CN106188556A - The method that cement water reducing agent prepared by the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting - Google Patents
The method that cement water reducing agent prepared by the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting Download PDFInfo
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- CN106188556A CN106188556A CN201610562936.2A CN201610562936A CN106188556A CN 106188556 A CN106188556 A CN 106188556A CN 201610562936 A CN201610562936 A CN 201610562936A CN 106188556 A CN106188556 A CN 106188556A
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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
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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
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- 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
- C08F120/22—Esters containing halogen
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- 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
- C08F126/04—Diallylamine
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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
- 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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- 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
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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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- Polymers & Plastics (AREA)
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Abstract
The method that cement water reducing agent prepared by the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting belongs to water reducer field.The present invention is by the first backbone polymerization method that modified carboxylic acid halides cationic side chain again is polymerized then graft reaction again, the compound side chain type cement water reducing agent material of poly carboxylic acid modified carboxylic acid halides grafting that processability is excellent, i.e. obtain polycarboxylic acids main chain with the radical polymerization of unsaturated carboxylic acid class monomer elder generation, hydroxy-acid group on main chain is modified as acyl halide group, then high price cerium salt is polymerized unsaturated cationic quaternary ammonium salt monomer with alcohol composition redox initiation system initiation and obtains terminal hydroxy group cationic side chain, again by the polycarboxylic acids main chain containing acyl halide group and terminal hydroxy group cationic side chain, Polyethylene Glycol compounds prepares through graft reaction.The present invention, by the way of poly carboxylic acid modified carboxylic acid halides grafted cation type side chain and side-chain of polyelycol, has synthesized compound side-chain structure, and course of reaction is simple and easy to control, efficient energy-saving, and the diminishing showing excellence protects the composite efficacy of the soil anti-stick with height that collapses.
Description
Technical field
The present invention relates to the technical field of a kind of compound side chain type cement water reducing agent, be related specifically to a kind of employing insatiable hunger
It is synthesized compound with the carboxylic acid monomer elder generation backbone polymerization modified acyl halide group the most main side chain graft of repolymerization cationic side chain again
The concrete preparation method of side chain type cement water reducing agent.
Background technology
As third generation water reducer, have become as in concrete with polycarboxylic acids for the polycarboxylate water-reducer of host molecule structure
Indispensable important component, the advantages such as volume is low, water-reducing rate is high, MOLECULE DESIGN degree of freedom is big that it has, for preparing and real
The good characteristic of existing high performance concrete has important contribution.Wide area along with auxiliary materials various in concrete so that
Cement water reducing agent becomes researchers' focus of attention for various raw-material adaptabilities.In concrete, sandstone aggregate can not
Certain clay can be carried with avoiding, the water reducer of polycarboxylic acid structure can be had significant negative effect, finally affect coagulation
The properties of soil, therefore, the side effect of clay rejection ability promoting polycarboxylic acid structure's water reducer has become concrete admixture
The task of top priority of industry.
The great advantage of polycarboxylic acid structure's type water reducer is to be joined by exchange polymerization monomeric species, change monomer
The method such as composition and division in a proportion and regulatory molecule structure functional group designs the product of different molecular structures and performance, its structure flexible design
Degree is big, performance regulation and control space is big.Therefore, it can contain the action character of mud problem for aggregate, design synthesis one has does not loses
Mistake diminishing originally is protected and is collapsed effect and have the cement water reducing agent of suppression side effect of clay concurrently, widens polycarboxylic acid structure's diminishing further
The range of agent, improves its raw material adaptability, strengthens performance advantage, drives its breakthrough performance and lifting with structure innovation.
Layer structure clay with negative charge is prone to adsorb the side chain macromole of the water reducer of polycarboxylic acid structure thus leads
The weakening causing diminishing function is even lost, and therefore, cationic structural is drawn by the present invention innovatively by Molecular Design method
Enter in polycarboxylic acid structure's water reducer field, synthesized the pure side-chain structure of strong cation, can electrically and protect by active balance electric charge
The macromolecule side chain of water-reduction, is obviously enhanced the inhibition to side effect of clay, and this will be to protection quality sand and stone aggregate, reality
The sustainable development of existing ecological resources, has great significance.
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.This patent is with poly glycol monomethyl ether as primary raw material, after being dissolved in dichloromethane, adds in ice-water bath
Acid binding agent and acryloyl chloride, decompression sucking filtration obtains polyalkylene glycol acrylate monomethyl ether ester, then obtains with acrylamide monomers combined polymerization
To the phase-changing energy storage material with pectination strand form.Phase-change material prepared by this invention can be with molten in hot procedure
The form flowing of body, its pectination strand form can reduce again its plasticization to matrix, and preparation technology is simple, production cost
Low.This invention takes full advantage of the response characteristic of acryloyl chloride and hydroxyl, and has synthesized comb-shaped polymer, and its main purpose is to close
Phase-changing energy storage material is become to reduce the energy consumption in the course of processing.But this invention is only with the reaction of acryloyl chloride Yu hydroxyl
Principle, is not applied in water reducer field be grafted the compound side chain of multi-efficiency, also fails to utilize grafted cation side chain
Method suppression side effect of clay, is also not carried out subversive transformation and innovation on structural nature.
