CN106188558B - The method for preparing cement water reducing agent as monomer using p styrene sulfonic acid salt - Google Patents
The method for preparing cement water reducing agent as monomer using p styrene sulfonic acid salt Download PDFInfo
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- CN106188558B CN106188558B CN201610563187.5A CN201610563187A CN106188558B CN 106188558 B CN106188558 B CN 106188558B CN 201610563187 A CN201610563187 A CN 201610563187A CN 106188558 B CN106188558 B CN 106188558B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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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
- C04B24/166—Macromolecular compounds comprising sulfonate or sulfate groups obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/38—Sulfohalogenation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
Belong to water-reducing agent field by the method that monomer prepares cement water reducing agent of p styrene sulfonic acid salt.The present invention obtains polycarboxylic acids-styrene sulfonate main chain with p styrene sulfonic acid salt and unsaturated carboxylic acid class monomer elder generation radical copolymerization; and then the benzene sulfonate on main chain is modified as benzene sulfonyl halogen group; then high price cerium salt is polymerize unsaturated cationic quaternary ammonium salt monomer with alcohol composition oxidation-reduction trigger system initiation and obtains terminal hydroxy group cation long-chain, then the polycarboxylic acids main chain of the group of halogen containing benzene sulfonyl and terminal hydroxy group cation long-chain, polyethylene glycols compound are made through sulfonylation.The present invention uses Molecular Design principle; by way of the modified benzene sulfonyl halogen of p styrene sulfonic acid salt and sulfonylation grafted cation side chain and side-chain of polyelycol; the novel concrete water reducing agent containing dual side-chain structure is successfully synthesized; reaction process is mild easily-controllable, energy-efficient, shows excellent diminishing guarantor and collapses and resist the multi-efficiencies such as clay.
Description
Technical field
The present invention relates to a kind of technical fields that cement water reducing agent is prepared using p styrene sulfonic acid salt as monomer, especially relate to
And to it is a kind of be modified again using unsaturated carboxylic acid monomer and p styrene sulfonic acid salt elder generation backbone polymerization benzene sulfonyl halogen polymerize again sun from
The specific preparation method of sub- side chain then main side chain sulfonylation synthesis cement water reducing agent.
Background technique
With the continuous development of technology of high performance concrete, the research of high-performance water reducing agent is also accordingly being promoted, with poly- carboxylic
Third generation cement water reducing agent --- the polycarboxylate water-reducer of molecular structure based on acid, with its volume is low, water-reducing rate is high, molecule
The advantages that design freedom is big, the most important a member being increasingly becoming in cement water reducing agent family, it is for preparing high-performance
Concrete has extremely important effect.However, the high susceptibility of polycarboxylate water-reducer becomes the big tug for restricting its development
Elbow, especially for the clay of high clay content, the forfeiture of workability is particularly evident.Therefore, urgent need prepares a kind of highly resistance clay
The cement water reducing agent of effect, to cope with concrete difference raw material bring adaptability problem.
Cement water reducing agent is made of high molecular material mostly, and great advantage is can be by exchanging polymerized monomer kind
Class changes the product that the methods of monomer match ratio and regulatory molecule structure functional group design different molecular structures and performance,
Its structure flexible design degree is big, performance regulation space is big.Therefore, it can be directed to the action character of aggregate problem containing mud, design is closed
Have effects that not lose script diminishing and protect to collapse and have both the cement water reducing agent for inhibiting side effect of clay at a kind of, further widen
The use scope of polycarboxylic acid structure's water-reducing agent improves its raw material adaptability, strengthens performance advantage, drives its property with structure innovation
It can break through and be promoted.
Subsidiary clay especially bentonite is usually have negative electrical charge laminar structured in sandstone aggregate, is easy to adsorb
The side chain macromolecular of cement water reducing agent is even lost so as to cause the weakening of working performance, and in view of this, the present invention is innovative
Cationic backbone is introduced into cement water reducing agent field by ground by Molecular Design method, and it is pure to have synthesized strong cation
Side-chain structure active balance charge electrical property and can protect the macromolecule side chain of water-reduction, significantly increase to side effect of clay
Inhibitory effect, this has to the applicable range safeguarded quality sand and stone aggregate resources, widen cement water reducing agent actively and weighs
The meaning wanted.
Patent CN 102093552A (publication date: on June 15th, 2011) reports a kind of with double-key end group phase change monomer
Preparation method, be that acid binding agent and acryloyl chloride is added after polyethylene glycol is first dissolved in methylene chloride, it is heavy to be added after completion of the reaction
Shallow lake agent and the phase change monomer that filters and must have double-key end group.The present invention is simple, and production cost is low, the monomer of synthesis
Active high, enthalpy of phase change and heat resistance are higher, are easily copolymerized with other monomers or polymer or graft reaction prepares solid-solid phase-change
Material.But the invention product generates corresponding polymeric monomer with the reaction of alkenyl acid chloride groups only with hydroxyl, has no conjunction
At the correlation means of subsequent polymer, the performance characteristic of special construction polymer molecule is not embodied, is not applied to coagulation yet
Native water-reducing agent field fails the control that cement water reducing agent performance is realized by structure design variation.
Patent CN 104446101A (publication date: on March 25th, 2015) reports the cation-modified polycarboxylic acids of one kind and subtracts
Aqua is by unitary unsaturated carboxylic acid and its derivatives monomer, cationic monomer, isoamyl alcohol polyoxyethylene ether monomer and two
Combined polymerization under the action of initiator and chain-transferring agent of first unsaturated carboxylic acid and its derivatives monomer forms.The invention product is added
When into concrete, it can be adsorbed on positively charged and negatively charged cement minerals surface simultaneously, embody and be superior to anion
The characteristics of type polycarboxylate water-reducer, moreover, product strand in cement slurry alkaline environment extends, absorption shape is more
Unfold, water-reducing rate is more excellent.But the invention product be only introduced in the main chain of molecular structure cationic monomer (and
The long side chain of introducing polycation of non-present invention), certain diminishing dispersion effect is improved, compound side chain is not given full play to
Structure feature shows the multiple actions effects such as highly resistance mud performance while diminishing dispersion to realize, also fails to reach molecule knot
The purpose of structure design method realization chemical admixture functionalization.
