CN106117564A - A kind of preparation method of the height anti-chamotte mould cement dispersants of graft esterification cationic side chain - Google Patents
A kind of preparation method of the height anti-chamotte mould cement dispersants of graft esterification cationic side chain Download PDFInfo
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- CN106117564A CN106117564A CN201610563315.6A CN201610563315A CN106117564A CN 106117564 A CN106117564 A CN 106117564A CN 201610563315 A CN201610563315 A CN 201610563315A CN 106117564 A CN106117564 A CN 106117564A
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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
- C04B24/24—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
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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
- 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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- 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
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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
- C04B2103/48—Foam stabilisers
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Abstract
一种酯化接枝阳离子侧链的高抗泥型水泥分散剂的制备方法属于分散剂领域。本发明以不饱和羧酸类单体为反应物，在引发剂和链转移剂作用下进行自由基聚合得到聚羧酸主链，然后以不饱和阳离子季铵盐单体为反应物，在高价铈盐与醇组成的氧化‑还原引发体系下自由基聚合得到端羟基阳离子侧链，再将聚羧酸主链与端羟基阳离子侧链、聚乙二醇类化合物在催化剂的作用下通过酯化接枝反应制得。本发明过程简单易控、成本低廉、节能高效、环保无污染，通过分子结构设计改性合成复合侧链结构，成功实现侧链空间位阻效应和阳离子电荷排布，表现出比普通聚羧酸减水剂更加优异的减水保坍特性和抑制粘土副作用能力，具有广阔的市场前景和推广应用潜力。The invention discloses a preparation method of a high mud-resistant cement dispersant with esterification and grafted cationic side chains, belonging to the field of dispersants. The present invention uses unsaturated carboxylic acid monomers as reactants, carries out free radical polymerization under the action of initiator and chain transfer agent to obtain polycarboxylic acid main chain, and then uses unsaturated cationic quaternary ammonium salt monomers as reactants, at high price Under the oxidation-reduction initiation system composed of cerium salt and alcohol, free radical polymerization is carried out to obtain hydroxyl-terminated cationic side chains, and then the polycarboxylic acid main chain, hydroxyl-terminated cationic side chains, and polyethylene glycol compounds are esterified under the action of a catalyst. prepared by grafting reaction. The process of the invention is simple and easy to control, low in cost, energy-saving and high-efficiency, and environmentally friendly and pollution-free. The composite side chain structure is synthesized through molecular structure design modification, and the steric hindrance effect of the side chain and the arrangement of cationic charges are successfully realized. The superplasticizer has more excellent water-reducing and slump-preserving properties and the ability to inhibit the side effects of clay, and has broad market prospects and potential for promotion and application.
Description
Technical field
The present invention relates to a kind of cement concrete technical field with high anti-chamotte mould dispersant, be related specifically to a kind of employing
Unsaturated carboxylic acid monomer is first polymerized polycarboxylic acids main chain repolymerization cationic side chain then master chain graft esterification and synthesizes high anti-chamotte mould
The concrete preparation method of cement dispersants.
Background technology
Fast development along with concrete science Yu engineering, it is possible to be obviously improved workability of concrete, durability etc.
The cement concrete chemical admixture of performance increasingly comes into one's own and favors, but, concrete raw material is to chemical admixture
Application performance important, especially during admixture aggregate, a small amount of clay of being brought into can be to the mobility of concrete, strong
The aspects such as degree, impermeability have negative effect, and this has become keeping in check of restriction cement concrete chemical admixture popularization and application.
Due to the most in short supply of high-quality aggregate resources and the continuous increase of carrying capacity of environment, develop a kind of high anti-chamotte mould cement and mix
Solidifying soil dispersant has been the task of top priority.The great advantage of high-molecular type dispersing agent be can by exchange polymerization monomeric species,
Change the method such as monomer match ratio and regulatory molecule structure functional group and design the product of different molecular structures and performance, thus
It it is the dispersant kind that a kind of structure flexible design degree is big, performance regulation and control space is big.Therefore, the grinding of cement concrete dispersant
Study carefully and apply more and more extensive, more notable towards usefulness, feature is distincter, functional higher, the wider array of direction of subject range not
Disconnected development.
