CN107043442A - High-thin arch dam, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent - Google Patents
High-thin arch dam, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent Download PDFInfo
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- CN107043442A CN107043442A CN201710101277.7A CN201710101277A CN107043442A CN 107043442 A CN107043442 A CN 107043442A CN 201710101277 A CN201710101277 A CN 201710101277A CN 107043442 A CN107043442 A CN 107043442A
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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 diminishing, anti-stick soil type modified naphthalene series water-reducing agent preparation method, comprise the following steps：Naphthalene water reducer is soluble in water, pH value of solution is adjusted, heats up and reaction is hydrolyzed, calcium hydroxide is then added and stirs, filter to take supernatant, pH=7 is neutralized to phosphoric acid, produce wire parent N；A certain amount of initiator A is added into the wire parent N aqueous solution, 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 the 1h of stirring reaction 0.5, cooling produces final products.Water reducer product water-reducing rate produced by the present invention is high, slump retaining is good, and stability is good, can further reduce the existing dependence with water reducer to oxirane, the clay adaptability for now using water reducer is improved, promotes water reducer industry 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 diminishing, anti-stick soil type are modified
The preparation method of naphthalene water reducer.
Background technology
In concrete using additive be it is a kind of it is putative can improve intensity, improve working performance of concrete,
Save the effective measures of energy consumption.Current water reducer is divided into three generations, and compare main flow is polycarboxylic acid super-plasticizer, but polycarboxylic acids is super
Plasticiser has the shortcomings that very sensitive to clay, expensive and various regions base material 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, so can undoubtedly increase the preparation cost of its concrete.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 because its price remains high always, this just seriously constrains polycarboxylic acids and surpassed
Plasticiser is promoted the use of.In addition, when high-grade concrete and high grade prefabricated components is prepared, being prepared 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 mix high grade
The viscosity for coagulating soil is relatively low, and can also be to well adapting to property of clay, and price is also relatively cheap.But naphthalene water reducer is with gathering
Carboxylic acid super plasticizer is compared, and it haves the shortcomings that water-reducing rate is relatively low and concrete retention property is bad.But as long as overcoming this shortcoming,
Naphthalene water reducer will have good application prospect.
Publication No. CN105271887A and CN103804620A individually disclose a kind of naphthalene water reducer, both basic classes
Seemingly, its main distinction is that adsorption group one has used carboxylate radical one to use phosphate radical, but the position introduced be all
On naphthalene nucleus, and 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 have a strong impact on entringite crystal formation simultaneously.Publication No. CN101759393A patent uses naphthalene system
Water reducer is compounded with oxidation-etherification starch, Publication No. CN105236789A patent 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 reducer will not be very superior.Publication No. CN105807186A patent employs phenol to be modified
The agent structure of naphthalene water reducer, is then compounded with black liquid, and the main component of black liquid is sulfomethylated lignin
Barbiturates material and carbohydrate, its main function are slow settings, if making concrete keep effect good simply by deferred action
Words, it is possible that the setting time of concrete be also less than, but slump without situation occur, here it is with
The drawbacks of retarder is to adjust concrete retention property.
Therefore the additive for having both naphthalene water reducer and polycarboxylic acid super-plasticizer advantage is prepared as this area urgent need to resolve
A technical problem.
The content of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of high-thin arch dam, high diminishing, anti-stick soil type modified naphthalene series
The preparation method of water reducer, this method is adjusted from the structure of additive, and repetition stability is good, and production cost is low, is made
Modified naphthalene series water-reducing agent product water-reducing rate it is high, slump retaining is good, and stability is good, can further reduce it is existing with water reducer to epoxy second
The dependence of alkane, improves the clay adaptability for now using water reducer, promotes water reducer industry to high-quality, high-level, low energy consumption and low
The direction of cost is developed.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of high-thin arch dam, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent, it is characterised 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, 130-150 DEG C is then heated to
3-5h is hydrolyzed, calcium hydroxide is added, stirs 5~15min, filters to take supernatant, it is 7 that pH is neutralized to phosphoric acid, i.e.,
Obtain the wire parent N aqueous solution；At 65-80 DEG C, initiator A is added into the wire parent N aqueous solution, the amount of addition is to draw
The 20-40% of agent A total amounts is sent out, is stirred 20-40 minutes；Instill first aqueous solution and second aqueous solution simultaneously in 1-2h, then
It is stirred for after reaction 0.5-1h, cooling is the high-thin arch dam, high diminishing, anti-stick soil type modified naphthalene series water-reducing agent；
Wherein, first aqueous solution is the addition of the aqueous solution, wherein monomer B dissolved with monomer B, monomer C and monomer D
For the 10-20% of monomer B total amounts；Second aqueous solution is dissolved with chain-transferring agent T, the initiator A of surplus and surplus
The monomer B aqueous solution；
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10-15；
The general structure of the wire parent N is：
Wherein, n=10-15；
The general structure of the monomer B is：
R in formula1For H or-CH3, R2For-CH2O- or-CH2CH2O-, a=5-10, b=0-3；
The general structure of the monomer C is：
R in formula1For H or-CH3；
The general structure of the monomer D is：
R in formula3For-OCH3、-OCH2CH2OH、-OCH2CH(CH3) OH ,-OCO-CH=CH2Or
As further preferred embodiment, the molecular weight of the modified naphthalene series water-reducing agent is 20000-35000, molecule
Amount breadth coefficient is 1.5-2.0.