Patent CN 104446101A (publication date: on March 25th, 2015) reports a kind of cation-modified polycarboxylic acids and subtracts
Water preparation, is by unitary unsaturated carboxylic acid and derivatives monomer, cationic monomer, isopentenol polyoxyethylene ether 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 be only introduce in the main chain of molecular structure cationic monomer (and
The long side chain of introducing polycation of non-invention), improve certain diminishing dispersion effect, do not give full play to compound side chain
Architectural feature, to realize showing the multiple action effects such as high anti-mud performance diminishing is scattered simultaneously, also fails to reach molecule knot
Structure design method realizes the purpose of chemical admixture functionalization.
It is high that patent CN 104031216 A (publication date: on JIUYUE 10th, 2014) reports a kind of polyether-amide type polycarboxylic acids
Effect water reducer and preparation method thereof, is to first pass through polyetheramine to obtain polyetheramine monomer with acyl chlorides monomer reaction, is subsequently adding polyoxy
Vinyl ether monomers and carboxylic monomer carry out radical copolymerization under the conditions of initiator and chain-transferring agent in aqueous to be had
There is the polyether-amide type high-efficiency water-reducing agent of poly-carboxylic acid of good dispersion and slump retaining.This invention is to utilize amino and acid chloride groups
React and obtain polymeric monomer, then obtain the poly-of polyether-amide structure with polyoxyethylene ether polymeric monomer and carboxylic acid minor comonomer copolymerization
Carboxylic acid water reducer.This inventive method also has a compound side-chain structure, and preparation method is simple, cost of material is low, do not used
Machine solvent, has significant economic benefit and environmental benefit.But this invention product realizes height in addition to diminishing characteristic the most simultaneously
The compound action effect of anti-mud, and this invention is to synthesize by the way of first synthesizing polymeric monomer copolymerization again, wayward poly-carboxylic
Acid backbone length and monomer conversion, affect its at cement particle surface adsorption effect, fail from pectination molecular structure is controlled
Property angle realize having diminishing-anti-mud multiple action effect of cement water reducing agent.
Each polycarboxylate water-reducer described in above patent is provided with the service behaviours such as certain mobility, dispersibility.So
And, the product that above-mentioned synthetic method obtains all has a certain degree of weak point, from the angle of Molecular Design synthesis, research
Person fails by polycarboxylic acid structure's modification carboxylic acid halides and to be grafted the method for polymeric cationic side chain under high price cerium salt inducement system real
Now integrate diminishing-guarantor to collapse-disperse-complex function type chemical admixture of the application performance such as anti-mud.Draw only by main chain
Enter the method for cationic block significantly to limit its application and improve effect, through fact proved that synthesis has the compound official of multiple action
Type molecular structure can be rolled into a ball and can significantly improve application performance effect of polymer.Therefore, this just requires that the water reducer of synthesis is dividing
The innovation of minor structure aspect essence, is not limited to traditional synthesis mode, utilizes carboxyl acid modified carboxylic acid halides, at high price cerium innovatively
Salt inducement polycation long-chain and carboxylic acid halides are grafted polycation side chain and the synthetic route of polyether lateral chain and feature, both possess
Diminishing protects the-compound service behaviour of anti-mud of collapsing, and also helps industrialized production and popularization and application simultaneously, and relevant this respect works state
Inside and outside have no report.
Summary of the invention
It is an object of the invention to provide the synthesis of the compound side chain type cement water reducing agent of a kind of poly carboxylic acid modified carboxylic acid halides grafting
Technique, carries out radical polymerization by unsaturated carboxylic acid class monomer and obtains polycarboxylic acids main chain, and then hydroxy-acid group is modified as acyl
Halogen group, is then polymerized unsaturated cationic quaternary ammonium salt monomer by high price cerium salt with alcohol composition oxidation-reduction trigger system initiation
Obtain terminal hydroxy group cationic side chain, then by the polycarboxylic acids main chain containing carboxylic acid halides and terminal hydroxy group cationic side chain, polyethylene glycols chemical combination
Thing obtains the compound side chain type cement water reducing agent of excellent performance through graft reaction.The present invention is to go out from design theory of molecular structure
Send out, add hydroxy-acid group modification acyl halide group and high price cerium salt-ol is polymeric cationic under redox initiation system
Two steps of side chain, and successfully realize reactive grafting, polycarboxylic acids main chain is connected with cationic side chain and side-chain of polyelycol
Form the novel concrete water reducing agent with the multiple action effect such as high diminishing and the anti-mud of height, it is achieved that by molecule master together
The purpose of chain side chain its work efficiency of dual modified raising, enriches polymer architecture-performance study additional at chemistry of concrete
The application in agent field.The cement water reducing agent 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 side-chain of polyelycol can realize excellent diminishing by sterically hindered effect and protect effect of collapsing, its sun
It is electrical that ionic side chains structure can change electric charge in the concrete system of high clay content, prevents side-chain of polyelycol further
It is inhaled into clay interlayer and loses effect, thus the adverse effect suppressing clay that dispersion flows performance is produced, show ratio general
Operating characteristic that logical polycarboxylate water-reducer is the most excellent and action effect.
