CN106117564B - A kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain - Google Patents

A kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain Download PDF

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CN106117564B
CN106117564B CN201610563315.6A CN201610563315A CN106117564B CN 106117564 B CN106117564 B CN 106117564B CN 201610563315 A CN201610563315 A CN 201610563315A CN 106117564 B CN106117564 B CN 106117564B
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side chain
added
acid
methyl
esterification
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CN106117564A (en
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刘晓
管佳男
王子明
申和庆
薛龙
庞晓凡
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Beijing University of Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • 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
    • 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
    • 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
    • C08F126/00—Homopolymers 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/02—Homopolymers 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • 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
    • C04B2103/48—Foam stabilisers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

A kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain belongs to dispersing agent field.The present invention is using unsaturated carboxylic acid class monomer as reactant, free radical polymerization, which is carried out, under initiator and chain-transferring agent effect obtains polycarboxylic acids main chain, then using unsaturated cationic quaternary ammonium salt monomer as reactant, free radical polymerization obtains terminal hydroxy group cationic side chain under the oxidation-reduction trigger system of high price cerium salt and alcohol composition, then polycarboxylic acids main chain is passed through graft esterification with terminal hydroxy group cationic side chain, polyethylene glycols compound under the effect of the catalyst and reacts obtained.Process of the present invention is simple and easy to control, low in cost, energy-efficient, environment friendly and pollution-free, pass through the compound side-chain structure of Molecular Design modified synthesis, side chain space steric effect and cationic charge arrangement are realized in success, it shows the diminishing more excellent than common polycarboxylate water-reducer and protects collapse characteristic and inhibition side effect of clay ability, have a vast market foreground and promote and apply potentiality.

Description

A kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain
Technical field
The present invention relates to a kind of cement concrete technical fields of highly resistance chamotte mould dispersing agent, are related specifically to a kind of use Unsaturated carboxylic acid monomer first polymerize polycarboxylic acids main chain polymerizing cationically side chain then main side chain graft esterification synthesis highly resistance chamotte mould again The specific preparation method of cement dispersants.
Background technique
With the fast development of concrete science and engineering technology, workability of concrete, durability etc. can be obviously improved The cement concrete chemical admixture of performance is increasingly taken seriously and favors, however, concrete raw material is to chemical admixture Application performance have an important influence, especially admixture aggregate when a small amount of clay for being brought into can mobility to concrete, strong Degree, impermeability etc. have negative effect, this, which has become, restricts keeping in check for cement concrete chemical admixture popularization and application.
Due to the continuous increase serious in short supply and carrying capacity of environment of high-quality aggregate resources, it is mixed to develop a kind of highly resistance chamotte mould cement Solidifying soil dispersing agent has been the task of top priority.The great advantage of high-molecular type dispersing agent be can by exchange polymerized monomer type, Change the product that the methods of monomer match ratio and regulatory molecule structure functional group design different molecular structures and performance, thus It is the dispersing agent kind that a kind of structure flexible design degree is big, performance regulation space is big.Therefore, cement concrete dispersing agent is ground Study carefully and apply it is more and more extensive, towards efficiency is more significant, feature is distincter, functionality is stronger, the wider array of direction of adaptation range not Disconnected development.
Molecular Design method is introduced into the synthesis field of cement concrete dispersing agent, development can inhibit clay pair The highly resistance chamotte mould dispersing agent of effect not only has the excellent working performance of traditional dispersing agent, while also having and resisting clay pair work Peculiar advantage feature can sufficiently alleviate the imbalance between supply and demand of high-quality aggregate, realize ecological environmental protection and natural resources section It can lower consumption, show good application prospect.