As further preferred embodiment, the general structure of the modified naphthalene series water-reducing agent is：
N in formula:c:d:E is 10:20-40:0-8:0-3.
As further preferred embodiment, the sour S is phosphoric acid (85%) or sulfuric acid.
As further preferred embodiment, the initiator A be benzoyl peroxide, ammonium persulfate, potassium peroxydisulfate,
One or both of sodium peroxydisulfate.
As further preferred embodiment, the mole of the initiator A and wire parent N, monomer B, monomer C and
The ratio of monomer D integral molar quantities is 1:8-25；The addition mole of the wire parent N and described monomer B, C and D addition mole
The ratio of amount is 1:1-3:20-40:1-8.
As further preferred embodiment, the chain-transferring agent T is methylpropene sodium sulfonate, TGA, sulfydryl
One or both of propionic acid and sodium hypophosphite.
It is used as further preferred embodiment, mole and wire parent N, monomer B, the monomer C of the chain-transferring agent T
Ratio with monomer D integral molar quantities 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 to concrete substrate, the resistivity to clay is very good, the high grade coagulation prepared
The cohesiveness of soil is preferable), while the concrete that ratio of viscosities polycarboxylic acid super-plasticizer is prepared is much lower, excellent working performance,
And price is lower than polycarboxylic acid super-plasticizer, it can further weaken such polymeric monomer such as methyl allyl polyoxyethylene ether and epoxy second
Influence of the alkane to water reducer price；The advantages of being also equipped with the high water reducing rate and high-collapse-retentivity energy of polycarboxylic acid super-plasticizer simultaneously.
Embodiment
Below to a preferred embodiment of the present invention will be described in detail.
Explanation：The number content of the component of each in following examples refers to molfraction.Calcium hydroxide in each embodiment
Addition is usually excessive, until mixed solution system display is alkaline (pH is preferably 9 or so).
Embodiment 1
The preferred embodiment of the present invention 1 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 for 85% phosphoric acid with volumetric concentration, then heated to
3h is hydrolyzed at 130 DEG C, calcium hydroxide is then added, stirs 10min, filters to take supernatant, pH is neutralized to phosphoric acid
=7, produce wire parent N；At 65 DEG C, 0.184 part of benzoyl peroxide is added into the 1 part of wire parent N aqueous solution, is stirred
20 minutes are mixed, then by dissolved with 0.1 part of monomer B, 20 parts of monomer C and 1 part of monomer D aqueous solution 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, wherein (is dripped while instilling in 1h
Finish), then it is stirred for after reaction 0.5h, cooling is the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its molecular weight is
20010, molecular weight distribution index is 1.8, numbering LYNP-1.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 2
The preferred embodiment of the present invention 2 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats at 135 DEG C and enters water-filling
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 75 DEG C, 1.3 parts of ammonium persulfates are added into the 1 part of wire parent N aqueous solution, are stirred 40 minutes, then will be dissolved with
0.6 part of monomer B, 40 parts of monomer C and 8 parts of monomer D aqueous solution and dissolved with 8.67 parts of TGAs, 5.2 parts of ammonium persulfates and 2.4
Part monomer B aqueous solution, is instilled wherein in 2h respectively, is then stirred for after reaction 1h, and the cooling as high-thin arch dam, height subtract
Water type modified naphthalene series water-reducing agent, its molecular weight is 34850, and molecular weight distribution index is 2.0, numbering LYNP-2.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 3
The preferred embodiment of the present invention 3 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with phosphoric acid (85%), then heats to and enters at 140 DEG C
Water-filling solution 5h, then adds calcium hydroxide, stirs 10min, filters to take supernatant, pH=7 is neutralized to phosphoric acid, produce line
Shape parent N；At 80 DEG C, 0.368 part of potassium peroxydisulfate of addition into the 1 part of wire parent N aqueous solution, stirring 30 minutes, then
By dissolved with 0.3 part of monomer B, 40 parts of monomer C and 8 parts of monomer D aqueous solution 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, is instilled wherein in 1.5h respectively, is then stirred for after reaction 1h, and cooling is the height