Patent CN 102516471A (publication date: on June 27th, 2012) reports a kind of pectination high polymer phase-change accumulation energy material
The preparation method of material.The patent after being dissolved in methylene chloride in ice-water bath, is added using poly glycol monomethyl ether as primary raw material
Acid binding agent and acryloyl chloride, decompression filters to obtain polyalkylene glycol acrylate monomethyl ether ester, then obtains with acrylamide monomers combined polymerization
To the phase-changing energy storage material with pectination molecule chain form.The phase-change material of invention preparation can be in hot procedure with molten
The form of body flows, and pectination molecule chain form can reduce its plasticization to matrix again, and preparation process is simple, production cost
It is low.The invention takes full advantage of the response characteristic of acryloyl chloride and hydroxyl, and has synthesized comb-shaped polymer, and main purpose is to close
The energy consumption in process is reduced at phase-changing energy storage material, improves plasticization effect.It but is a kind of common on the inventive nature
First start with the synthesis mode being copolymerized again from poly glycol monomethyl ether synthesis polymeric monomer, is difficult to control backbone length and monomer conversion
Rate influences it in the adsorption effect of cement particle surface, and the invention product fails the compound side chain of grafting multi-efficiency simultaneously
Inhibit side effect of clay applied to the method in water-reducing agent field, also failed to using grafted cation side chain, designs this from structure
The innovations and breakthroughs for reaching chain type on rear side of first main chain are also failed to from the point of view of matter.
Each invention product described in the above patent is provided with certain excellent characteristics.However, above-mentioned synthetic method obtains
Product have a degree of shortcoming, the angle synthesized from Molecular Design, researcher fails through carboxylic acid-benzene second
The structurally-modified benzene sulfonyl halogen of alkene co-polymer of sulfonate and the method for being grafted polymeric cationic side chain under high price cerium salt initiation system
Realize that integrating diminishing-guarantor is collapsed-disperses-complex function type chemical admixture of the application performances such as anti-mud.Above only by
Acylation reaction synthesizes polymeric monomer, or the method that synthesis simple function side chain or main chain introduce cationic block, limits significantly
Its apply improvement, warp facts proved that synthesis have multiple action complex function group type molecular structure can significantly improve it is poly-
Close the application performance of object.Therefore, this requires the water-reducing agents of synthesis in the innovation of molecular structure level essence, is not limited to pass
The synthesis mode of system innovatively causes polycation long-chain and benzene using the modified benzene sulfonyl halogen of benzene sulfonate, high price cerium salt
Sulfonic acid halide is grafted the synthetic route and feature of polycation side chain and polyether lateral chain, had both had diminishing and has protected-compound the work of anti-mud of collapsing
Make performance, while also helping industrial application, related this respect work has not been reported both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of synthesis works that cement water reducing agent is obtained using p styrene sulfonic acid salt as monomer
Skill carries out radical copolymerization by unsaturated carboxylic acid class monomer and p styrene sulfonic acid salt and obtains polycarboxylic acids-styrene sulfonic acid
Salt main chain, and then benzene sulfonate is modified as benzene sulfonyl halogen group, high price cerium salt and alcohol are then formed into redox initiator body
System, which causes, to be polymerize unsaturated cationic quaternary ammonium salt monomer and obtains terminal hydroxy group cationic side chain, then by the polycarboxylic acids master of the halogen containing benzene sulfonyl
Chain and terminal hydroxy group cationic side chain, polyethylene glycols compound through sulfonylation had excellent performance containing compound side chain
Cement water reducing agent.The present invention is to increase benzene sulfonate from design theory of molecular structure and be copolymerized and be modified benzene sulfonyl halogen
Group and high price cerium salt -ol are polymeric cationic side chain under redox initiation system, and successfully realize sulphonyl
Change grafting, polycarboxylic acids main chain and cationic side chain and side-chain of polyelycol are joined together to form with high water reduction and highly resistance mud
The novel concrete water reducing agent of equal multiple actions effect is realized through the dual modified raising working performance of molecular backbone side chain
Purpose enriches polymer architecture-performance study in the application in concrete chemical admixture field.Using the mixed of this method synthesis
Solidifying soil water-reducing agent has compound side-chain structure, different from the single side chain form of conventional polycarboxylate water-reducer, polyethylene glycol side
Chain can be acted on by steric hindrance and realize that excellent diminishing protects effect of collapsing, and cationic side chain structure can be in high clay content
Concrete system in change charge electrical, further prevent side-chain of polyelycol to be inhaled into clay interlayer and lose effect, from
And the adverse effect for inhibiting clay to generate dispersion flows performance, show work more more excellent than common polycarboxylate water-reducer
Characteristic and function and effect.