Patent CN 104402292A (publication date: on March 11st, 2015) reports a kind of preparation of modified starch water-reducing agent Method.The patent is to carry out degradation modification using starch as primary raw material with oxidant and sodium carbonate, monomer and initiation is then added Agent carries out graft polymerization and prepares modified starch dispersing agent, and water-reducing rate is 3-4 hours up to 26-28%, retarding time, can be effective Ground prevents phenomena such as bleeding, isolation.The advantages of invention is using safety and environmental protection and native starch from a wealth of sources is former as reaction Material, realizes the purpose for reducing cost, simultaneously as it is partially modified in structure, therefore water can also be improved to a certain extent The workability of cement concrete and adaptability containing argillaceous sand stone.But the invention product still need in net slurry mortar concrete The additives such as polycarboxylate water-reducer are used cooperatively, and are not able to achieve the anti-mud multifunctional all of diminishing, do not have on structural level The unique advantage of standby complex function type, the progress and innovation in structure that can not inherently realize.
Patent CN 104311743A (publication date: on January 28th, 2015) reports a kind of low cost for wastewater treatment The preparation method of modified flocculant.The invention is caused based on hydroxymethyl starch by the way that ammonium ceric nitrate is added as initiator Acrylamide monomer reacts to obtain modified flocculant with formaldehyde and dimethylamine again in hydroxymethyl starch surface grafting polymerization, product. The advantages of invention be using the extensive hydroxymethyl starch in source as key reaction raw material, it is low in cost, the pH value scope of application is wide, Flocculating property is excellent, and the ammonium ceric nitrate initiator used can also effectively utilize the advantage of the initiation system.But it should Invention product neither has the ability of diminishing dispersion as excellent flocculant, does not also have highly resistance mud effect, therefore although utilize The initiation system of ammonium ceric nitrate, still can not be applied to cement concrete anti-mud water-reducing agent field.
Patent CN104446101A (publication date: on March 25th, 2015) reports the cation-modified polycarboxylic acids of one kind and subtracts Aqua is by isoamyl alcohol polyoxyethylene ether monomer, unitary unsaturated carboxylic acid and its derivatives monomer, cationic 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 is only to introduce cationic monomer in the main chain of molecular structure, is mentioned High diminishing dispersion effect centainly, and be not implemented while diminishing dispersion and show highly resistance mud performance etc. using feature, Fail to achieve the purpose that Molecular Design method realizes chemical admixture functionalization.
Cement concrete described in most patents has been provided with the works such as good mobility, dispersibility with diminishing dispersing agent Make performance.However, the product that above-mentioned synthetic method obtains has a degree of shortcoming, researcher focuses mostly on to be subtracted in realization Water dispersion, anti-mud, flocculation a certain item performance therein, and seldom pass through the cationic that is graft-polymerized under high price cerium salt initiation system The method of side chain realizes that integrating diminishing-guarantor is collapsed-disperses-complex function type chemical admixture of the application performances such as anti-mud.Only It is only limited in water reducer of cement concrete field by simple backbone modification or synthetic starch base diminishing dispersant material Popularization and application, warp facts proved that synthesis have multiple action complex function group type molecular structure can significantly improve polymer Application performance effect.Therefore, this requires the cement concrete dispersing agents of synthesis to realize the innovation of molecular structure, not only to have Standby diminishing protects the-compound working performance of anti-mud of collapsing, while also can guarantee convenient and fast technological operation, cheap preparation cost, letter The reaction raw materials being singly easy to get, are conducive to industrialized production and popularization and application, and 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 of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain Skill carries out free radical polymerization by unsaturated carboxylic acid class monomer and obtains polycarboxylic acids main chain, then forms high price cerium salt and alcohols Oxidation-reduction trigger system, which causes, to be polymerize unsaturated cationic quaternary ammonium salt monomer and obtains terminal hydroxy group cationic side chain, then by poly- carboxylic The highly resistance chamotte mould cement that sour main chain and terminal hydroxy group cationic side chain, polyethylene glycols compound graft esterification are had excellent performance is mixed Solidifying soil dispersing agent.The present invention is to increase from design theory of molecular structure using high price cerium salt -ol as Redox Initiator The step of polymeric cationic side chain and successfully graft esterification is realized under system, and polycarboxylic acids main chain is connected to cationic side chain It is formed together the new polycarboxylic acid water reducer with the multiple actions such as high water reduction and highly resistance mud, realizes and passes through molecular side chain The modified purpose for improving its work efficiency, enriches polymer architecture-performance study answering in concrete chemical admixture field With.There is compound side-chain structure using the cement concrete diminishing dispersing agent of this method synthesis, subtract different from conventional polycarboxylic acids The side chain of aqua forms, and polyether lateral chain can be acted on by steric hindrance realizes that excellent diminishing protects effect of collapsing, cation Side-chain structure can also change charge electrical property in the concrete system of high clay content, and polyether lateral chain is further prevented to be adsorbed Into clay interlayer, the adverse effect that can effectively inhibit clay to generate dispersion flows performance is shown than common polycarboxylic acids The more excellent working characteristics of water-reducing agent and function and effect.