Guarantor is collapsed, high water reducing type modified naphthalene series water-reducing agent, and its molecular weight is 30025, and molecular weight distribution index is 1.5, numbering LYNP-3.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 4
The preferred embodiment of the present invention 4 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats at 150 DEG C and enters water-filling
3h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 65 DEG C, 2.6 parts of sodium peroxydisulfates are added into the 1 part of wire parent N aqueous solution, are stirred 40 minutes, then will be dissolved with
0.2 part of monomer B, 20 parts of monomer C and 1 part of monomer D aqueous solution and dissolved with 5 parts of sodium hypophosphites, 3.6 parts of sodium peroxydisulfates and
0.8 part of the monomer B aqueous solution, is instilled wherein in 1h respectively, is then stirred for after reaction 1h, and cooling is the high guarantor
Collapse, high water reducing type modified naphthalene series water-reducing agent, its molecular weight be 33250, molecular weight distribution index is 2.0, numbering LYNP-4.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 5
The preferred embodiment of the present invention 5 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with phosphoric acid (85%), then heats to and enters at 130 DEG C
Water-filling solution 5h, then adds calcium hydroxide, stirs 10min, filters to take supernatant, pH=7 is neutralized to phosphoric acid, produce line
Shape parent N；At 75 DEG C, 1 part of benzoyl peroxide and 0.5 part of ammonium persulfate are added into the 1 part of wire parent N aqueous solution,
Stirring 30 minutes, then by dissolved with 0.5 part of monomer B, 20 parts of monomer C and 5 parts of monomer D aqueous solution and dissolved with 1 part of methyl-prop
Alkene sodium sulfonate, 2 parts of TGAs, 2 parts of benzoyl peroxides, 1.5 parts of ammonium persulfates and 2.5 parts of monomer the B aqueous solution, respectively
Instill wherein, be then stirred for after reaction 0.5h in 1h, cooling is the high-thin arch dam, high water reducing type modified naphthalene series diminishing
Agent, its molecular weight is 20078, and molecular weight distribution index is 1.9, numbering LYNP-5.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 6
The preferred embodiment of the present invention 6 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 with the concentrated sulfuric acid, then heats at 150 DEG C and enters water-filling
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 80 DEG C, 1.3 parts of benzoyl peroxides and 0.65 part of potassium peroxydisulfate are added into the 1 part of wire parent N aqueous solution, is stirred
30 minutes are mixed, then by dissolved with 0.6 part of monomer B, 30 parts of monomer C and 8 parts of monomer D aqueous solution 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
Interior instillation wherein, is then stirred for after reaction 1h, and cooling is the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its point
Son amount is 22520, and molecular weight distribution index is 1.6, numbering LYNP-6.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 7
The preferred embodiment of the present invention 7 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with phosphoric acid (85%), then heats to and enters at 140 DEG C
Water-filling solution 4h, then adds calcium hydroxide, stirs 10min, filters to take supernatant, pH=7 is neutralized to phosphoric acid, produce line
Shape parent N；At 80 DEG C, 0.5 part of benzoyl peroxide and 0.4 part of persulfuric acid are added into the 1 part of wire parent N aqueous solution
Sodium, is stirred 40 minutes, then by dissolved with 0.6 part of monomer B, 20 parts of monomer C and 5 parts of monomer D aqueous solution 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
Do not instill wherein, be then stirred for after reaction 1h in 2h, cooling is the high-thin arch dam, high water reducing type modified naphthalene series diminishing
Agent, its molecular weight is 29985, and molecular weight distribution index is 1.6, numbering LYNP-7.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 8
The preferred embodiment of the present invention 8 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with phosphoric acid (85%), then heats to and enters at 140 DEG C
Water-filling solution 3h, then adds calcium hydroxide, stirs 10min, filters to take supernatant, pH=7 is neutralized to phosphoric acid, produce line
Shape parent N；At 65 DEG C, 1 part of ammonium persulfate and 0.6 part of potassium peroxydisulfate, stirring are added into the 1 part of wire parent N aqueous solution
30 minutes, then by dissolved with 0.3 part of monomer B, 30 parts of monomer C and 8 parts of monomer D aqueous solution and dissolved with 2 parts of TGAs, 2 parts