The invention provides the method that cement water reducing agent prepared by the compound side chain of a kind of poly carboxylic acid modified carboxylic acid halides grafting, pass through
First backbone polymerization modified carboxylic acid halides cationic side chain more again is polymerized the method synthesis cement water reducing agent material of then graft reaction, bag
Include following 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) modified carboxylic acid halides: by moisture in step (1) products therefrom polycarboxylic acids main chain aqueous solution evacuation removing system, add
Enter organic solvent, stir 5-20 minute, under the conditions of ice-water bath, in 0.5-1 hour, thionyl halide is added dropwise to reactor, continue
Isothermal reaction 2-5 hour at being warming up to 40-70 DEG C, siphons away reaction with the alkaline solution that mass fraction is 10-50% simultaneously and produces
Gas, obtain polycarboxylic acids-acyl halide solution；
(3) 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；
(4) graft reaction: by water in step (3) products therefrom terminal hydroxy group cationic side chain aqueous solution evacuation removing system
Point, it is sequentially added into step (2) products therefrom polycarboxylic acids-acyl halide solution, Polyethylene Glycol compounds, is warming up to 50-60 DEG C, stirring
20-40 minute, being continuously heating to 85-120 DEG C, add methanol after reacting 1.5-5 hour, cyclic washing precipitates 3-5 time, will precipitation
Thing is dried under vacuum to constant weight at 40-80 DEG C, be eventually adding water dilute the poly carboxylic acid modified carboxylic acid halides grafting of desired concn is compound
The cement water reducing agent solution of side chain.
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 (methyl) acrylic acid described in step (1) or its mixture quality with unsaturated carboxylic acid and 80-200%；Step
Suddenly the molecular weight regulator described in (1) is TGA, mercaptopropionic acid, methylpropene sodium sulfonate, sodium allylsulfonate or just
Lauryl mercaptan, (methyl) acrylic acid described in consumption and step (1) or its mixture with unsaturated carboxylic acid mole
Ratio is 0.01-0.15:1；Initiator persulfate described in step (1) is Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate, uses
Amount is 0.01-0.1:1 with the mol ratio of (methyl) acrylic acid described in step (1) or its mixture with unsaturated carboxylic acid.
Organic solvent described in above-mentioned steps (2) is dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane or dimethylformamide, uses
Sulfurous described in amount and (methyl) acrylic acid described in step (1) or its mixture with unsaturated carboxylic acid and step (2)
The ratio of carboxylic acid halides quality sum is 1-5:1；Thionyl halide described in step (2) is thionyl chloride or thionyl bromide, consumption and step
(1) (methyl) acrylic acid described in or its mol ratio with the mixture of unsaturated carboxylic acid are 0.15-0.4:1；Institute in step (2)
The solute of the alkaline solution stated is sodium hydroxide or potassium hydroxide, the mol ratio of the thionyl halide described in consumption and step (2)
For 3.5-5:1.
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 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 (3)；Institute in step (3)
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, the mol ratio of the thionyl halide described in consumption and step (2) is 0.2-0.5:
1；High price cerium salt described in step (3) is ammonium ceric nitrate or Cericammoniumsulfate, consumption and the lower aliphatic alcohols described in step (3)
Mol ratio be 0.03-1:1.
Polyethylene Glycol compounds described in above-mentioned steps (4) is Polyethylene Glycol or methoxy poly (ethylene glycol), consumption with
The mol ratio of the thionyl halide described in step (2) is 0.5-0.8:1；In methanol usage described in step (4) and step (1)
Described (methyl) acrylic acid or its with the mixture of unsaturated carboxylic acid, step (3) described in unsaturated cation quaternary ammonium salt
It is 5-10:1 with the ratio of the polyethylene glycols compound quality sum described in step (4).