Molecular Design method being incorporated in the synthesis field of cement concrete dispersant, development can suppress clay secondary
The height anti-chamotte mould dispersant of effect, not only has the excellent service behaviour of traditional dispersant, the most also has opposing clay pair and makees
Peculiar advantage feature, can fully alleviate the imbalance between supply and demand of high-quality aggregate, it is achieved ecological environmental protection and natural resources joint
Can lower consumption, show good application prospect.
Patent CN 104402292A (publication date: on March 11st, 2015) reports the preparation of a kind of modified starch water reducer
Method.This patent is with starch as primary raw material, carries out degradation modification with oxidant and sodium carbonate, then adds monomer and initiation
Agent carries out glycerol polymerization and prepares modified starch dispersant, and water-reducing rate is 3-4 hour up to 26-28%, slow setting time, it is possible to effectively
Prevent the phenomenon such as bleeding, isolation.The advantage of this invention is former as reaction using the native starch of safety and environmental protection and wide material sources
Material, it is achieved that reduce the purpose of cost, simultaneously as partially modified in structure, therefore can also improve water to a certain extent
The workability of cement concrete and the adaptability containing argillaceous sand stone.But this invention product need nonetheless remain for and only starch in mortar concrete
The additives such as polycarboxylate water-reducer with the use of, fail to realize diminishing anti-mud multifunctional all, structural level do not have
The unique advantage of standby complex function type, it is impossible to the progress in structure inherently realized and innovation.
Patent CN 104311743A (publication date: on January 28th, 2015) reports a kind of low cost processed for waste water
The preparation method of modified flocculant.This invention, based on hydroxymethyl starch, causes as initiator by adding ammonium ceric nitrate
Acrylamide monomer is at hydroxymethyl starch surface grafting polymerization, and product reacts with formaldehyde and dimethylamine and obtains modified flocculant.
The advantage of this invention be using originate widely hydroxymethyl starch as dominant response raw material, with low cost, pH value scope of application width,
Flocculating property is excellent, and the ammonium ceric nitrate initiator used also is able to effectively utilize the advantage of this initiator system.But should
Invention product, as excellent flocculant, neither possesses the scattered ability of diminishing, does not the most possess high anti-mud effect, although therefore utilizing
The initiator system of ammonium ceric nitrate, still cannot be applied to cement concrete anti-mud water reducer field.
Patent CN104446101A (publication date: on March 25th, 2015) reports a kind of cation-modified polycarboxylic acids and subtracts
Water preparation, is by isopentenol polyoxyethylene ether monomer, unitary unsaturated carboxylic acid and derivatives monomer, cationic monomer and two
Unit's unsaturated carboxylic acid and derivatives monomer combined polymerization under the effect of initiator and chain-transferring agent thereof form.This invention product adds
Time in concrete, can adsorb on positively charged and electronegative cement minerals surface simultaneously, embody and be superior to anion
The feature of type polycarboxylate water-reducer, and, this product extends at cement slurry alkaline environment Middle molecule chain, and absorption shape is more
Unfolding, water-reducing rate is more excellent.But this invention product is only to introduce cationic monomer in the main chain of molecular structure, carries
High diminishing dispersion effect necessarily, and unrealized in the scattered application features such as high anti-mud performance that show of diminishing simultaneously, also
Fail to reach Molecular Design method and realize the purpose of chemical admixture functionalization.