The present invention provides a kind of preparation methods of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain, pass through First backbone polymerization again cationic side chain polymerization then graft esterification method synthesize highly resistance chamotte mould cement dispersants material, including with Lower condition and step:
(1) backbone polymerization: sequentially added into reactor (methyl) acrylic acid or its mixture with unsaturated carboxylic acid, Water, molecular weight regulator, the initiator persulfate aqueous solution that mass fraction is 1-30%, and when each feeding interval stirring Between 5-20 minutes, be warming up at 55-90 DEG C and carry out polymerization reaction, react 1.5-8 hours to get polycarboxylic acids main chain aqueous solution；
(2) cationic side chain polymerize: monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols being 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 cationic side chain aqueous solution；
(3) graft esterification: by step (1) products therefrom polycarboxylic acids main chain aqueous solution and step (2) products therefrom terminal hydroxy group Cationic side chain aqueous solution mixes, and adds polyethylene glycols compound, is warming up to 50-70 DEG C, to polyethylene glycols chemical combination Object is in a liquid state, and vacuumizes moisture in removing system, and catalyst is added, and stirs 5-20 minutes, temperature is increased to add at 80-100 DEG C Enter water entrainer, be continuously heating to carry out esterification at 100-150 DEG C, separates reaction gained water while reaction, instead Water entrainer is sloughed by vacuumizing after answering 2-10 hours, esterification reaction product is obtained, is cooled to 25-40 DEG C, it is dilute to be eventually adding water Release needed for concentration graft esterification cationic side chain cement dispersants solution.
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；Addition water described in step (1) Quality be in step (1) (methyl) acrylic acid or its mixture quality with unsaturated carboxylic acid and 80-200%；In step (1) The molecular weight regulator is thioacetic acid, mercaptopropionic acid, methylpropene sodium sulfonate, Sodium Allyl Sulfonate or dodecyl The molar ratio of mercaptan, (methyl) acrylic acid that dosage and step (1) are added or itself and the mixture of unsaturated carboxylic acid is 0.01- 0.15:1；Initiator persulfate described in step (1) is ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate, dosage and step (1) molar ratio of (methyl) acrylic acid or itself and the mixture of unsaturated carboxylic acid that are added is 0.01-0.1:1.
Unsaturated cation quaternary ammonium salt described in above-mentioned steps (2) 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 (2) are 10-1000:1；Institute in step (2) 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, (methyl) acrylic acid that dosage and step (1) are added or itself and unsaturated carboxylic acid Mixture molar ratio be 0.1-0.25:1；High price cerium salt described in step (2) is ammonium ceric nitrate or Cericammoniumsulfate, dosage Molar ratio with lower aliphatic alcohols described in step (2) is 0.03-1:1.
Polyethylene glycols compound described in above-mentioned steps (3) be polyethylene glycol or methoxy poly (ethylene glycol), dosage with The molar ratio of (methyl) acrylic acid or itself and the mixture of unsaturated carboxylic acid that step (1) is added is 0.15-0.25:1；Step (3) catalyst described in is p-methyl benzenesulfonic acid, phosphoric acid or sulfamic acid, and dosage is polyethylene glycols compound in step (3) The 2.5-20% of quality；Water entrainer described in step (3) is hexamethylene, benzene or toluene, and dosage is reactant in esterification The 8-30% of gross mass, signified reactant are products therefrom polycarboxylic acids main chain in step (1), products therefrom end in step (2) Polyethylene glycols compound in hydroxyl cationic side chain and step (3).
