of high-thin arch dam according to claim 1, high water reduction, anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized by: the ratio of the mole of the chain-transferring agent T and linear parent N, monomer B, monomer C and monomer D integral molar quantity
For 1:6-15.
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| CN103804620A (en) * | 2013-12-30 | 2014-05-21 | 广东红墙新材料股份有限公司 | Naphthalene polycarboxylate slump-keeping water reducing agent and preparation method thereof |
| CN105271887A (en) * | 2015-10-20 | 2016-01-27 | 江苏苏博特新材料股份有限公司 | Slump-retaining modified naphthalene water reducer and preparation method thereof |
| CN106186781A (en) * | 2016-06-29 | 2016-12-07 | 南京瑞迪高新技术有限公司 | A kind of preparation method of modified naphthalene series water-reducing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804620A (en) * | 2013-12-30 | 2014-05-21 | 广东红墙新材料股份有限公司 | Naphthalene polycarboxylate slump-keeping water reducing agent and preparation method thereof |
| CN105271887A (en) * | 2015-10-20 | 2016-01-27 | 江苏苏博特新材料股份有限公司 | Slump-retaining modified naphthalene water reducer and preparation method thereof |
| CN106186781A (en) * | 2016-06-29 | 2016-12-07 | 南京瑞迪高新技术有限公司 | A kind of preparation method of modified naphthalene series water-reducing agent |
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