Cement concrete diminishing dispersant described in most patents has been provided with the works such as good mobility, dispersibility
Make performance.But, the product that above-mentioned synthetic method obtains all has a certain degree of weak point, and researcher focuses mostly on and subtracts in realization
Mud water-dispersible, anti-, a certain item performance therein of flocculating, and seldom by glycerol polymerization cationic under high price cerium salt inducement system
The method of side chain realizes integrating diminishing-guarantor and collapses-disperse-complex function type chemical admixture of the application performance such as anti-mud.Only
Only limit it in water reducer of cement concrete field by simple backbone modification or synthetic starch base diminishing dispersant material
Popularization and application, through fact proved that synthesis has the complex function group type molecular structure of multiple action and can significantly improve polymer
Application performance effect.Therefore, this just requires that the cement concrete dispersant of synthesis realizes the innovation of molecular structure, not only to have
Standby diminishing protects the-compound service behaviour of anti-mud of collapsing, and the most also can guarantee that technological operation easily, cheap preparation cost, letter
The reaction raw materials being singly easy to get, beneficially industrialized production and popularization and application, the work of relevant this respect has no report both at home and abroad.
Summary of the invention
It is an object of the invention to provide the synthesis work of the height anti-chamotte mould cement dispersants of a kind of graft esterification cationic side chain
Skill, carries out radical polymerization by unsaturated carboxylic acid class monomer and obtains polycarboxylic acids main chain, then formed with alcohols by high price cerium salt
Oxidation-reduction trigger system causes the unsaturated cationic quaternary ammonium salt monomer of polymerization to obtain terminal hydroxy group cationic side chain, then by poly-carboxylic
Acid main chain and terminal hydroxy group cationic side chain, Polyethylene Glycol compounds graft esterification obtain the height anti-chamotte mould cement of excellent performance to be mixed
Solidifying soil dispersant.The present invention is from design theory of molecular structure, adds with high price cerium salt-ol as redox initiation
The step of polymeric cationic side chain successfully realize graft esterification under system, is connected to polycarboxylic acids main chain with cationic side chain
Form the new polycarboxylic acid water reducer with the multiple action effect such as high diminishing and the anti-mud of height together, it is achieved that pass through molecular side chain
The modified purpose improving its work efficiency, enriches polymer architecture-performance study answering in concrete chemical admixture field
With.The cement concrete diminishing dispersant using this method synthesis has compound side-chain structure, is different from conventional polycarboxylic acids and subtracts
The side chain composition of water preparation, its polyether lateral chain can realize excellent diminishing by sterically hindered effect and protect effect of collapsing, its cation
It is electrical that side-chain structure can also change electric charge in the concrete system of high clay content, prevents polyether lateral chain to be adsorbed further
Enter clay interlayer, the adverse effect that can effectively suppress clay that dispersion flows performance is produced, show than common polycarboxylic acids
Operating characteristic that water reducer is the most excellent and action effect.
The invention provides the preparation method of the height anti-chamotte mould cement dispersants of a kind of graft esterification cationic side chain, pass through
First backbone polymerization cationic side chain again is polymerized the method for then graft esterification and is synthesized high anti-chamotte mould cement dispersants material, including with
Lower condition and step:
(1) backbone polymerization: be sequentially added in reactor (methyl) acrylic acid or its mixture with unsaturated carboxylic acid,
Water, molecular weight regulator, mass fraction are the initiator persulfate aqueous solution of 1-30%, and when feeding interval stirs every time
Between 5-20 minute, carry out polyreaction at being warming up to 55-90 DEG C, react 1.5-8 hour, obtain polycarboxylic acids main chain aqueous solution；
(2) cationic side chain polymerization: monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols are added another
In reactor, add water and be configured to the aqueous solution that mass concentration is 2-10%, reactor inflated with nitrogen 3-5 deoxygenation 10-repeatedly
Seal after 30 minutes, add oxidant high price cerium salt, stir and within 10-30 minute, treat its mix homogeneously, at being continuously heating to 10-60 DEG C
Carry out polyreaction, react 6-16 hour, obtain 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
The water-soluble liquid-phase mixing of cationic side chain, adds Polyethylene Glycol compounds, is warming up to 50-70 DEG C, treats polyethylene glycols chemical combination
Thing is in a liquid state, moisture in evacuation removing system, adds catalyst, stirs 5-20 minute, and temperature is increased to when 80-100 DEG C add
Enter water entrainer, at being continuously heating to 100-150 DEG C, carry out esterification, while reaction, reaction gained water is separated, instead
Slough water entrainer by evacuation after answering 2-10 hour, obtain esterification reaction product, be cooled to 25-40 DEG C, be eventually adding water dilute
Release to obtain the cement dispersants solution of graft esterification cationic side chain of desired concn.