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. the present invention is from design theory of molecular structure, using unsaturated cationic quaternary ammonium salt monomer as reactant, in height Free radical polymerization obtains cationic side chain under the oxidation-reduction trigger system of valence cerium salt and alcohol composition, this is from conventional polyethers The unique design that side chain develops to diversification, the compound side chain of multifunction, is on comb shape diminishing dispersant molecule structure direction Innovation and breakthrough, change of the dispersing agent in terms of application performance not only may be implemented in novel special structure, but also advantageous In expanding Polymer supported catalyst-structure-performance intension of theory, other new types of Cernent point are developed to a deeper level to be subsequent Powder 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 highly resistance chamotte mould cement dispersants of the graft esterification cationic side chain of synthesis have a large amount of quaternary ammonium salt cationic polymerization macromolecule chains, Electrostatic adsorption can be generated with the interlayer of electronegative clay particle and surface, be conducive to be adsorbed on clay interlayer, meanwhile, The interlamination region volume of clay is not infinity, can be to avoid other polyethers sides after having adsorbed a large amount of cationic side chain Chain enters clay interlayer, does not lose so that the diminishing of the cement dispersants be protected to protect effect of collapsing, to show high water reduction, highly resistance The function and effect of mud.The product can also diversification expanded application in the fields such as fine chemistry industry and surfactant, be a kind of tool There is the cement concrete dispersing agent of peculiar advantage and distinguishing feature, has a good application prospect and the market competitiveness.
3. synthetic method of the present invention is compared with the traditional method, raw materials required for the reaction is common to be easy to get, and entire synthesis process is simple Controllably, esterification used and polymerization procedure are also normal operations technique, without special operation or expensive auxiliary agent, enrich synthesis The preparation method of cement concrete chemical admixture has the characteristics that apparent efficient and convenient, it is easy to accomplish industrialized production. The synthesis process, without particular/special requirement, and remains with the functional group of high water reduction contained by tradition and high-thin arch dam effect to equipment, and Have many advantages, such as that molecule can designed capacity be strong, molecular weight is controllable, narrow molecular weight distribution, the degree of polymerization are high, have promote well it is latent Power and application value.
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 etc., the polymerization under the initiation system is anti- Process is answered mildly to stablize, side reaction is few, and can substantially reduce the activation energy in polymerization process, it has a extensive future, A kind of method of new initiation polymerization is provided with dispersing agent for cement concrete.
5. low energy consumption for a synthesis process, mild condition, safety and environmental protection, solvent-free murder by poisoning, cleanliness without any pollution, water entrainer used It can also continue to be recycled after liquid separation-standing-separation, greatly reduce wastage of material, saved production cost.Water entrainer It is condensed back the temperature plateau that can also keep reaction system, and the viscosity of reaction system can be reduced, makes to be stirred more It is even abundant, improve the esterification yield and reaction rate of system.Meanwhile the unsaturated carboxylic acid class monomer used and unsaturated cationic season The suitable molecular weight range of ammonium salt monomer raw material is wide, is conducive to the large-scale popularization and application of Diversified Products, increases highly resistance chamotte mould The market share occupancy volume of cement concrete dispersing agent.