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, by the polymerization of unsaturated carboxylic acid class monomer and through thionyl halide modification
For the polycarboxylic acids main chain containing acyl halide group, meanwhile, with unsaturated cationic quaternary ammonium salt monomer as reactant, at high price cerium salt and alcohol
Under the oxidation-reduction trigger system of composition, radical polymerization obtains cationic side chain, and this is from conventional polycarboxylic acids main chain-polyethers
Side chain, to diversification, the unique design of multifunction composite modified Backbone-side chain development, is at comb shape polycarboxylate water-reducer molecule
Innovation on structure direction and breakthrough, its novel special structure is possible not only to the change realizing dispersant in terms of application performance
Leather, and be conducive to expanding the intension of theory of Polymer supported catalyst-structure-performance, develop other to a deeper level for follow-up
New varieties cement water reducing agent 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 compound side chain type water reducer of synthesis has a large amount of quaternary ammonium salt cationic polymerization macromolecule chain, it is possible to electronegative clay particle
Interlayer and surface produce electrostatic adsorption, be conducive to absorption at clay interlayer, meanwhile, the interlamination region volume of clay is not
Infinitely-great, after having adsorbed substantial amounts of cationic side chain, other side-chain of polyelycol can be avoided to enter clay interlayer, protection
The diminishing of this water reducer is protected effect of collapsing and is not lost, thus shows high diminishing, the action effect of high anti-mud.This product also can be polynary
Change ground expanded application, in the field such as fine chemistry industry and surfactant, is a kind of concrete with peculiar advantage and distinguishing feature
Water reducer, has good application prospect and the market competitiveness.
3. the synthetic method of the present invention is compared with traditional method, and needed raw material is common is easy to get in reaction, the letter of whole building-up process
Single controlled, the most convenient, polymerization, modification and grafting step used the most all belongs to normal operations technique, it is not necessary to special operational or high
Your auxiliary agent, enriches the preparation method of synthesis cement water reducing agent, it is easy to accomplish industrialized production.This building-up process to equipment without
Particular/special requirement, and remain with compound high diminishing and the functional group of high-thin arch dam effect, and have molecule can designed capacity strong, poly-
The advantages such as right height, molecular weight are controlled, narrow molecular weight distribution, have good promotion potential 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 of polymerization process, has a extensive future, for
Cement water reducing agent provides a kind of new method causing polymerization.
5. this building-up process energy consumption is little, mild condition, safety and environmental protection, production cost are low, cleanliness without any pollution, whole reacts
Journey temperature fluctuation range is little, is conducive to maintaining steadily carrying out of reaction system, reduces the generation of side reaction, it is ensured that product
Yield.Meanwhile, the unsaturated carboxylic acid class monomer of use and the suitable molecular weight scope of unsaturated cation quaternary ammonium salt raw material monomer
The large-scale popularization of width, beneficially Diversified Products and application, increase the market share occupancy volume of high anti-chamotte mould cement water reducing agent.
6. have than conventional polycarboxylate water-reducer more according to the compound side chain type cement water reducing agent of the inventive method synthesis
Add the workability of excellence, diminishing protects collapse ability and anti-mud effect, remains to when high clay content show preferable mobility and guarantor
Hold ability, and the cement of different cultivars is shown the strongest adaptability.Additionally, this water reducer Product Status is stable, highly concentrated
Degree is not stratified after standing down, does not crystallizes and performance is the most unaffected under low temperature after storage.This synthetic method is simple the most same
Time, products obtained therefrom still has the property indices of excellence, beneficially industrial application, therefore has good economy
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 be sequentially added into 7.21g acrylic acid in reactor, 10.81g water, 0.96g mercaptopropionic acid, 7.94g mass are divided
Number is the sodium persulfate aqueous solution of 12%, and feeding interval mixing time 11 minutes every time, is warming up at 68 DEG C be polymerized
Reaction, reacts 6 hours, obtains polycarboxylic acids main chain aqueous solution；By water in gained polycarboxylic acids main chain aqueous solution evacuation removing system
Point, add 45.45g1,4-dioxane, stir 11 minutes, in 0.9 hour, 4.16g thionyl bromide is dripped under the conditions of ice-water bath
Add reactor, be continuously heating to isothermal reaction 4 hours at 50 DEG C, be the potassium hydroxide of 25% with 20.2g mass fraction simultaneously
Solution siphons away the gas that reaction produces, and obtains polycarboxylic acids-acylbromide solution；By 29.91g methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium and 0.48g isopropanol add in another reactor, add 568.27g water and are configured to the aqueous solution that mass concentration is 5%, instead
Answer 4 deoxygenations repeatedly of device inflated with nitrogen to seal after 20 minutes, add 1.32g ammonium ceric nitrate, stir and treat its mix homogeneously in 15 minutes, continue
Continue and be warming up at 35 DEG C carry out polyreaction, react 12 hours, obtain terminal hydroxy group cationic side chain aqueous solution；By gained terminal hydroxy group
Moisture in cationic side chain aqueous solution evacuation removing system, is sequentially added into gained polycarboxylic acids-acylbromide solution, the poly-second of 25.2g two
Alcohol (molecular weight=1800), is warming up to 52 DEG C, stirs 25 minutes, is continuously heating to 100 DEG C, adds 436.2 first after reacting 4 hours
Alcohol, cyclic washing precipitates 3 times, at 55 DEG C, precipitate is dried under vacuum to constant weight, is eventually adding 156.22g water and i.e. obtains quality and divide
Number is the cement water reducing agent solution of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting of 30%.