Unsaturated carboxylic acid described in above-mentioned steps (1) is the one or several in itaconic acid, maleic acid (acid anhydride), fumaric acid
Kind, consumption is 0.1-5:1 with (methyl) acrylic acid mol ratio of addition in step (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)
Described molecular weight regulator is TGA, mercaptopropionic acid, methylpropene sodium sulfonate, sodium allylsulfonate or dodecyl
Mercaptan, (methyl) acrylic acid that consumption and step (1) add or its mol ratio with the mixture of unsaturated carboxylic acid are 0.01-
0.15:1；Initiator persulfate described in step (1) is Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate, consumption and step
(1) mol ratio of (methyl) acrylic acid added or its mixture with unsaturated carboxylic acid 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 bromination ammonium, methylacryoyloxyethyl dimethyl dodecyl
Base ammonium bromide, acryloxyethyldimethyl cetyl ammonium bromide, methylacryoyloxyethyl dimethyl hexadecyl bromide
One or more in ammonium, consumption is 10-1000:1 with the mol ratio of the high price cerium salt described in step (2)；Institute in step (2)
The lower aliphatic alcohols stated is normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-fourth
Alcohol, 2,2-dimethyl-1-propanol or Hexalin, (methyl) acrylic acid that consumption and step (1) add or itself and unsaturated carboxylic acid
The mol ratio of mixture be 0.1-0.25:1；High price cerium salt described in step (2) is ammonium ceric nitrate or Cericammoniumsulfate, consumption
It is 0.03-1:1 with the mol ratio of the lower aliphatic alcohols described in step (2).
Polyethylene Glycol compounds described in above-mentioned steps (3) is Polyethylene Glycol or methoxy poly (ethylene glycol), consumption with
(methyl) acrylic acid that step (1) adds or its mol ratio with the mixture of unsaturated carboxylic acid are 0.15-0.25:1；Step
(3) catalyst described in is p-methyl benzenesulfonic acid, phosphoric acid or sulfamic acid, and consumption is Polyethylene Glycol compounds in step (3)
The 2.5-20% of quality；Water entrainer described in step (3) is hexamethylene, benzene or toluene, and consumption is reactant in esterification
The 8-30% of gross mass, the reactant of indication is products therefrom end in products therefrom polycarboxylic acids main chain in step (1), step (2)
Polyethylene Glycol compounds in hydroxyl cationic side chain and step (3).
The number-average molecular weight of the Polyethylene Glycol compounds in the inventive method is 500-3000.
The inventive method compared with prior art has the advantages that
1. the present invention is from design theory of molecular structure, with unsaturated cationic quaternary ammonium salt monomer as reactant, at height
Valency cerium salt obtains cationic side chain with radical polymerization under the oxidation-reduction trigger system of alcohol composition, and this is from conventional polyethers
Side chain is combined, to diversification, multifunction, the unique design that side chain develops, and is on comb shape diminishing dispersant molecule structure direction
Innovation and breakthrough, its novel special structure is possible not only to the change realizing dispersant in terms of application performance, and favorably
In the intension of theory of expansion Polymer supported catalyst-structure-performance, divide for follow-up other new types of Cernent of developing to a deeper level
Powder has widened Research Thinking and developing direction.