6. the highly resistance chamotte mould cement dispersing agent according to the method for the present invention synthesis has more than common polycarboxylate water-reducer Excellent workability, diminishing guarantor are collapsed ability and anti-mud effect, remain to show preferable mobility and holding in high clay content Ability, and very strong adaptability is shown to the cement of different cultivars.In addition, the cement dispersants Product Status is stablized, it is high It is not stratified after being stood under concentration, it is not crystallized after being stored under low temperature and performance is unaffected.The synthetic method is simple direct Meanwhile products obtained therefrom still has excellent performance indexes, is conducive to industrial application, therefore has warp well Benefit of helping 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
The ammonium persulfate for being first 18% by 7.21g acrylic acid, 8.65g water, 0.91g thioacetic acid and 5.1g mass fraction It is added in reactor, each feeding interval 9 minutes is warming up at 75 DEG C and carries out polymerization reaction, reacts 7 hours to get polycarboxylic acids Main chain aqueous solution；Then successively into another reactor be added 12.89g trimethylallylammonium chloride, 1.41g n-butanol and 700.41g water, 4 deoxygenations seal reactor inflated with nitrogen after 15 minutes repeatedly, be added 0.52g ammonium ceric nitrate, stirring 25 minutes to It is uniformly mixed, and is continuously heating to carry out polymerization reaction at 35 DEG C, and reaction 12 hours water-soluble to get terminal hydroxy group cationic side chain Liquid, then be separately added into reactor gained polycarboxylic acids main chain aqueous solution and 50.4g methoxy poly (ethylene glycol) (molecular weight= 2400) 60 DEG C, are warming up to, is in a liquid state to methoxy poly (ethylene glycol) (molecular weight=2400), is vacuumized moisture in removing system, add Enter 6.05g p-methyl benzenesulfonic acid, stir 15 minutes, temperature is increased to that 14.38g hexamethylene is added at 90 DEG C, is continuously heating to 120 DEG C Reaction gained water is separated while reaction, sloughs hexamethylene by vacuumizing after reaction 6 hours by lower carry out esterification Alkane obtains esterification reaction product, is cooled to 35 DEG C, is eventually adding the graft esterification that 106.77g water is 40% up to mass fraction The cement dispersants solution of cationic side chain.
Embodiment 2
After the cement dispersants solution that the concentration that embodiment 1 is obtained is 40% is stored 20 days at 6 DEG C, its implementation is measured Effect.
Embodiment 3
First by 7.83g methacrylic acid, 1.18g itaconic acid, 13.51g water, 1.38g mercaptopropionic acid and 12.29g mass The ammonium persulfate that score is 22% is added in reactor, and each feeding interval 20 minutes is warming up at 55 DEG C and carries out polymerization reaction, Reaction 8 hours to get polycarboxylic acids main chain aqueous solution；Then 29.80g methacryl propyl is successively added into another reactor Trimethyl ammonium chloride, 0.88g n-amyl alcohol and 736.35g water, 3 deoxygenations seal reactor inflated with nitrogen after twenty minutes repeatedly, are added 5.37g Cericammoniumsulfate is uniformly mixed to it, is continuously heating to carry out polymerization reaction at 50 DEG C, react 8 hours for stirring 18 minutes, Up to terminal hydroxy group cationic side chain aqueous solution, then gained polycarboxylic acids main chain aqueous solution and the poly- second of 30g are separately added into reactor Glycol (molecular weight=1200), is warming up to 68 DEG C, is in a liquid state, is vacuumized in removing system to polyethylene glycol (molecular weight=1200) 2.4g phosphoric acid is added in moisture, stirs 10 minutes, and 17.32g benzene is added when temperature is increased to 80 DEG C, be continuously heating at 140 DEG C into Reaction gained water is separated while reaction, sloughs benzene by vacuumizing after reaction 5 hours, obtain ester by row esterification Change reaction product, be cooled to 30 DEG C, is eventually adding the graft esterification cationic side chain that 102.99g water is 40% up to mass fraction Cement dispersants solution.
Embodiment 4
After the cement dispersants solution that the concentration that embodiment 3 obtains is 40% is stored 20 days at 5 DEG C, its implementation is measured Effect.