Embodiment 2
After the cement water reducing agent solution that mass fraction is 30% embodiment 1 obtained deposits 30 days at 6 DEG C, measure
Its implementation result.
Embodiment 3
First in reactor, it is sequentially added into 4.8g acrylic acid, 3.87g fumaric acid, 8.67g water, 2.16g allyl sulphonic acid
Sodium, 8.56g mass fraction are the ammonium persulfate aqueous solution of 8%, and feeding interval mixing time 8 minutes every time, are warming up to 55
Carry out polyreaction at DEG C, react 7 hours, obtain polycarboxylic acids main chain aqueous solution；By gained polycarboxylic acids main chain aqueous solution evacuation
Moisture in removing system, adds 16.99g dimethylformamide, stirs 18 minutes, will in 0.5 hour under the conditions of ice-water bath
8.31g thionyl bromide is added dropwise to reactor, is continuously heating to isothermal reaction 4.5 hours at 40 DEG C, divide by 16.83g mass simultaneously
Number be 48% potassium hydroxide solution siphon away reaction produce gas, obtain polycarboxylic acids-acylbromide solution；By 48.8g acryloyl-oxy
Ethyl-trimethyl salmiac and 0.84g Hexalin add in another reactor, add 648.41g water and are configured to mass concentration and are
The aqueous solution of 7%, 5 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 10 minutes, added 0.14g ammonium ceric nitrate, stirred 18 minutes
Treat its mix homogeneously, be continuously heating at 10 DEG C carry out polyreaction, react 15 hours, obtain terminal hydroxy group cationic side chain water-soluble
Liquid；By moisture in gained terminal hydroxy group cationic side chain aqueous solution evacuation removing system, it is sequentially added into gained polycarboxylic acids-acylbromide molten
Liquid, 12.4g Polyethylene Glycol (molecular weight=500), be warming up to 54 DEG C, stirs 40 minutes, is continuously heating to 120 DEG C, and reaction 1.5 is little
Adding 698.78 methanol time after, cyclic washing precipitates 5 times, at 70 DEG C, precipitate is dried under vacuum to constant weight, is eventually adding
118.55g water i.e. obtains the cement water reducing agent solution of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting that mass fraction is 40%.
Embodiment 4
After the cement water reducing agent solution that concentration is 40% embodiment 3 obtained deposits 30 days at 5 DEG C, measure in fact
Execute effect.
Embodiment 5
First be sequentially added in reactor 6g acrylic acid, 2.17g itaconic acid, 16.35g water, 0.27g TGA,
13.52g mass fraction is the persulfate aqueous solution of 20%, and feeding interval mixing time 5 minutes every time, is warming up to 60 DEG C
Under carry out polyreaction, react 8 hours, obtain polycarboxylic acids main chain aqueous solution；Gained polycarboxylic acids main chain aqueous solution evacuation is removed
Remove moisture in system, add 61.69g dimethyl sulfoxide, stir 5 minutes, in 0.8 hour, 4.16g is sub-under the conditions of ice-water bath
Chlorosulfuric acid is added dropwise to reactor, is continuously heating to isothermal reaction 5 hours at 45 DEG C, is 50% with 13.75g mass fraction simultaneously
Potassium hydroxide solution siphons away the gas that reaction produces, and obtains polycarboxylic acids-solution of acid chloride；By 56.58g dimethyl diallyl chlorination
Ammonium and 0.52g isobutanol add in another reactor, add 650.72g water and are configured to the aqueous solution that mass concentration is 8%, instead
Answer 3 deoxygenations repeatedly of device inflated with nitrogen to seal after 30 minutes, add 4.18g Cericammoniumsulfate, stir and treat its mix homogeneously in 10 minutes, continue
Continue and be warming up at 25 DEG C carry out polyreaction, react 16 hours, obtain terminal hydroxy group cationic side chain aqueous solution；By gained terminal hydroxy group
Moisture in cationic side chain aqueous solution evacuation removing system, is sequentially added into gained polycarboxylic acids-solution of acid chloride, 21g Polyethylene Glycol
(molecular weight=1200), are warming up to 58 DEG C, stir 20 minutes, are continuously heating to 85 DEG C, add 428.79 first after reacting 4.5 hours
Alcohol, cyclic washing precipitates 4 times, at 65 DEG C, precipitate is dried under vacuum to constant weight, is eventually adding 90.44g water and i.e. obtains quality and divide
Number is the cement water reducing agent solution of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting of 50%.