Mercaptopropionic acid, 0.4 part of ammonium persulfate, 2 parts of potassium peroxydisulfates and 2.7 parts of monomer B aqueous solution, are instilled wherein in 1.5h respectively,
Then it is stirred for after reaction 1h, cooling is the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its molecular weight is 33254,
Molecular weight distribution index is 1.5, numbering LYNP-8.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 9
The preferred embodiment of the present invention 9 provides a kind of high-thin arch dam, high diminishing, the preparation side of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats at 150 DEG C and enters water-filling
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 70 DEG C, 0.6 part of ammonium persulfate and 0.6 part of sodium peroxydisulfate, stirring 30 are added into the 1 part of wire parent N aqueous solution
Minute, then by dissolved with 0.3 part of monomer B, 40 parts of monomer C and 5 parts of monomer D aqueous solution 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, are instilled wherein, so in 2h respectively
After be stirred for reaction 1h after, cooling be the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its molecular weight be 26658, point
Son amount breadth coefficient is 1.8, numbering LYNP-9.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 10
The preferred embodiment of the present invention 10 provides a kind of high-thin arch dam, high diminishing, the preparation of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with the concentrated sulfuric acid, then heats at 145 DEG C and enters water-filling
4h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 80 DEG C, 2 parts of potassium peroxydisulfates and 0.2 part of sodium peroxydisulfate are added into the 1 part of wire parent N aqueous solution, 40 points are stirred
Clock, then by dissolved with 0.2 part of monomer B, 40 parts of monomer C and 5 parts of monomer D aqueous solution and dissolved with 3 parts of TGAs, 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, are instilled wherein, so in 2h respectively
After be stirred for reaction 0.5h after, cooling be the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its molecular weight be 34522,
Molecular weight distribution index is 1.9, numbering LYNP-10.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 11
The preferred embodiment of the present invention 11 provides a kind of high-thin arch dam, high diminishing, the preparation of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with phosphoric acid (85%), then heats to and enters at 130 DEG C
Water-filling solution 4h, then adds calcium hydroxide, stirs 10min, filters to take supernatant, pH=7 is neutralized to phosphoric acid, produce line
Shape parent N；At 80 DEG C, 0.5 part of benzoyl peroxide and 0.7 part of persulfuric acid are added into the 1 part of wire parent N aqueous solution
Ammonium, is stirred 30 minutes, then by dissolved with 0.6 part of monomer B, 40 parts of monomer C and 1 part of monomer D aqueous solution 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, are instilled wherein, so in 1h respectively
After be stirred for reaction 0.5h after, cooling be the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its molecular weight be 22350,
Molecular weight distribution index is 1.6, numbering LYNP-11.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 12
The preferred embodiment of the present invention 12 provides a kind of high-thin arch dam, high diminishing, the preparation of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with phosphoric acid (85%), then heats to and enters at 140 DEG C
Water-filling solution 5h, then adds calcium hydroxide, stirs 10min, filters to take supernatant, pH=7 is neutralized to phosphoric acid, produce line
Shape parent N；At 75 DEG C, 1 part of ammonium persulfate and 0.8 part of potassium peroxydisulfate, stirring are added into the 1 part of wire parent N aqueous solution
30 minutes, then by dissolved with 0.5 part of monomer B, 20 parts of monomer C and 1 part of monomer D aqueous solution and dissolved with 7 parts of TGAs, 1 part
The aqueous solution of ammonium persulfate, 0.2 part of potassium peroxydisulfate and 2.5 parts of monomer B, is instilled wherein in 1h respectively, is then stirred for reaction
After 0.5h, cooling is the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, and its molecular weight is 32500, molecular weight distribution system
Number is 2.0, numbering LYNP-12.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 13
The preferred embodiment of the present invention 13 provides a kind of high-thin arch dam, high diminishing, the preparation of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 with the concentrated sulfuric acid, then heats at 145 DEG C and enters water-filling