The present invention provides a kind of methods for preparing cement water reducing agent as monomer using p styrene sulfonic acid salt, pass through the former head
The method that chain polymerization is modified benzene sulfonyl halogen cationic long chain polymeric then sulfonylation again again synthesizes cement water reducing agent material,
Including the following conditions and step:
(1) (methyl) acrylic acid or its mixture with unsaturated carboxylic acid, right backbone polymerization: are sequentially added into reactor
Styrene sulfonate, water, molecular weight regulator, the initiator persulfate aqueous solution that mass fraction is 1-30%, and every time
It feeding interval mixing time 5-20 minutes, is warming up at 55-90 DEG C and carries out polymerization reaction, react 1.5-8 hours to get poly- carboxylic
Acid-styrene sulfonic acid saline solution；
(2) step (1) products therefrom polycarboxylic acids-styrene sulfonic acid saline solution modified benzene sulfonyl halogen: is vacuumized into removing
Organic solvent is added in moisture in system, stirs 5-20 minutes, and thionyl halide is added dropwise in 0.5-1 hours under the conditions of ice-water bath
Enter reactor, controls temperature and at 2-8 DEG C after isothermal reaction 10-20 hours, methanol is added and washs precipitating repeatedly 3-5 times, will sink
Starch is dried under vacuum to constant weight at 40-80 DEG C to get polycarboxylic acids-styrene sulfonic acid halide；
(3) cationic long chain polymeric: monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols are added another
In reactor, adds water and be configured to the aqueous solution that mass concentration is 2-10%, reactor inflated with nitrogen 3-5 deoxygenation 10- repeatedly
It is sealed after 30 minutes, oxidant high price cerium salt is added, be uniformly mixed within stirring 10-30 minutes, be continuously heating at 10-60 DEG C to it
Polymerization reaction is carried out, reacts 6-16 hours to get terminal hydroxy group cation long-chain aqueous solution；
(4) sulfonylation: step (3) products therefrom terminal hydroxy group cation long-chain aqueous solution is vacuumized in removing system
Moisture sequentially adds sulfonylation solvent, polyethylene glycols compound, triethylamine, step (2) products therefrom polycarboxylic acids-styrene
Sulfonic acid halide stirs 20-40 minutes, after being warming up to 30-60 DEG C, back flow reaction 6-12 hours, ether is added and washs precipitating 3-5 repeatedly
It is secondary, sediment is dried under vacuum to constant weight at 40-80 DEG C, be eventually adding water dilute needed for concentration cement water reducing agent it is molten
Liquid.
Unsaturated carboxylic acid described in above-mentioned steps (1) is one of itaconic acid, maleic acid (acid anhydride), fumaric acid or several
Kind, the molar ratio of (methyl) acrylic acid being added in dosage and step (1) is 0.1-5:1；To styrene described in step (1)
Sulfonate is sodium p styrene sulfonate or p styrene sulfonic acid potassium, (methyl) acrylic acid described in dosage and step (1) or its with
The molar ratio of the mixture of unsaturated carboxylic acid is 0.15-0.4:1；It is in step (1) that the quality of water is added described in step (1)
The total matter of p styrene sulfonic acid salt described in (methyl) acrylic acid or its mixture and step (1) with unsaturated carboxylic acid
Measure the 80-200% of sum；Molecular weight regulator described in step (1) be thioacetic acid, mercaptopropionic acid, methylpropene sodium sulfonate,
Sodium Allyl Sulfonate or n-dodecyl mercaptan, (methyl) acrylic acid described in dosage and step (1) or itself and unsaturated carboxylic
The ratio of the sum of p styrene sulfonic acid salt molal quantity described in the mixture and step (1) of acid is 0.01-0.15:1；Step (1)
Described in initiator persulfate be ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate, (first described in dosage and step (1)
The sum of base) p styrene sulfonic acid salt molal quantity described in acrylic acid or its mixture and step (1) with unsaturated carboxylic acid
Than for 0.01-0.1:1.
Organic solvent described in above-mentioned steps (2) is dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane or dimethylformamide, is used
To benzene described in (methyl) acrylic acid described in amount and step (1) or its mixture and step (1) with unsaturated carboxylic acid
Vinyl sulfonate gross mass and the ratio between be 1-5:1；Thionyl halide described in step (2) is thionyl chloride or thionyl bromide, is used
Amount and the molar ratio of p styrene sulfonic acid salt described in step (1) are 1-1.5:1；Methanol usage and step described in step (2)
Suddenly (methyl) acrylic acid described in (1) or its mixture with unsaturated carboxylic acid, p styrene sulfonic acid described in step (1)
Thionyl halide quality described in salt and step (2) and the ratio between be 5-10:1.
Unsaturated cation quaternary ammonium salt described in above-mentioned steps (3) is trimethylallylammonium chloride, dimethyl diene
Propyl ammonium chloride, tetra allyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium, methacryl hydroxypropyltrimonium chloride, acryloxyethyldimethyl butylammonium bromide, methylacryoyloxyethyl two
Methyl butyl ammonium bromide, acryloxyethyldimethyl dodecyl ammonium bromide, methylacryoyloxyethyl dimethyl dodecyl
Base ammonium bromide, acryloxyethyldimethyl cetyl ammonium bromide, methylacryoyloxyethyl dimethyl hexadecyl bromide
One or more of ammonium, the molar ratio of high price cerium salt described in dosage and step (3) are 10-1000:1；Institute in step (3)
The lower aliphatic alcohols stated are normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-fourth
Alcohol, 2,2- dimethyl -1- propyl alcohol or cyclohexanol, dosage and the molar ratio of p styrene sulfonic acid salt described in step (1) are
0.2-0.5:1；High price cerium salt described in step (3) is ammonium ceric nitrate or Cericammoniumsulfate, and dosage is low with described in step (3)
The molar ratio of grade fatty alcohol is 0.03-1:1.
Sulfonylation solvent described in above-mentioned steps (4) is carbon tetrachloride, methylene chloride or tetrahydrofuran, dosage and step
(1) (methyl) acrylic acid described in or its mixture with unsaturated carboxylic acid, p styrene sulfonic acid described in step (1)
Polyethylene glycols compound quality described in unsaturated cation quaternary ammonium salt described in salt, step (3) and step (4) and it
Than for 1-2.5:1；Polyethylene glycols compound described in step (4) be polyethylene glycol or methoxy poly (ethylene glycol), dosage with
The molar ratio of p styrene sulfonic acid salt described in step (1) is 0.5-0.8:1；Triethylamine dosage described in step (4) with
The molar ratio of p styrene sulfonic acid salt described in step (1) is 1-1.5:1；Ether dosage described in step (4) and step (1)
Described in (methyl) acrylic acid or its mixture with unsaturated carboxylic acid, p styrene sulfonic acid salt described in step (1), step
Suddenly polyethylene glycols compound quality described in unsaturated cation quaternary ammonium salt described in (3) and step (4) and the ratio between be
3-5:1.