Embodiment 6
After the cement water reducing agent solution that mass fraction is 50% embodiment 5 obtained deposits 20 days at 5 DEG C, measure it
Implementation result.
Embodiment 7
First be sequentially added in reactor 8.61g methacrylic acid, 15.5g water, 0.2g n-dodecyl mercaptan,
6.09g mass fraction is the ammonium persulfate aqueous solution of 30%, and feeding interval mixing time 15 minutes every time, is warming up to 75 DEG C
Under carry out polyreaction, react 5 hours, obtain polycarboxylic acids main chain aqueous solution；Gained polycarboxylic acids main chain aqueous solution evacuation is removed
Remove moisture in system, add 23.45g dimethylformamide, stir 13 minutes, by 3.12g in 0.7 hour under the conditions of ice-water bath
Thionyl bromide is added dropwise to reactor, is continuously heating to isothermal reaction 3.5 hours at 60 DEG C, is 20% with 15g mass fraction simultaneously
Sodium hydroxide solution siphon away reaction produce gas, obtain polycarboxylic acids-acylbromide solution；By 33.11g methacryl propyl group three
Ammonio methacrylate and 0.56g n-butyl alcohol add in another reactor, and adding 794.67g water and being configured to mass concentration is 4%
Aqueous solution, 3 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 25 minutes, added 0.89g Cericammoniumsulfate, stirred and within 25 minutes, treat that it mixes
Close uniformly, be continuously heating at 45 DEG C carry out polyreaction, react 11 hours, obtain terminal hydroxy group cationic side chain aqueous solution；Will
Moisture in gained terminal hydroxy group cationic side chain aqueous solution evacuation removing system, be sequentially added into gained polycarboxylic acids-acylbromide solution,
21.6g methoxy poly (ethylene glycol) (molecular weight=2400), is warming up to 55 DEG C, stirs 35 minutes, is continuously heating to 110 DEG C, reaction
Adding 506.55 methanol after 3.5 hours, cyclic washing precipitates 4 times, at 60 DEG C, precipitate is dried under vacuum to constant weight, finally adds
Enter 100.49g water and i.e. obtain the cement water reducing agent solution of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting that mass fraction is 40%.
Embodiment 8
After the cement water reducing agent solution that mass fraction is 40% embodiment 7 obtained deposits 20 days at 6 DEG C, measure it
Implementation result.
Embodiment 9
First in reactor, it is sequentially added into 0.78g methacrylic acid, 11.33g maleic acid, 13.6g water, 1.11g methyl
Sodium allylsulfonate, 9.01g mass fraction are the persulfate aqueous solution of 18%, and feeding interval mixing time 20 points every time
Clock, is warming up at 85 DEG C carry out polyreaction, reacts 1.5 hours, obtains polycarboxylic acids main chain aqueous solution；By gained polycarboxylic acids main chain
Moisture in aqueous solution evacuation removing system, adds 44.71g dimethyl sulfoxide, stirs 8 minutes, under the conditions of ice-water bath 1 hour
Interior 3.57g thionyl chloride is added dropwise to reactor, is continuously heating to isothermal reaction 2 hours at 70 DEG C, uses 13.72g mass simultaneously
Mark be 35% sodium hydroxide solution siphon away reaction produce gas, obtain polycarboxylic acids-solution of acid chloride；By 8.83g methyl-prop
Alkene acyloxyethyl dimethylbutyl ammonium bromide and 0.45g normal propyl alcohol add in another reactor, add 432.48g water and are configured to
Mass concentration is the aqueous solution of 2%, and 4 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 10 minutes, added 1.79g Cericammoniumsulfate,
Stir and treat its mix homogeneously in 30 minutes, be continuously heating at 55 DEG C carry out polyreaction, react 6 hours, obtain terminal hydroxy group sun from
Sub-side chain aqueous solution；By moisture in gained terminal hydroxy group cationic side chain aqueous solution evacuation removing system, it is sequentially added into gained and gathers
Carboxylic acid-solution of acid chloride, 24g Polyethylene Glycol (molecular weight=1000), be warming up to 60 DEG C, stirs 38 minutes, is continuously heating to 90 DEG C,
Adding 264.96 methanol after reacting 5 hours, cyclic washing precipitates 3 times, at 80 DEG C, precipitate is dried under vacuum to constant weight, finally
The cement water reducing agent that addition 112.42g water i.e. obtains the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting that mass fraction is 30% is molten
Liquid.