2. be different from other inventive method only a small amount of cationic structural of copolymerization in molecular backbone, the inventive method
The height anti-chamotte mould cement dispersants of the graft esterification cationic side chain of synthesis has a large amount of quaternary ammonium salt cationic polymerization macromolecule chain,
Electrostatic adsorption can be produced with the interlayer of electronegative clay particle and surface, be conducive to adsorbing at clay interlayer, meanwhile,
The interlamination region volume of clay is not infinitely-great, after having adsorbed substantial amounts of cationic side chain, can avoid other polyethers side
Chain enters clay interlayer, thus protects the diminishing of this cement dispersants to protect effect of collapsing and do not lose, thus shows high diminishing, high anti-
The action effect of mud.This product also can diversification ground expanded application in the field such as fine chemistry industry and surfactant, be a kind of tool
There is the cement concrete dispersant of peculiar advantage and distinguishing feature, there is good application prospect and the market competitiveness.
Synthetic method the most of the present invention is compared with traditional method, and needed raw material is common is easy to get in reaction, and whole building-up process is simple
Controlled, esterification used and polymerization procedure are also normal operations technique, it is not necessary to special operational or expensive auxiliary agent, enrich synthesis
The preparation method of cement concrete chemical admixture, has feature the most easily, it is easy to accomplish industrialized production.
This building-up process without particular/special requirement, and remains with the high diminishing contained by tradition and the functional group of high-thin arch dam effect to equipment, and
Have that molecule can designed capacity be strong, molecular weight is controlled, narrow molecular weight distribution, degree of polymerization advantages of higher, have well promote latent
Power and using value.
4. the inventive method uses the redox initiation system of high price cerium salt-ol class innovatively, utilizes high price cerium salt
Strong oxidizing property and possess the characteristic causing Organic substance to produce free free radical, has abandoned traditional one-component thermal initiation system, list
The one high price initiator system of cerium salt, oxidation-reduction trigger system such as hydrogen peroxide-VC systems etc., the polymerization under this initiator system is anti-
Answering process gentleness stable, side reaction is few, and can be substantially reduced the activation energy in polymerization process, has a extensive future,
A kind of new method causing polymerization is provided for cement concrete dispersant.
5. this building-up process energy consumption is low, mild condition, safety and environmental protection, solvent-free murder by poisoning, cleanliness without any pollution, water entrainer used
Can also continue to recycle after separatory-standing-separation, greatly reduce wastage of material, saved production cost.Water entrainer
Condensing reflux can also keep the temperature plateau of reaction system, and can reduce the viscosity of reaction system, makes stirring mixing more equal
Even fully, improve the esterification yield of system and reaction rate.Meanwhile, the unsaturated carboxylic acid class monomer of use and unsaturated cation season
The large-scale popularization of the suitable molecular weight wide ranges of ammonium salt monomer raw material, beneficially Diversified Products and application, increase high anti-chamotte mould
The market share occupancy volume of cement concrete dispersant.
6. have than conventional polycarboxylate water-reducer more according to the height anti-chamotte mould cement dispersant of the inventive method synthesis
Excellent workability, diminishing protect collapse ability and anti-mud effect, remain to when high clay content show preferable mobility and holding
Ability, and the cement of different cultivars is shown the strongest adaptability.Additionally, this cement dispersants Product Status is stable, high
After standing under concentration not stratified, do not crystallize and performance is the most unaffected after storage under low temperature.This synthetic method is simple direct
Meanwhile, products obtained therefrom still has the property indices of excellence, beneficially industrial application, therefore has good warp
Ji benefit and social benefit.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but the enforcement of the present invention is not limited to this.