The number-average molecular weight of polyethylene glycols compound in the method for the present invention is 500-3000.
The method of the present invention has the advantages that compared with prior art
1. p styrene sulfonic acid salt and unsaturated carboxylic acid monomer are copolymerized simultaneously by the present invention from design theory of molecular structure
The polycarboxylic acids main chain of the group of halogen containing benzene sulfonyl is modified as through thionyl halide, meanwhile, it is anti-with unsaturated cationic quaternary ammonium salt monomer
Object is answered, free radical polymerization obtains cationic side chain under the oxidation-reduction trigger system of high price cerium salt and alcohol composition, this is from normal
The unique design that polycarboxylic acids main chain-polyether lateral chain of rule develops to diversification, the composite modified main side chain of multifunction, is in comb shape
Dispersing agent not only may be implemented in application performance in innovation and breakthrough on water-reducing agent molecular structure direction, novel special structure
The promotion of aspect, and be conducive to expand Polymer supported catalyst-structure-performance intension of theory, for it is subsequent to a deeper level
It develops other new varieties cement water reducing agents and has widened Research Thinking and developing direction.
2. being different from other inventive methods being only to be copolymerized a small amount of cationic structural in molecular backbone, the method for the present invention
The compound side chain type water-reducing agent of synthesis contains a large amount of quaternary ammonium salt cationic polymerization macromolecule chains, can be with electronegative clay layer
Electrostatic adsorption is generated, is conducive to be adsorbed on clay interlayer, simultaneously as the interlamination region limited volume of clay, absorption is a large amount of
Cationic side chain can enter clay interlayer to avoid other side-chain of polyelycol, protect the diminishing of the water-reducing agent to protect effect of collapsing and do not lose
It loses, to show the function and effect of high water reduction, highly resistance mud.The product can also diversification expanded application in fine chemistry industry and table
The fields such as face activating agent are a kind of cement water reducing agents with peculiar advantage and distinguishing feature, have good market competition
Power and application prospect.
3. synthetic method of the invention is compared with the traditional method, raw materials required for the reaction is common to be easy to get, and entire synthesis process connects
It is easily-controllable, efficiently convenient to continue, and polymerization, modification and sulfonylation grafting step used also belongs to common process, without special operation or
Expensive auxiliary agent enriches the preparation method of synthesis cement water reducing agent, it is easy to accomplish industrialized production.The synthesis process is to equipment
Without particular/special requirement, and compound high water reduction and high-thin arch dam functional group are remained with, and with molecular weight is controllable, the degree of polymerization is high, divides
Son amount narrowly distributing, molecule can designed capacity it is strong the advantages that, have good application value and development potentiality.
4. the method for the present invention innovatively uses the redox initiation system of high price cerium salt -ol class, high price cerium salt is utilized
Strong oxidizing property and the characteristic for having the free free radical of initiation organic matter generation, have abandoned traditional one-component hot initiator system, list
The initiation system of one high price cerium salt, oxidation-reduction trigger system (such as hydrogen peroxide-VC system), the polymerization under the initiation system
Reaction process is mildly stablized, and side reaction is few, and can substantially reduce the activation energy of polymerization process, has a extensive future, and is mixed
Solidifying soil water-reducing agent provides a kind of method of new initiation polymerization.
5. synthetic technological condition is mild, easily operated, production cost is low, entire reaction process under medium and low temperature into
Row, production energy consumption is low, and temperature fluctuation range is small, is conducive to the steady progress for maintaining reaction system, reduces the generation of side reaction, protects
Demonstrate,prove the yield of reaction product.Meanwhile p styrene sulfonic acid salt, unsaturated carboxylic acid monomer and the unsaturated cation quaternary ammonium salt used
The suitable molecular weight range of raw material monomer is wide, is conducive to the large-scale popularization and application of Diversified Products, increases highly resistance chamotte mould coagulation
The market share occupancy volume of native water-reducing agent.
6. there is diminishing and the dual side chain of anti-mud according to the cement water reducing agent of the method for the present invention synthesis, than conventional polycarboxylic acids
The workability of water-reducing agent, diminishing slump retaining and anti-mud effect are more excellent, remain to show preferable mobility in high clay content
And holding capacity, and very strong adaptability is shown to the cement of different cultivars.In addition, the water-reducing agent Product Status is stablized,
It is not stratified after being stood under high concentration, it is not crystallized after being stored under low temperature and performance is unaffected.The synthetic method is convenient and easy
While, products obtained therefrom still has excellent performance indexes, is conducive to industrialization promotion and application, therefore have fine
Economic and social benefit.
Specific embodiment
The present invention is described in further detail below with reference to embodiment, but implementation of the invention is without being limited thereto.