Embodiment 10
After the cement water reducing agent solution that mass fraction is 30% embodiment 9 obtained deposits 40 days at 7 DEG C, measure it
Implementation result.
Embodiment 11
First in reactor, it is sequentially added into 2.15g methacrylic acid, 3.25g itaconic acid, 2.45g maleic anhydride, 2.9g
Fumaric acid, 8.61g water, 0.91g TGA, 23.81g mass fraction are the sodium persulfate aqueous solution of 1%, and feed every time
Interval mixing time 17 minutes, is warming up at 90 DEG C carry out polyreaction, reacts 2 hours, obtain polycarboxylic acids main chain aqueous solution；Will
Moisture in gained polycarboxylic acids main chain aqueous solution evacuation removing system, adds 19.35g1,4-dioxane, stirs 20 minutes,
In 0.6 hour, 2.14g thionyl chloride is added dropwise to reactor under the conditions of ice-water bath, is continuously heating to isothermal reaction 3 at 65 DEG C little
Time, siphon away, with the sodium hydroxide solution that 21.61g mass fraction is 10%, the gas that reaction produces simultaneously, obtain polycarboxylic acids-acyl chlorides
Solution；58.6g trimethylallylammonium chloride and 0.76g n-amyl alcohol are added in another reactor, adds 527.37g water and join
Making the aqueous solution that mass concentration is 10%, 5 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 15 minutes, added 0.47g nitric acid
Cerium ammonium, stirs and treats its mix homogeneously in 28 minutes, is continuously heating at 60 DEG C carry out polyreaction, reacts 7 hours, obtains terminal hydroxy group
Cationic side chain aqueous solution；By moisture in gained terminal hydroxy group cationic side chain aqueous solution evacuation removing system, it is sequentially added into institute
Obtain polycarboxylic acids-solution of acid chloride, 19.8g methoxy poly (ethylene glycol) (molecular weight=2000), be warming up to 50 DEG C, stir 30 minutes, continue
Continuing and be warming up to 115 DEG C, add 802.39 methanol after reacting 3 hours, cyclic washing precipitates 5 times, by precipitate vacuum at 40 DEG C
It is dried to constant weight, is eventually adding 92.06g water and i.e. obtains the mixed of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting that mass fraction is 50%
Solidifying soil water reducer solution.
Embodiment 12
After the cement water reducing agent solution that concentration is 50% embodiment 11 obtained deposits 20 days at 7 DEG C, measure it
Implementation result.
Implementation result:
1. flowing degree of net paste of cement
For investigating the cement water reducing agent solution of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting of present invention synthesis to cement
Mobility action effect, test determination each embodiment paste flowing degree to reference cement under identical volume.Test is pressed
GB/T8077-2012 " Methods for testing uniformity of concrete admixture " is carried out, W/C=0.29, and volume is the solid volume of folding.Select existing
Commercially available traditional 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 concrete of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting of the inventive method synthesis subtracts
Aqua, the ratio of mud and the folding of 0.30% 0.29 are consolidated under volume, all can show excellent dispersibility and cement is fitted
Ying Xing.
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 concrete of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting of the inventive method synthesis subtracts
Aqua all can show excellent divergence and the slump and holding capacity in concrete system.
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 concrete of the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting of the inventive method synthesis subtracts
Aqua all can show preferable divergence and the slump and holding capacity under the clay additive of 1.8%.