Embodiment 1
First it is the Ammonium persulfate. of 18% by 7.21g acrylic acid, 8.65g water, 0.91g TGA and 5.1g mass fraction
Add in reactor, each feeding interval 9 minutes, it is warming up at 75 DEG C carry out polyreaction, reacts 7 hours, obtain polycarboxylic acids
Main chain aqueous solution；The most successively in another reactor add 12.89g trimethylallylammonium chloride, 1.41g n-butyl alcohol and
700.41g water, 4 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 15 minutes, added 0.52g ammonium ceric nitrate, stirred and treat for 25 minutes
Its mix homogeneously, is continuously heating at 35 DEG C carry out polyreaction, reacts 12 hours, obtains terminal hydroxy group cationic side chain water-soluble
Liquid, then be separately added in reactor gained polycarboxylic acids main chain aqueous solution and 50.4g methoxy poly (ethylene glycol) (molecular weight=
2400), it is warming up to 60 DEG C, treats that methoxy poly (ethylene glycol) (molecular weight=2400) is in a liquid state, moisture in evacuation removing system, add
Entering 6.05g p-methyl benzenesulfonic acid, stir 15 minutes, temperature is increased to when 90 DEG C add 14.38g hexamethylene, is continuously heating to 120 DEG C
Under carry out esterification, while reaction, reaction gained water is separated, after reacting 6 hours, sloughs hexamethylene by evacuation
Alkane, obtains esterification reaction product, is cooled to 35 DEG C, is eventually adding 106.77g water and i.e. obtains the graft esterification that mass fraction is 40%
The cement dispersants solution of cationic side chain.
Embodiment 2
After the cement dispersants solution that concentration is 40% embodiment 1 obtained deposits 20 days at 6 DEG C, measure it and implement
Effect.
Embodiment 3
First by 7.83g methacrylic acid, 1.18g itaconic acid, 13.51g water, 1.38g mercaptopropionic acid and 12.29g mass
Mark is in the Ammonium persulfate. addition reactor of 22%, and each feeding interval 20 minutes is warming up at 55 DEG C carry out polyreaction,
React 8 hours, obtain polycarboxylic acids main chain aqueous solution；29.80g methacryl propyl group is added the most successively in another reactor
Trimethyl ammonium chloride, 0.88g n-amyl alcohol and 736.35g water, 3 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 20 minutes, added
5.37g Cericammoniumsulfate, stirs and treats its mix homogeneously in 18 minutes, is continuously heating at 50 DEG C carry out polyreaction, reacts 8 hours,
Obtain terminal hydroxy group cationic side chain aqueous solution, then in reactor, be separately added into gained polycarboxylic acids main chain aqueous solution and the poly-second of 30g
Glycol (molecular weight=1200), is warming up to 68 DEG C, treats that Polyethylene Glycol (molecular weight=1200) is in a liquid state, in evacuation removing system
Moisture, adds 2.4g phosphoric acid, stirs 10 minutes, and temperature is increased to when 80 DEG C add 17.32g benzene, is continuously heating at 140 DEG C enter
Row esterification, separates reaction gained water while reaction, sloughs benzene by evacuation, obtain ester after reacting 5 hours
Change product, be cooled to 30 DEG C, be eventually adding 102.99g water and i.e. obtain the graft esterification cationic side chain that mass fraction is 40%
Cement dispersants solution.
Embodiment 4
After the cement dispersants solution that concentration is 40% embodiment 3 obtained deposits 20 days at 5 DEG C, measure it and implement
Effect.
Embodiment 5
First by 1.2g acrylic acid, 8.17g maleic anhydride, 18.74g water, 0.7908g methylpropene sodium sulfonate and 23.81g
Mass fraction is in the sodium peroxydisulfate addition reactor of 1%, and each feeding interval 12 minutes is warming up at 65 DEG C carry out polymerization anti-
Should, react 3 hours, obtain polycarboxylic acids main chain aqueous solution；46.73g methacryl is added the most successively in another reactor
Oxy-ethyl-trimethyl salmiac, 0.9g isopropanol and 632.84g water, 5 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 10 minutes,
Adding 0.36g Cericammoniumsulfate, stir and treat its mix homogeneously in 25 minutes, be continuously heating at 55 DEG C carry out polyreaction, reaction 6 is little
Time, obtain terminal hydroxy group cationic side chain aqueous solution, then in reactor, be separately added into gained polycarboxylic acids main chain aqueous solution and 57g first
Epoxide Polyethylene Glycol (molecular weight=3000), is warming up to 55 DEG C, treats that methoxy poly (ethylene glycol) (molecular weight=3000) is in a liquid state, takes out
Moisture in vacuum removing system, adds 1.43g sulfamic acid, stirs 8 minutes, and temperature is increased to when 95 DEG C add 9.12g toluene,
It is continuously heating at 145 DEG C carry out esterification, while reaction, reaction gained water is separated, pass through after reacting 2 hours
Evacuation sloughs toluene, obtains esterification reaction product, is cooled to 28 DEG C, is eventually adding 264.58g water and i.e. obtains mass fraction and is
The cement dispersants solution of the graft esterification cationic side chain of 30%.