Embodiment 1
1.43g methacrylic acid, 10.84g itaconic acid, 6.19g p styrene sulfonic acid are sequentially added into reactor first
Sodium, 14.77g water, 1.23g methylpropene sodium sulfonate, the sodium persulfate aqueous solution that 21.67g mass fraction is 10%, and every time
It feeding interval mixing time 5 minutes, is warming up at 60 DEG C and carries out polymerization reaction, react 6.5 hours to get polycarboxylic acids-styrene
Sulfonic acid saline solution；Gained polycarboxylic acids-styrene sulfonic acid saline solution is vacuumized into moisture in removing system, 64.61g bis- is added
Methylformamide stirs 12 minutes, 6.24g thionyl bromide is added dropwise to reactor in 0.7 hour under the conditions of ice-water bath, controls
Temperature after isothermal reaction 17 hours, is added 123.49g methanol and washs precipitating repeatedly 3 times at 3 DEG C, and sediment is true at 80 DEG C
Sky drying is to constant weight to get polycarboxylic acids-styrene sulfonic acid bromide；By 18.69g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and
0.53g n-amyl alcohol is added in another reactor, adds 461.33g water and is configured to the aqueous solution that mass concentration is 4%, reactor
3 deoxygenations seal inflated with nitrogen after 30 minutes repeatedly, and 1.07g Cericammoniumsulfate is added, and are uniformly mixed to it within stirring 30 minutes, after of continuing rising
Temperature reacts 12 hours to polymerization reaction is carried out at 50 DEG C to get terminal hydroxy group cation long-chain aqueous solution；By gained terminal hydroxy group sun from
Sub- long-chain aqueous solution vacuumizes moisture in removing system, sequentially adds 176.7g tetrahydrofuran, 43.5g polyethylene glycol (molecular weight
=1800), 4.25g triethylamine, gained polycarboxylic acids-styrene sulfonic acid bromide stir 35 minutes, are warming up to 55 DEG C, back flow reaction 8 is small
Shi Hou is added 321.42g ether and washs precipitating repeatedly 4 times, sediment is dried under vacuum to constant weight at 40 DEG C, is eventually adding
The cement water reducing agent solution prepared by monomer of p styrene sulfonic acid salt that 223.63g water is 30% up to mass fraction.
Embodiment 2
After the cement water reducing agent solution that the mass fraction that embodiment 1 is obtained is 30% is stored 30 days at 6 DEG C, measurement
Its implementation result.
Embodiment 3
2.87g methacrylic acid, 4.34g itaconic acid, 3.87g maleic acid, 5.15g pairs are sequentially added into reactor first
Sodium styrene sulfonate, 16.23g water, 0.57g thioacetic acid, the ammonium persulfate aqueous solution that 7.13g mass fraction is 20%, and
It each feeding interval mixing time 11 minutes, is warming up at 75 DEG C and carries out polymerization reaction, react 4.5 hours to get polycarboxylic acids-benzene
Vinyl sulfonic acid saline solution；Gained polycarboxylic acids-styrene sulfonic acid saline solution is vacuumized into moisture in removing system, is added
40.57g dimethyl sulfoxide stirs 14 minutes, 3.57g thionyl chloride is added dropwise to reaction in 0.6 hour under the conditions of ice-water bath
Device controls temperature and at 4 DEG C after isothermal reaction 16 hours, 158.39g methanol is added and washs precipitating repeatedly 5 times, sediment is existed
Constant weight is dried under vacuum at 65 DEG C to get polycarboxylic acids-styrenesulphonyl chloride；By 43.58g acrylyl oxy-ethyl-trimethyl salmiac
It is added in another reactor with 0.56g isobutanol, adds 507.51g water and be configured to the aqueous solution that mass concentration is 8%, reaction
4 deoxygenations seal device inflated with nitrogen after twenty minutes repeatedly, and 0.41g ammonium ceric nitrate is added, and are uniformly mixed within stirring 20 minutes, continue to it
It is warming up at 40 DEG C and carries out polymerization reaction, react 13 hours to get terminal hydroxy group cation long-chain aqueous solution；By gained terminal hydroxy group sun
Ion long-chain aqueous solution vacuumizes moisture in removing system, sequentially adds 152.71g carbon tetrachloride, 42g methoxy poly (ethylene glycol)
(molecular weight=2400), 3.04g triethylamine, gained polycarboxylic acids-styrenesulphonyl chloride stir 30 minutes, are warming up to 50 DEG C, reflux
After reaction 9 hours, 305.42g ether is added and washs precipitating repeatedly 5 times, sediment is dried under vacuum to constant weight at 60 DEG C, most
Afterwards be added 167.06g water up to mass fraction be 40% the cement water reducing agent prepared by monomer of p styrene sulfonic acid salt it is molten
Liquid.
Embodiment 4
After the cement water reducing agent solution that the concentration that embodiment 3 obtains is 40% is stored 20 days at 5 DEG C, measurement is in fact
Apply effect.
Embodiment 5
1.8g acrylic acid, 3.25g itaconic acid, 2.45g maleic anhydride, 2.9g richness horse are sequentially added into reactor first
Acid, the over cure that 3.33g p styrene sulfonic acid potassium, 20.61g water, 3.49g n-dodecyl mercaptan, 26.24g mass fraction are 1%
Sour aqueous ammonium, and feeding interval mixing time 17 minutes every time, it is warming up at 90 DEG C and carries out polymerization reaction, reaction 1.5 is small
When to get polycarboxylic acids-styrene sulfonic acid saline solution；Gained polycarboxylic acids-styrene sulfonic acid saline solution is vacuumized into removing body
Moisture in being, is added 68.71g1, and 4- dioxane stirs 20 minutes, by 4.37g sulfurous in 0.5 hour under the conditions of ice-water bath
Acylbromide is added dropwise to reactor, controls temperature and at 2 DEG C after isothermal reaction 20 hours, 162.96g methanol is added and washs precipitating 3 repeatedly
It is secondary, sediment is dried under vacuum to constant weight at 50 DEG C to get polycarboxylic acids-styrene sulfonic acid bromide；By 16.56g methacryl
Hydroxypropyltrimonium chloride and 0.75g cyclohexanol are added in another reactor, add 848.03g water and are configured to mass concentration and are
2% aqueous solution, 5 deoxygenations seal reactor inflated with nitrogen after 25 minutes repeatedly, and 4.11g ammonium ceric nitrate is added, and stir 18 minutes
It is uniformly mixed to it, is continuously heating to carry out polymerization reaction at 60 DEG C, reaction 8 hours water-soluble to get terminal hydroxy group cation long-chain
Liquid；Gained terminal hydroxy group cation long-chain aqueous solution is vacuumized into moisture in removing system, sequentially add 131.99g methylene chloride,
22.5g methoxy poly (ethylene glycol) (molecular weight=3000), 2.28g triethylamine, gained polycarboxylic acids-styrene sulfonic acid bromide, stirring 28
Minute, after being warming up to 60 DEG C, back flow reaction 6 hours, 263.99g ether is added and washs precipitating repeatedly 4 times, by sediment at 70 DEG C
Under be dried under vacuum to constant weight, being eventually adding 158.8g water up to mass fraction is 30% using p styrene sulfonic acid salt as monomer system
Standby cement water reducing agent solution.