3h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 70 DEG C, 1 part of potassium peroxydisulfate and 1 part of sodium peroxydisulfate are added into the 1 part of wire parent N aqueous solution, is stirred 40 minutes,
Then by dissolved with 0.2 part of monomer B, 30 parts of monomer C and 5 parts of monomer D aqueous solution 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, is instilled wherein in 1.5h respectively, is then stirred for after reaction 1h, drop
Temperature is the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, and its molecular weight is 28570, and molecular weight distribution index is 1.9,
Numbering LYNP-13.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 14
The preferred embodiment of the present invention 14 provides a kind of high-thin arch dam, high diminishing, the preparation of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 3 with phosphoric acid (85%), then heats to and enters at 130 DEG C
Water-filling solution 3h, then adds calcium hydroxide, stirs 10min, filters to take supernatant, pH=7 is neutralized to phosphoric acid, produce line
Shape parent N；At 70 DEG C, 0.2 part of benzoyl peroxide and 0.25 part of persulfuric acid are added into the 1 part of wire parent N aqueous solution
Sodium, is stirred 40 minutes, then by dissolved with 0.6 part of monomer B, 40 parts of monomer C and 8 parts of monomer D aqueous solution 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, are instilled in 2h respectively
Wherein, then it is stirred for after reaction 1h, cooling is the high-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its molecular weight is
25400, molecular weight distribution index is 1.7, numbering LYNP-14.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 15
The preferred embodiment of the present invention 15 provides a kind of high-thin arch dam, high diminishing, the preparation of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 4 with the concentrated sulfuric acid, then heats at 140 DEG C and enters water-filling
5h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 80 DEG C, 1.2 parts of ammonium persulfates are added into the 1 part of wire parent N aqueous solution, are stirred 20 minutes, then will be dissolved with
0.1 part of monomer B, 20 parts of monomer C and 1 part of monomer D aqueous solution and dissolved with 5.5 parts of sodium hypophosphites, 2.8 parts of ammonium persulfates and
The 0.9 part of monomer B aqueous solution, is instilled wherein in 1h respectively, is then stirred for after reaction 0.5h, and cooling is the high guarantor
Collapse, high water reducing type modified naphthalene series water-reducing agent, its molecular weight be 29855, molecular weight distribution index is 1.5, numbering LYNP-15.
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Embodiment 16
The preferred embodiment of the present invention 16 provides a kind of high-thin arch dam, high diminishing, the preparation of anti-stick soil type modified naphthalene series water-reducing agent
Method, be specially：
Naphthalene water reducer is soluble in water, pH value of solution is adjusted to 5 with the concentrated sulfuric acid, then heats at 150 DEG C and enters water-filling
5h is solved, calcium hydroxide is then added, 10min is stirred, filters to take supernatant, pH=7 is neutralized to phosphoric acid, wire is produced female
Body N；At 65 DEG C, 0.9 part of potassium peroxydisulfate is added into the 1 part of wire parent N aqueous solution, is stirred 40 minutes, then will be dissolved with
0.5 part of monomer B, 30 parts of monomer C and 5 parts of monomer D aqueous solution and dissolved with 2 parts of TGAs, 2.5 parts of mercaptopropionic acids, 2.1 parts of mistakes
The aqueous solution of potassium sulfate and 2.5 parts of monomer B, is instilled wherein in 2h respectively, is then stirred for after reaction 1h, and cooling is described
High-thin arch dam, high water reducing type modified naphthalene series water-reducing agent, its molecular weight are 32540, and molecular weight distribution index is 1.8, numbering LYNP-
16。
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=15；
The structural formula of the monomer B is：
The structural formula of the monomer C is：
The structural formula of the monomer D is：
Comparative example 1
1.2mol crude naphthalene 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, occur 1h hydrolysis, be then cooled to 90 DEG C, add 1.2mol formalin, the condensation reaction at 100 DEG C
5h, reaction is finished, and is added in sodium hydroxide solution and pH to 7-8, that is, is obtained conventional naphthalene water reducer, numbering NF-DB.