Embodiment 5
First by 1.2g acrylic acid, 8.17g maleic anhydride, 18.74g water, 0.7908g methylpropene sodium sulfonate and 23.81g The sodium peroxydisulfate that mass fraction is 1% is added in reactor, each feeding interval 12 minutes, is warming up at 65 DEG C and polymerize instead It answers, reacts 3 hours to get polycarboxylic acids main chain aqueous solution；Then 46.73g methacryl is successively added into another reactor Oxy-ethyl-trimethyl salmiac, 0.9g isopropanol and 632.84g water, 5 deoxygenations seal reactor inflated with nitrogen after ten minutes repeatedly, 0.36g Cericammoniumsulfate is added, is uniformly mixed to it within stirring 25 minutes, is continuously heating to carry out polymerization reaction at 55 DEG C, reaction 6 is small When to get terminal hydroxy group cationic side chain aqueous solution, then be separately added into reactor gained polycarboxylic acids main chain aqueous solution and 57g first Oxygroup polyethylene glycol (molecular weight=3000), is warming up to 55 DEG C, is in a liquid state to methoxy poly (ethylene glycol) (molecular weight=3000), takes out Moisture in system is removed in vacuum, 1.43g sulfamic acid is added, stirs 8 minutes, temperature is increased to that 9.12g toluene is added at 95 DEG C, It is continuously heating to carry out esterification at 145 DEG C, separate reaction gained water while reaction, reaction passes through after 2 hours It vacuumizes and sloughs toluene, obtain esterification reaction product, be cooled to 28 DEG C, being eventually adding 264.58g water up to mass fraction is The cement dispersants solution of 30% graft esterification cationic side chain.
Embodiment 6
The cement dispersants solution that the mass fraction that embodiment 5 is obtained is 30% is after 5 DEG C are stored 30 days, and measurement is in fact Apply effect.
Embodiment 7
First by 4.3g methacrylic acid, 5.8g fumaric acid, 10.11g water, 1.1528g Sodium Allyl Sulfonate and 6.09g matter It measures the ammonium persulfate that score is 30% to be added in reactor, each feeding interval 15 minutes is warming up at 60 DEG C and polymerize instead It answers, reacts 5 hours to get polycarboxylic acids main chain aqueous solution；Then two allyl of 58.2g dimethyl is successively added into another reactor Ammonium chloride, 0.89g isobutanol and 652.84g water, 3 deoxygenations seal reactor inflated with nitrogen after 25 minutes repeatedly, and 0.2g is added Ammonium ceric nitrate, stirring 10 minutes to its be uniformly mixed, be continuously heating to carry out polymerization reaction at 30 DEG C, react 16 hours to get Terminal hydroxy group cationic side chain aqueous solution, then it is separately added into reactor gained polycarboxylic acids main chain aqueous solution and 46g methoxyl group is poly- Ethylene glycol (molecular weight=2000), is warming up to 50 DEG C, is in a liquid state to methoxy poly (ethylene glycol) (molecular weight=2000), vacuumizes and remove Moisture in system to be removed, 9.2g p-methyl benzenesulfonic acid is added, is stirred 20 minutes, temperature is increased to that 19.11g toluene is added at 85 DEG C, after Continuous be warming up at 115 DEG C carries out esterification, and reaction while separates reaction gained water, and reaction passed through pumping after 8 hours Vacuum sloughs toluene, obtains esterification reaction product, is cooled to 25 DEG C, and being eventually adding 295.8g water up to mass fraction is 30% The cement dispersants solution of graft esterification cationic side chain.
Embodiment 8
The cement dispersants solution that the mass fraction that embodiment 7 is obtained is 30% is after 6 DEG C are stored 40 days, and measurement is in fact Apply effect.
Embodiment 9
First by 1.6g acrylic acid, 2.89g itaconic acid, 2.58 maleic acids, 3.87g fumaric acid, 8.75g water, 0.72g positive ten The sodium peroxydisulfate that dialkyl group mercaptan and 23.81g mass fraction are 3% is added in reactor, each feeding interval 8 minutes, heating Polymerization reaction is carried out to 80 DEG C, reacts 1.5 hours to get polycarboxylic acids main chain aqueous solution；Then successively into another reactor Addition 48.42g acrylyl oxy-ethyl-trimethyl salmiac, 1.5g normal propyl alcohol and 695.14g water, reactor inflated with nitrogen 5 times repeatedly Deoxygenation seals after 18 minutes, be added 13.71g ammonium ceric nitrate, stirring 30 minutes to its be uniformly mixed, be continuously heating at 60 DEG C into Row polymerization reaction reacts 6.5 hours to get terminal hydroxy group cationic side chain aqueous solution, then is separately added into gained into reactor and gathers Carboxylic acid main chain aqueous solution and 8.5g polyethylene glycol (molecular weight=500), are warming up to 70 DEG C, to polyethylene glycol (molecular weight=500) It is in a liquid state, vacuumizes moisture in removing system, 0.26g p-methyl benzenesulfonic acid is added, stir 13 minutes, when temperature is increased to 100 DEG C 32.78g hexamethylene is added, is continuously heating to carry out esterification at 135 DEG C, separates out reaction gained moisture while reaction It goes, sloughs hexamethylene by vacuumizing after reaction 10 hours, obtain esterification reaction product, be cooled to 40 DEG C, be eventually adding The cement dispersants solution for the graft esterification cationic side chain that 108.53g water is 50% up to mass fraction.