Embodiment 6
The cement water reducing agent solution that the mass fraction that embodiment 5 is obtained is 30% measures it after 6 DEG C are stored 40 days
Implementation result.
Embodiment 7
7.21g acrylic acid, 8.25g sodium p styrene sulfonate, 27.82g water, 0.28g are sequentially added into reactor first
N-dodecyl mercaptan, the sodium persulfate aqueous solution that 13.33g mass fraction is 25%, and feeding interval mixing time 8 every time
Minute, it is warming up at 85 DEG C and carries out polymerization reaction, react 2.5 hours to get polycarboxylic acids-styrene sulfonic acid saline solution；By institute
It obtains polycarboxylic acids-styrene sulfonic acid saline solution and vacuumizes moisture in removing system, 61.81g dimethylformamide, stirring 16 is added
Minute, 7.14g thionyl chloride is added dropwise to reactor in 0.9 hour under the conditions of ice-water bath, control temperature constant temperature at 7 DEG C is anti-
After answering 10 hours, be added 135.55g methanol wash repeatedly precipitates 5 times, sediment is dried under vacuum at 60 DEG C constant weight to get
Polycarboxylic acids-styrenesulphonyl chloride；By 70.61g methylacryoyloxyethyl dimethyl dodecyl base ammonium bromide and 0.96g isopropanol
It is added in another reactor, adds 723.65g water and be configured to the aqueous solution that mass concentration is 9%, reactor inflated with nitrogen repeatedly 3
Secondary deoxygenation seals after twenty minutes, and 0.29g Cericammoniumsulfate is added, and is uniformly mixed within stirring 25 minutes, is continuously heating at 10 DEG C to it
Polymerization reaction is carried out, reacts 16 hours to get terminal hydroxy group cation long-chain aqueous solution；Gained terminal hydroxy group cation long-chain is water-soluble
Liquid vacuumizes moisture in removing system, sequentially adds 176.51g tetrahydrofuran, 12g polyethylene glycol (molecular weight=500), 4.05g
Triethylamine, gained polycarboxylic acids-styrenesulphonyl chloride stir 40 minutes, after being warming up to 30 DEG C, back flow reaction 12 hours, are added
343.22g ether washs precipitating 3 times repeatedly, and sediment is dried under vacuum to constant weight at 65 DEG C, is eventually adding 171.17g water i.e.
Obtain the cement water reducing agent solution prepared by monomer of p styrene sulfonic acid salt that mass fraction is 40%.
Embodiment 8
The cement water reducing agent solution that the mass fraction that embodiment 7 is obtained is 40% measures it after 7 DEG C are stored 30 days
Implementation result.
Embodiment 9
Sequentially added first into reactor 8.61g methacrylic acid, 7.78g p styrene sulfonic acid potassium, 19.66g water,
1.95g Sodium Allyl Sulfonate, the persulfate aqueous solution that 10.95g mass fraction is 30%, and when each feeding interval stirring
Between 20 minutes, be warming up at 60 DEG C and carry out polymerization reaction, react 8 hours to get polycarboxylic acids-styrene sulfonic acid saline solution；It will
Gained polycarboxylic acids-styrene sulfonic acid saline solution vacuumizes moisture in removing system, and 16.38g dimethyl sulfoxide, stirring 5 is added
Minute, 4.58g thionyl chloride is added dropwise to reactor in 1 hour under the conditions of ice-water bath, controls temperature isothermal reaction at 8 DEG C
After 11 hours, 146.73g methanol is added and washs precipitating repeatedly 5 times, sediment is dried under vacuum to constant weight at 70 DEG C to get poly-
Carboxylic acid-styrenesulphonyl chloride；59.34g trimethylallylammonium chloride and 0.53g normal propyl alcohol are added in another reactor, then
688.48g water is added and is configured to the aqueous solution that mass concentration is 8%, 4 deoxygenations seal reactor inflated with nitrogen after 15 minutes repeatedly,
0.24g ammonium ceric nitrate is added, is uniformly mixed to it within stirring 10 minutes, is continuously heating to carry out polymerization reaction at 55 DEG C, reaction 10
Hour is to get terminal hydroxy group cation long-chain aqueous solution；Gained terminal hydroxy group cation long-chain aqueous solution is vacuumized in removing system
Moisture sequentially adds 107.22g carbon tetrachloride, 31.5g polyethylene glycol (molecular weight=1200), 3.9g triethylamine, the poly- carboxylic of gained
Acid-styrenesulphonyl chloride stirs 20 minutes, after being warming up to 45 DEG C, back flow reaction 10 hours, 343.11g ether is added and washes repeatedly
It washs precipitating 5 times, sediment is dried under vacuum to constant weight at 80 DEG C, being eventually adding 121.69g water up to mass fraction is 50%
The cement water reducing agent solution prepared using p styrene sulfonic acid salt as monomer.
Embodiment 10
The cement water reducing agent solution that the mass fraction that embodiment 9 is obtained is 50% measures it after 5 DEG C are stored 40 days
Implementation result.