Embodiment 6
After the cement dispersants solution that mass fraction is 30% embodiment 5 obtained deposits 30 days at 5 DEG C, measure in fact
Execute effect.
Embodiment 7
First by 4.3g methacrylic acid, 5.8g fumaric acid, 10.11g water, 1.1528g sodium allylsulfonate and 6.09g matter
Amount mark is in the Ammonium persulfate. addition reactor of 30%, and each feeding interval 15 minutes is warming up at 60 DEG C carry out polymerization anti-
Should, react 5 hours, obtain polycarboxylic acids main chain aqueous solution；58.2g dimethyl two allyl is added the most successively in another reactor
Ammonium chloride, 0.89g isobutanol and 652.84g water, 3 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 25 minutes, added 0.2g
Ammonium ceric nitrate, stirs and treats its mix homogeneously in 10 minutes, is continuously heating at 30 DEG C carry out polyreaction, reacts 16 hours, to obtain final product
Terminal hydroxy group cationic side chain aqueous solution, then in reactor, be separately added into gained polycarboxylic acids main chain aqueous solution and 46g methoxyl group gather
Ethylene glycol (molecular weight=2000), is warming up to 50 DEG C, treats that methoxy poly (ethylene glycol) (molecular weight=2000) is in a liquid state, and evacuation removes
Removing moisture in system, add 9.2g p-methyl benzenesulfonic acid, stir 20 minutes, temperature is increased to when 85 DEG C add 19.11g toluene, continues
Continue and be warming up at 115 DEG C carry out esterification, while reaction, reaction gained water is separated, by taking out after reacting 8 hours
Vacuum sloughs toluene, obtains esterification reaction product, is cooled to 25 DEG C, and being eventually adding 295.8g water and i.e. obtaining mass fraction is 30%
The cement dispersants solution of graft esterification cationic side chain.
Embodiment 8
After the cement dispersants solution that mass fraction is 30% embodiment 7 obtained deposits 40 days at 6 DEG C, measure in fact
Execute 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
Dialkyl group mercaptan and the sodium peroxydisulfate that 23.81g mass fraction is 3% add in reactor, and each feeding interval 8 minutes heats up
At 80 DEG C, carry out polyreaction, react 1.5 hours, obtain polycarboxylic acids main chain aqueous solution；The most successively in another reactor
Add 48.42g acrylyl oxy-ethyl-trimethyl salmiac, 1.5g normal propyl alcohol and 695.14g water, reactor inflated with nitrogen 5 times repeatedly
Deoxygenation sealed after 18 minutes, adds 13.71g ammonium ceric nitrate, stirs and treat its mix homogeneously in 30 minutes, be continuously heating at 60 DEG C enter
Row polyreaction, reacts 6.5 hours, obtains terminal hydroxy group cationic side chain aqueous solution, then it is poly-to be separately added into gained in reactor
Carboxylic acid main chain aqueous solution and 8.5g Polyethylene Glycol (molecular weight=500), be warming up to 70 DEG C, treats Polyethylene Glycol (molecular weight=500)
It is in a liquid state, moisture in evacuation removing system, add 0.26g p-methyl benzenesulfonic acid, stir 13 minutes, when temperature is increased to 100 DEG C
Add 32.78g hexamethylene, be continuously heating at 135 DEG C carry out esterification, while reaction, reaction gained moisture separated out
Go, slough hexamethylene by evacuation after reacting 10 hours, obtain esterification reaction product, be cooled to 40 DEG C, be eventually adding
108.53g water i.e. obtains the cement dispersants solution of the graft esterification cationic side chain that mass fraction is 50%.