Embodiment 10
The cement dispersants solution that the mass fraction that embodiment 9 is obtained is 50% is after 7 DEG C are stored 40 days, and measurement is in fact Apply effect.
Embodiment 11
First by 2.46g methacrylic acid, 3.72g itaconic acid, 2.8 maleic anhydrides, 1.66g fumaric acid, 19.15g water, The sodium peroxydisulfate that 1.37g thioacetic acid and 13.52g mass fraction are 10% is added in reactor, each feeding interval 5 minutes, It is warming up at 90 DEG C and carries out polymerization reaction, react 3.5 hours to get polycarboxylic acids main chain aqueous solution；Then successively to another reaction 76.49g methylacryoyloxyethyl dimethylbutyl ammonium bromide, 1.3g cyclohexanol and 700.15g water, reactor are added in device to fill 4 deoxygenations seal nitrogen after 30 minutes repeatedly, and 3.1g Cericammoniumsulfate is added, and are uniformly mixed within stirring 13 minutes to it, continue to heat up Polymerization reaction is carried out to 10 DEG C, is reacted 15 hours and is added respectively to get terminal hydroxy group cationic side chain aqueous solution, then into reactor Enter gained polycarboxylic acids main chain aqueous solution and 12g polyethylene glycol (molecular weight=800), 65 DEG C is warming up to, to polyethylene glycol (molecular weight =800) it is in a liquid state, vacuumizes moisture in removing system, 1.8g phosphoric acid is added, stir 5 minutes, temperature is increased to addition at 98 DEG C 10.43g benzene is continuously heating to carry out esterification at 150 DEG C, separates reaction gained water while reaction, reaction 4 is small When after slough benzene by vacuumizing, obtain esterification reaction product, be cooled to 38 DEG C, be eventually adding 99.93g water up to mass fraction For the cement dispersants solution of 50% graft esterification cationic side chain.
Embodiment 12
After the cement dispersants solution that the concentration that embodiment 11 is obtained is 50% is stored 30 days at 6 DEG C, measurement is in fact Apply effect.
Implementation result:
1. flowing degree of net paste of cement
The mobility of cement is made to investigate the cement dispersants solution for the graft esterification cationic side chain that the present invention synthesizes With effect, test determines under identical volume each embodiment to the paste flowing degree of reference cement.GB/T8077- is pressed in test 2012 " Methods for testing uniformity of concrete admixture " carry out, W/C=0.29, and volume is to roll over solid volume.It selects existing commercially available Traditional 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 dispersants solution of the graft esterification cationic side chain of the method for the present invention synthesis, 0.29 ratio of mud and 0.25% folding are consolidated under volume, and excellent dispersibility and cement adaptability can be shown.
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 dispersants solution of the graft esterification cationic side chain of the method for the present invention synthesis exists Excellent divergence and the slump and holding capacity can be shown 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 dispersants solution of the graft esterification cationic side chain of the method for the present invention synthesis exists Preferable divergence and the slump and holding capacity can have been shown under 1.8% clay additive.