Embodiment 11
Sequentially added first into reactor 6.55g acrylic acid, 1.06g fumaric acid, 4.45g p styrene sulfonic acid potassium,
24.1g water, 1.15g mercaptopropionic acid, the persulfate aqueous solution that 6.49g mass fraction is 15%, and feeding interval stirs every time
It mixes the time 15 minutes, is warming up at 70 DEG C and carries out polymerization reaction, reaction 5 hours water-soluble to get polycarboxylic acids-styrene sulfonate
Liquid；Gained polycarboxylic acids-styrene sulfonic acid saline solution is vacuumized into moisture in removing system, is added 36.16g1,4- dioxy oneself
Ring stirs 18 minutes, and 5.4g thionyl bromide is added dropwise to reactor in 0.8 hour under the conditions of ice-water bath, controls temperature at 6 DEG C
After lower isothermal reaction 13 hours, 174.57g methanol is added and washs precipitating repeatedly 3 times, sediment is dried under vacuum at 40 DEG C
Constant weight is to get polycarboxylic acids-styrene sulfonic acid bromide；45.27g dimethyl diallyl ammonium chloride and 0.52g n-butanol are added another
In one reactor, adds 869.94g water and be configured to the aqueous solution that mass concentration is 5%, 5 deoxygenations repeatedly of reactor inflated with nitrogen
It seals after ten minutes, 0.84g Cericammoniumsulfate is added, be uniformly mixed to it within stirring 15 minutes, be continuously heating to be gathered at 30 DEG C
Reaction is closed, reacts 14 hours to get terminal hydroxy group cation long-chain aqueous solution；Gained terminal hydroxy group cation long-chain aqueous solution is taken out true
Moisture in empty removing system, sequentially add 166.64g methylene chloride, 26g methoxy poly (ethylene glycol) (molecular weight=2000),
2.63g triethylamine, gained polycarboxylic acids-styrene sulfonic acid bromide stir 25 minutes, after being warming up to 40 DEG C, back flow reaction 11 hours, add
Enter 374.94g ether and wash precipitating repeatedly 3 times, sediment is dried under vacuum to constant weight at 55 DEG C, is eventually adding 94.83g water
The cement water reducing agent solution prepared by monomer of p styrene sulfonic acid salt for being 50% up to mass fraction.
Embodiment 12
After the cement water reducing agent solution that the concentration that embodiment 11 is obtained is 50% is stored 20 days at 7 DEG C, it is measured
Implementation result.
Implementation result:
1. flowing degree of net paste of cement
To investigate flowing of the cement water reducing agent solution of the invention prepared by monomer of p styrene sulfonic acid salt to cement
Property function and effect, test determines under identical volume each embodiment to the paste flowing degree of reference cement.GB/ is pressed in test
T8077-2012 " Methods for testing uniformity of concrete admixture " is carried out, W/C=0.29, and volume is to roll over solid volume.It selects existing
Commercially available tradition comb shape poly carboxylic acid series water reducer (comparative example) is as a comparison sample, and test result is shown in Table 1.
1 pulp flowage results of property of table
From table 1 it follows that the cement water reducing agent that the method for the present invention is prepared using p styrene sulfonic acid salt as monomer is molten
Liquid can show excellent dispersibility and cement adaptability in the case where 0.29 ratio of mud and 0.35% folding consolidate volume.
2. concrete slump and divergence
Test determines the divergence and the slump and retention property that each embodiment is shown in concrete system, tests
It the results are shown in Table 2.
2 concrete flowability energy result of table
From Table 2, it can be seen that the cement water reducing agent that the method for the present invention is prepared using p styrene sulfonic acid salt as monomer is molten
Liquid can show excellent divergence and the slump and holding capacity in concrete system.
3. agent on crack resistance of concrete mud performance
Test determines the divergence and the slump and retention property that each embodiment is shown in concrete system, tests
It the results are shown in Table 3.
3 concrete flowability energy result of table
From table 3 it is observed that the cement water reducing agent that the method for the present invention is prepared using p styrene sulfonic acid salt as monomer is molten
Liquid can show preferable divergence and the slump and holding capacity under 1.8% clay additive.
Claims (3)
1. a kind of method for preparing cement water reducing agent as monomer using p styrene sulfonic acid salt, which is characterized in that pass through first main chain
Polymerization is modified the benzene sulfonyl halogen cationic long chain polymeric then method synthesis cement water reducing agent material of sulfonylation again again
Condition and steps are as follows:
(1) backbone polymerization: sequentially added into reactor (methyl) acrylic acid or its with the mixture of unsaturated carboxylic acid, to benzene second
Alkene sulfonate, water, molecular weight regulator, mass fraction are the initiator persulfate aqueous solution of 1-30%, and feed every time
Interval mixing time 5-20 minutes, is warming up at 55-90 DEG C and carries out polymerization reaction, reacts 1.5-8 hours to get polycarboxylic acids-benzene
Vinyl sulfonic acid saline solution；
(2) step (1) products therefrom polycarboxylic acids-styrene sulfonic acid saline solution modified benzene sulfonyl halogen: is vacuumized into removing system
Organic solvent is added in interior moisture, stirs 5-20 minutes, is added dropwise to thionyl halide instead in 0.5-1 hours under the conditions of ice-water bath
Device is answered, temperature is controlled and at 2-8 DEG C after isothermal reaction 10-20 hours, methanol is added and washs precipitating repeatedly 3-5 times, by sediment
Constant weight is dried under vacuum at 40-80 DEG C to get polycarboxylic acids-styrene sulfonic acid halide；
(3) another reaction cationic long chain polymeric: is added in monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols
In device, adds water and be configured to the aqueous solution that mass concentration is 2-10%, 3-5 deoxygenation 10-30 divides reactor inflated with nitrogen repeatedly
It is sealed after clock, oxidant high price cerium salt is added, be uniformly mixed to it within stirring 10-30 minutes, be continuously heating to carry out at 10-60 DEG C
Polymerization reaction reacts 6-16 hours to get terminal hydroxy group cation long-chain aqueous solution；