Claims (3)
1. the method that cement water reducing agent prepared by the compound side chain of poly carboxylic acid modified carboxylic acid halides grafting, it is characterised in that by elder generation
Backbone polymerization modified carboxylic acid halides cationic side chain more again is polymerized the bar of the method synthesis cement water reducing agent material of then graft reaction
Part and step are as follows:
(1) backbone polymerization: be sequentially added in reactor (methyl) acrylic acid or its with the mixture of unsaturated carboxylic acid, water, point
Son amount regulator, mass fraction are the initiator persulfate aqueous solution of 1-30%, and feeding interval mixing time 5-every time
20 minutes, at being warming up to 55-90 DEG C, carry out polyreaction, react 1.5-8 hour, obtain polycarboxylic acids main chain aqueous solution；
(2) modified carboxylic acid halides: by moisture in step (1) products therefrom polycarboxylic acids main chain aqueous solution evacuation removing system, there was added
Machine solvent, stirs 5-20 minute, and thionyl halide is added dropwise in 0.5-1 hour under the conditions of ice-water bath reactor, continues to heat up
Isothermal reaction 2-5 hour at 40-70 DEG C, siphons away, with the alkaline solution that mass fraction is 10-50%, the gas that reaction produces simultaneously
Body, obtains polycarboxylic acids-acyl halide solution；
(3) cationic side chain polymerization: monomer unsaturation cation quaternary ammonium salt and reducing agent lower aliphatic alcohols are added another reaction
In device, adding water and be configured to the aqueous solution that mass concentration is 2-10%, reactor inflated with nitrogen 3-5 deoxygenation 10-30 repeatedly divides
Seal after clock, add oxidant high price cerium salt, stir and within 10-30 minute, treat its mix homogeneously, carry out at being continuously heating to 10-60 DEG C
Polyreaction, reacts 6-16 hour, obtains terminal hydroxy group cationic side chain aqueous solution；
(4) graft reaction: by moisture in step (3) products therefrom terminal hydroxy group cationic side chain aqueous solution evacuation removing system,
It is sequentially added into step (2) products therefrom polycarboxylic acids-acyl halide solution, Polyethylene Glycol compounds, is warming up to 50-60 DEG C, stir 20-
40 minutes, being continuously heating to 85-120 DEG C, add methanol after reacting 1.5-5 hour, cyclic washing precipitates 3-5 time, by precipitate
At 40-80 DEG C, it is dried under vacuum to constant weight, is eventually adding water and dilutes to obtain the compound side of poly carboxylic acid modified carboxylic acid halides grafting of desired concn
The cement water reducing agent solution of chain；
Wherein, the unsaturated carboxylic acid described in step (1) is one or more in itaconic acid, maleic acid (acid anhydride), fumaric acid, no
Saturated carboxylic acid can add or be added without, when added consumption and (methyl) acrylic acid mol ratio of addition in step (1)
For 0.1-5:1；The quality adding water described in step (1) is (methyl) acrylic acid described in step (1) or itself and insatiable hunger
80-200% with the mixture quality sum of carboxylic acid；Molecular weight regulator described in step (1) is TGA, sulfydryl third
Acid, methylpropene sodium sulfonate, sodium allylsulfonate or n-dodecyl mercaptan, consumption and (methyl) third described in step (1)
The mol ratio of olefin(e) acid or its mixture with unsaturated carboxylic acid is 0.01-0.15:1；Initiator persulfuric acid described in step (1)
Salt is Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate, (methyl) acrylic acid described in consumption and step (1) or it is with unsaturated
The mol ratio of the mixture of carboxylic acid is 0.01-0.1:1；
Organic solvent described in step (2) is dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane or dimethylformamide, consumption and step
(1) the thionyl halide quality described in (methyl) acrylic acid described in or its mixture with unsaturated carboxylic acid and step (2)
The ratio of sum is 1-5:1；Thionyl halide described in step (2) is thionyl chloride or thionyl bromide, described in consumption and step (1)
The mol ratio of (methyl) acrylic acid or its mixture with unsaturated carboxylic acid is 0.15-0.4:1；Alkalescence described in step (2)
The solute of solution is sodium hydroxide or potassium hydroxide, and consumption is 3.5-5 with the mol ratio of the thionyl halide described in step (2):
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 bromination ammonium, methylacryoyloxyethyl dimethyl dodecyl bromide
In ammonium, acryloxyethyldimethyl cetyl ammonium bromide, methylacryoyloxyethyl dimethyl hexadecyl base ammonium bromide
One or more, consumption is 10-1000:1 with the mol ratio of the high price cerium salt described in step (3)；Low described in step (3)
Level fatty alcohol be normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 2,2-
Dimethyl-1-propanol or Hexalin；High price cerium salt described in step (3) is ammonium ceric nitrate or Cericammoniumsulfate, consumption and step
(3) mol ratio of the lower aliphatic alcohols described in is 0.03-1:1；
Polyethylene Glycol compounds described in step (4) is Polyethylene Glycol or methoxy poly (ethylene glycol)；Described in step (4)
(methyl) acrylic acid described in methanol usage and step (1) or its with described in the mixture of unsaturated carboxylic acid, step (3)
The ratio of the polyethylene glycols compound quality sum described in unsaturated cation quaternary ammonium salt and step (4) is 5-10:1.
The side of cement water reducing agent prepared by the compound side chain of a kind of poly carboxylic acid modified carboxylic acid halides the most according to claim 1 grafting
Method, it is characterised in that the lower aliphatic alcohols described in step (3) is 0.2-with the mol ratio of the thionyl halide described in step (2)
0.5:1.
The side of cement water reducing agent prepared by the compound side chain of a kind of poly carboxylic acid modified carboxylic acid halides the most according to claim 1 grafting
Method, it is characterised in that the Polyethylene Glycol compounds described in step (4) and the mol ratio of the thionyl halide described in step (2)
For 0.5-0.8:1.
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