Claims (3)

1. a kind of preparation method of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain, which is characterized in that pass through elder generation Backbone polymerization again cationic side chain polymerization then graft esterification method synthesis highly resistance chamotte mould cement dispersants material condition and Steps are as follows:
(1) backbone polymerization: sequentially added into reactor (methyl) acrylic acid or its mixture with unsaturated carboxylic acid, water, point Son amount regulator, the initiator persulfate aqueous solution that mass fraction is 1-30%, and feeding interval mixing time 5- every time It 20 minutes, is warming up at 55-90 DEG C and carries out polymerization reaction, react 1.5-8 hours to get polycarboxylic acids main chain aqueous solution；
(2) cationic side chain polymerize: another reaction 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 cationic side chain aqueous solution；
(3) graft esterification: by step (1) products therefrom polycarboxylic acids main chain aqueous solution and step (2) products therefrom terminal hydroxy group sun from Sub- side chain aqueous solution mixes, and adds polyethylene glycols compound, is warming up to 50-70 DEG C, is in polyethylene glycols compound Liquid vacuumizes moisture in removing system, and catalyst is added, and stirs 5-20 minutes, temperature is increased to that band is added at 80-100 DEG C Aqua is continuously heating to carry out esterification at 100-150 DEG C, separates reaction gained water while reaction, reacts 2- Water entrainer is sloughed by vacuumizing after 10 hours, esterification reaction product is obtained, is cooled to 25-40 DEG C, be eventually adding water and dilute The cement dispersants solution of the graft esterification cationic side chain of required concentration；
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；The quality that water is added described in step (1) is (methyl) acrylic acid or itself and unsaturated carboxylic acid in step (1) The 80-200% of mixture quality sum；Molecular weight regulator described in step (1) is thioacetic acid, mercaptopropionic acid, methyl-prop Alkene sodium sulfonate, Sodium Allyl Sulfonate or n-dodecyl mercaptan, (methyl) acrylic acid that dosage and step (1) are added or its with not The molar ratio of the mixture of saturated carboxylic acid is 0.01-0.15:1；Initiator persulfate described in step (1) is persulfuric acid Ammonium, potassium peroxydisulfate or sodium peroxydisulfate, the mixture of (methyl) acrylic acid or itself and unsaturated carboxylic acid of dosage and step (1) addition Molar ratio be 0.01-0.1:1；Unsaturated cation quaternary ammonium salt described in step (2) is trimethylallylammonium chloride, two Methyl diallyl ammonium chloride, tetra allyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl three Ammonio methacrylate, methacryl hydroxypropyltrimonium chloride, acryloxyethyldimethyl butylammonium bromide, methacryl Oxygen ethyl dimethylbutyl ammonium bromide, acryloxyethyldimethyl dodecyl ammonium bromide, methylacryoyloxyethyl diformazan Base dodecyl ammonium bromide, acryloxyethyldimethyl cetyl ammonium bromide, methylacryoyloxyethyl dimethyl 16 One or more of alkyl bromination ammonium, the molar ratio of high price cerium salt described in dosage and step (2) are 10-1000:1；Step Suddenly lower aliphatic alcohols described in (2) are 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 (2) is ammonium ceric nitrate or sulfuric acid Cerium ammonium, the molar ratio of lower aliphatic alcohols described in dosage and step (2) are 0.03-1:1；Poly- second two described in step (3) Alcohol compound is polyethylene glycol or methoxy poly (ethylene glycol)；Catalyst described in step (3) be p-methyl benzenesulfonic acid, phosphoric acid or Sulfamic acid, dosage are the 2.5-20% of polyethylene glycols compound quality in step (3)；Water entrainer described in step (3) For hexamethylene, benzene or toluene, dosage is the 8-30% of reactant gross mass in esterification, and signified reactant is step (1) Polyethylene glycols in products therefrom terminal hydroxy group cationic side chain and step (3) in middle products therefrom polycarboxylic acids main chain, step (2) Close object.
2. a kind of preparation side of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain according to claim 1 Method, it is characterised in that (methyl) acrylic acid that lower aliphatic alcohols described in step (2) and step (1) are added or itself and unsaturation The molar ratio of the mixture of carboxylic acid is 0.1-0.25:1.
3. a kind of preparation side of the highly resistance chamotte mould cement dispersants of graft esterification cationic side chain according to claim 1 Method, it is characterised in that (methyl) acrylic acid that polyethylene glycols compound described in step (3) and step (1) are added or its with The molar ratio of the mixture of unsaturated carboxylic acid is 0.15-0.25:1.
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