(4) step (3) products therefrom terminal hydroxy group cation long-chain aqueous solution sulfonylation: is vacuumized into water in removing system
Point, sequentially add sulfonylation solvent, polyethylene glycols compound, triethylamine, step (2) products therefrom polycarboxylic acids-styrene sulphur
Carboxylic acid halides stirs 20-40 minutes, after being warming up to 30-60 DEG C, back flow reaction 6-12 hours, ether is added and washs precipitating 3-5 repeatedly
It is secondary, sediment is dried under vacuum to constant weight at 40-80 DEG C, be eventually adding water dilute needed for concentration cement water reducing agent it is molten
Liquid；
Wherein, unsaturated carboxylic acid described in step (1) is one or more of itaconic acid, maleic acid, fumaric acid, unsaturation
Carboxylic acid can be added or be added without, and dosage and the molar ratio of (methyl) acrylic acid being added in step (1) are when added
0.1-5:1；P styrene sulfonic acid salt described in step (1) be sodium p styrene sulfonate or p styrene sulfonic acid potassium, dosage with
The molar ratio of (methyl) acrylic acid described in step (1) or itself and the mixture of unsaturated carboxylic acid is 0.15-0.4:1；Step (1)
Described in addition water quality be (methyl) acrylic acid described in step (1) or itself and unsaturated carboxylic acid mixture and step
Suddenly the 80-200% of the gross mass sum of p styrene sulfonic acid salt described in (1)；Molecular weight regulator described in step (1) is mercapto
Guanidine-acetic acid, mercaptopropionic acid, methylpropene sodium sulfonate, Sodium Allyl Sulfonate or n-dodecyl mercaptan, dosage and institute in step (1)
P styrene sulfonic acid salt molal quantity described in (methyl) acrylic acid or its mixture and step (1) with unsaturated carboxylic acid stated
The sum of ratio be 0.01-0.15:1；Initiator persulfate described in step (1) is ammonium persulfate, potassium peroxydisulfate or over cure
Sour sodium, described in (methyl) acrylic acid described in dosage and step (1) or its mixture and step (1) with unsaturated carboxylic acid
The ratio of the sum of p styrene sulfonic acid salt molal quantity be 0.01-0.1:1；
Organic solvent described in step (2) is dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane or dimethylformamide, dosage and step
(1) p styrene sulfonic acid described in (methyl) acrylic acid or its mixture and step (1) with unsaturated carboxylic acid described in
Salt gross mass and the ratio between be 1-5:1；Thionyl halide described in step (2) is thionyl chloride or thionyl bromide, dosage and step
(1) molar ratio of the p styrene sulfonic acid salt described in is 1-1.5:1；Institute in methanol usage described in step (2) and step (1)
(methyl) acrylic acid stated or its mixture with unsaturated carboxylic acid, p styrene sulfonic acid salt and step described in step (1)
(2) thionyl halide quality described in and the ratio between be 5-10:1；
Unsaturated cation quaternary ammonium salt described in step (3) is trimethylallylammonium chloride, dimethyl diallyl chlorination
Ammonium, tetra allyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methyl
Acryloyl hydroxypropyltrimonium chloride, acryloxyethyldimethyl butylammonium bromide, methylacryoyloxyethyl dimethyl butyrate
Base ammonium bromide, acryloxyethyldimethyl dodecyl ammonium bromide, methylacryoyloxyethyl dimethyl dodecyl bromide
Ammonium, acryloxyethyldimethyl cetyl ammonium bromide, in methylacryoyloxyethyl dimethyl hexadecyl base ammonium bromide
One or more, the molar ratio of high price cerium salt described in dosage and step (3) are 10-1000:1；It is low described in step (3)
Grade fatty alcohol is normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-butanol, 2,2-
Dimethyl -1- propyl alcohol or cyclohexanol；High price cerium salt described in step (3) is ammonium ceric nitrate or Cericammoniumsulfate, dosage and step
(3) molar ratio of the lower aliphatic alcohols described in is 0.03-1:1；
Sulfonylation solvent described in step (4) is carbon tetrachloride, methylene chloride or tetrahydrofuran, institute in dosage and step (1)
(methyl) acrylic acid stated or its mixture with unsaturated carboxylic acid, p styrene sulfonic acid salt, step described in step (1)
(3) polyethylene glycols compound quality described in the unsaturated cation quaternary ammonium salt and step (4) described in and the ratio between be 1-
2.5:1；Polyethylene glycols compound described in step (4) is polyethylene glycol or methoxy poly (ethylene glycol)；Described in step (4)
Triethylamine dosage and step (1) described in p styrene sulfonic acid salt molar ratio be 1-1.5:1；Second described in step (4)
(methyl) acrylic acid described in ether dosage and step (1) or its mixture with unsaturated carboxylic acid, pair described in step (1)
Polyethylene glycols chemical combination described in unsaturated cation quaternary ammonium salt described in styrene sulfonate, step (3) and step (4)
Amount of substance and the ratio between be 3-5:1.
2. a kind of method that cement water reducing agent is prepared as monomer using p styrene sulfonic acid salt according to claim 1,
The molar ratio for being characterized in that lower aliphatic alcohols described in step (3) and p styrene sulfonic acid salt described in step (1) is
0.2-0.5:1.
3. a kind of method that cement water reducing agent is prepared as monomer using p styrene sulfonic acid salt according to claim 1,
It is characterized in that mole of p styrene sulfonic acid salt described in polyethylene glycols compound described in step (4) and step (1)
Than for 0.5-0.8:1.
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| CN103554496A (en) * | 2013-10-31 | 2014-02-05 | 上海台界化工有限公司 | Retarding and plastic-retaining type polycarboxylate superplasticizer and preparation method thereof |
| CN104129941A (en) * | 2014-07-28 | 2014-11-05 | 武汉理工大学 | Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof |
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| CN101531744A (en) * | 2009-04-28 | 2009-09-16 | 中国水利水电科学研究院 | Method for synthesizing polycarboxylic acid series concrete hyper-dispersant |
| CN103554496A (en) * | 2013-10-31 | 2014-02-05 | 上海台界化工有限公司 | Retarding and plastic-retaining type polycarboxylate superplasticizer and preparation method thereof |
| CN104129941A (en) * | 2014-07-28 | 2014-11-05 | 武汉理工大学 | Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof |
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