Embodiment 10
After the cement dispersants solution that mass fraction is 50% embodiment 9 obtained deposits 40 days at 7 DEG C, measure in fact
Execute effect.
Embodiment 11
First by 2.46g methacrylic acid, 3.72g itaconic acid, 2.8 maleic anhydrides, 1.66g fumaric acid, 19.15g water,
1.37g TGA and the sodium peroxydisulfate that 13.52g mass fraction is 10% add in reactor, each feeding interval 5 minutes,
It is warming up at 90 DEG C carry out polyreaction, reacts 3.5 hours, obtain polycarboxylic acids main chain aqueous solution；React to another the most successively
Adding 76.49g methylacryoyloxyethyl dimethylbutyl ammonium bromide, 1.3g Hexalin and 700.15g water in device, reactor fills
Nitrogen 4 deoxygenations repeatedly sealed after 30 minutes, added 3.1g Cericammoniumsulfate, stirred and within 13 minutes, treat its mix homogeneously, continue to heat up
At 10 DEG C, carry out polyreaction, react 15 hours, obtain terminal hydroxy group cationic side chain aqueous solution, then add respectively in reactor
Enter gained polycarboxylic acids main chain aqueous solution and 12g Polyethylene Glycol (molecular weight=800), be warming up to 65 DEG C, treat Polyethylene Glycol (molecular weight
=800) it is in a liquid state, moisture in evacuation removing system, add 1.8g phosphoric acid, stir 5 minutes, temperature is increased to when 98 DEG C add
10.43g benzene, is continuously heating at 150 DEG C carry out esterification, is separated by reaction gained water while reaction, and reaction 4 is little
Slough benzene by evacuation time after, obtain esterification reaction product, be cooled to 38 DEG C, be eventually adding 99.93g water and i.e. obtain mass fraction
It is the cement dispersants solution of the graft esterification cationic side chain of 50%.
Embodiment 12
After the cement dispersants solution that concentration is 50% embodiment 11 obtained deposits 30 days at 6 DEG C, measure in fact
Execute effect.
Implementation result:
1. flowing degree of net paste of cement
For investigating the cement dispersants solution of the graft esterification cationic side chain of present invention synthesis, the mobility of cement is made
By effect, test determination each embodiment paste flowing degree to reference cement under identical volume.GB/T8077-is pressed in test
2012 " Methods for testing uniformity of concrete admixture " are carried out, W/C=0.29, and volume is the solid volume of folding.Select existing commercially available
Tradition comb shape poly carboxylic acid series water reducer (comparative example) is as a comparison sample, and result of the test is shown in Table 1.
Table 1 pulp flowage results of property
From table 1 it follows that the cement dispersants solution of the graft esterification cationic side chain of the inventive method synthesis,
Under the ratio of mud of 0.29 and the solid volume of the folding of 0.25%, all can show dispersibility and the cement adaptability of excellence.
2. concrete slump and divergence
Divergence and the slump that each embodiment of test determination shows in concrete system and keep performance, test
The results are shown in Table 2.
Table 2 concrete flowability energy result
From Table 2, it can be seen that the cement dispersants solution of the graft esterification cationic side chain of the inventive method synthesis exists
Concrete system all can show excellent divergence and the slump and holding capacity.
3. agent on crack resistance of concrete mud performance
Divergence and the slump that each embodiment of test determination shows in concrete system and keep performance, test
The results are shown in Table 3.
Table 3 concrete flowability energy result
From table 3 it is observed that the cement dispersants solution of the graft esterification cationic side chain of the inventive method synthesis exists
Preferable divergence and the slump and holding capacity all can have been shown under the clay additive of 1.8%.
Claims (3)
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