Comparative example 2
220g methyl allyl polyoxyethylene ethers (M=2400) and 150g water are put into four-hole boiling flask, stirring in water bath adds
Heat is to 60 DEG C.3g TGAs are added in 60g water and are configured to solution A, 23g acrylic acid is configured into monomer with 35g water mixes
Thing solution B.After polymeric monomer is completely dissolved, 2g ammonium persulfates are poured into four-hole bottle, start that solution A and B are added dropwise simultaneously, and point
Di Jia not 3h, 3.5h.After completion of dropwise addition, isothermal reaction 1h.Less than 40 DEG C are cooled to, 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%, numbering PC-DB.
Experiment effect：
Experiment is according to GB/T8077-2000《Methods for testing uniformity of concrete admixture》Carry out, W/C=0.29, volume
For the solid volume of folding.Experiment determines each water reducer when reference cement mini-slump extension is 260 ± 5mm, required each water reducer
The solid volume of folding, is 2% while testing in montmorillonite volume, when mini-slump extension is 260 ± 5mm, and the folding of required water reducer is consolidated
Volume.And, specific test result is shown in Table 1 from naphthalene water reducer NF-DB and polycarboxylic acid super-plasticizer PC-DB as a comparison case.
Diminishing, holding and the anti-Property of Clay result of the different water reducer 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 compares 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, and its anti-stick native ability is better than polycarboxylate water-reducer, and situation about existing in clay
Under, it is superior that it starches retention property only.Therefore have high diminishing, high-thin arch dam and height anti-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.
Above-described is only the preferred embodiments of the present invention, and the explanation that should be understood that above example is to use
Understand the method and its core concept of the present invention in help, the protection domain being not intended to limit the present invention is all the present invention's
Any modification for being made within thought and principle, equivalent substitution etc., should be included in the scope of the protection.
Claims (8)
1. a kind of high-thin arch dam, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent, it is characterised 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, 130-150 DEG C of progress is then heated to
3-5h is hydrolyzed, calcium hydroxide is added, 5~15min is stirred, filters to take supernatant, it is 7 that pH is neutralized to phosphoric acid, produces line
The shape parent N aqueous solution；At 65-80 DEG C, initiator A is added into the wire parent N aqueous solution, the amount of addition is initiator
The 20-40% of A total amounts, is stirred 20-40 minutes；First aqueous solution and second aqueous solution are instilled simultaneously and are dripped in 1-2h
Finish, be then stirred for after reaction 0.5-1h, cooling is the high-thin arch dam, high diminishing, 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 monomer B addition is single
The 10-20% of body B total amounts；Second aqueous solution is the monomer B dissolved with chain-transferring agent T, the initiator A of surplus and surplus
The aqueous solution；
The structural formula of the naphthalene water reducer NSF is：
Wherein, n=10-15；
The general structure of the wire parent N is：
Wherein, n=10-15；
The general structure of the monomer B is：
R in formula1For H or-CH3, R2For-CH2O- or-CH2CH2O-, a=5-10, b=0-3；
The general structure of the monomer C is：
R in formula1For H or-CH3；
The general structure of the monomer D is：
R in formula3For-OCH3、-OCH2CH2OH、-OCH2CH(CH3) OH ,-OCO-CH=CH2Or
2. a kind of high-thin arch dam according to claim 1, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized in that：The molecular weight of the modified naphthalene series water-reducing agent is 20000-35000, and molecular weight distribution index is 1.5-2.0.
3. a kind of high-thin arch dam according to claim 1, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized in that：The general structure of the modified naphthalene series water-reducing agent is：
N in formula:c:d:E is 10:20-40:0-8:0-3.
4. a kind of high-thin arch dam according to claim 1, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized in that：The sour S is phosphoric acid (85%) or sulfuric acid.
5. a kind of high-thin arch dam according to claim 1, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized in that：The initiator A is one kind or two in benzoyl peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate
Kind.
6. a kind of high-thin arch dam according to claim 1, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized in that：The mole of the initiator A and the ratio of wire parent N, monomer B, monomer C and monomer D integral molar quantities are
1:8-25；The addition mole of the wire parent N is 1 with described monomer B, C and D ratio for adding mole:1-3:20-
40:1-8。
7. a kind of high-thin arch dam according to claim 1, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized in that：The chain-transferring agent T is one in methylpropene sodium sulfonate, TGA, mercaptopropionic acid and sodium hypophosphite
Plant or two kinds.
8. a kind of high-thin arch dam according to claim 1, high diminishing, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent,
It is characterized in that：The mole of the chain-transferring agent T and the ratio of wire parent N, monomer B, monomer C and monomer D integral molar quantities
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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| 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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