CN106188557A - The method that unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain prepares high anti-chamotte mould polycarboxylate dispersant - Google Patents
The method that unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain prepares high anti-chamotte mould polycarboxylate dispersant Download PDFInfo
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- 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
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- 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
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- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- 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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- 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
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- 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
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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Abstract
The method that unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain prepares high anti-chamotte mould polycarboxylate dispersant belongs to dispersant field.The present invention uses unsaturated carboxylic acid monomer, unsaturated halogenated hydrocarbons monomer, unsaturated cationic quaternary ammonium salt monomer, the raw materials such as Polyethylene Glycol compounds, the method being finally etherified grafting by first copolymerization main chain repolymerization cationic side chain then functionalization, height anti-chamotte mould polycarboxylate dispersant's material of the unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain that synthesis performance is excellent, i.e. with unsaturated carboxylic acid with unsaturated halogenated hydrocarbons as reactant, carboxylic acid halogenated hydrocarbons copolymer chain is obtained by free-radical polymerized, the unsaturated cationic quaternary ammonium salt monomer of polymerization is caused to obtain terminal hydroxy group cationic side chain with high price cerium salt alcohol, again by terminal hydroxy group cationic side chain, polyethylene glycols is compound modified obtains ftmctionalized sidechains, carboxylic acid halogenated hydrocarbons copolymer chain is etherified graft-functionalized side chain prepare.Present invention achieves high diminishing to protect and collapse and the multi-efficiency such as high opposing clay.
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 is first copolymerized into main chain cationic side chain again with unsaturated halogenated hydrocarbons be polymerized and functionalization then master chain is etherified and connects
Branch synthesizes the concrete preparation method of high anti-chamotte mould polycarboxylate dispersant.
Background technology
The fast development of construction material and concrete works technology, accelerate the further investigation of concrete chemical admixture with
The chemical admixture of systematic study, especially polycarboxylic acid, water-reducing rate advantages of higher little with its volume, extensively should gradually obtain
With, but it greatly have impact on the performance of its workability and usefulness to the sensitivity of aggregate clay content, constrains it and exists further
Concrete mixing and the important function of performance in forming process.
In order to avoid the negative effect of clay content, although concrete works often using quality sand and stone aggregate solve to ask
Topic, but from the point of view of environmental conservation and sustainable development, it is necessary to research and develop a kind of high anti-chamotte mould polycarboxylate dispersant.
The great advantage of high-molecular type dispersing agent is can be by exchanging polymerization monomeric species, changing monomer match ratio and regulation and control point
The methods such as minor structure functional group design the product of different molecular structures and performance, thus be a kind of structure flexible design degree big,
The dispersant kind that performance regulation and control space is big.Therefore, the high-performance poly carboxylic dispersants with multi-efficiency has become as coagulation
Requisite component in soil technology.
High anti-chamotte mould polycarboxylate dispersant is the synthesis that Molecular Design method is incorporated into cement concrete dispersant
In field, develop the novel agent that can suppress side effect of clay, not only there is the excellent service behaviour of traditional dispersant, also simultaneously
There is the peculiar advantage feature of opposing side effect of clay, can fully alleviate the imbalance between supply and demand of high-quality aggregate, it is achieved ecological environment
Protection and natural resources are saved energy and reduce the cost, and show good popularizing application prospect.
Patent CN104987472A (publication date: on October 21st, 2015) reports a kind of cement concrete that strengthens and protects spy of collapsing
The water reducer of property.This patent is that to obtain halogenated polyether with unsaturated polyoxyethylene ether and unsaturation halogenated hydrocarbons generation esterification big
Monomer, then by halogenated polyether polymeric monomer and unsaturated carboxylic acid by radical polymerization obtain long-chain be polyacrylic acid, side chain be ester
Change the pectination long-chain macromolecule water reducer of enol class polyoxyethylene ether.In its molecular structure, the main chain rich in carboxyl adsorption group carries
For adsorption, the preferable micro-crosslinking sidechain of hydrophilic provides sterically hindered effect.The advantage of this invention is at polycarboxylic acids diminishing
Introduce a large amount of hydrolyzable branched group on agent main chain, under the conditions of concrete alkalescence, discharge carboxylic hydrolyzate, from
And reach to disperse slow setting the effect of viscosity reduction.But this patent of invention is from the perspective of Molecular Design, the most fully sends out
Wave the breakthrough in terms of the structure innovation effect of unsaturated halogenated hydrocarbons realizes anti-mud effect, fail to be played even by halogenated hydrocarbons functional group
Connect the pivotal role of master chain functional groups.
Patent CN104311743A (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 concrete and use polycarboxylate dispersant 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, additionally, this product extends at cement slurry alkaline environment Middle molecule chain, 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 multi-functional.
Concrete dispersant described in most patents has been provided with the service behaviours such as good mobility, dispersibility.
But, the product that above-mentioned synthetic method obtains all has a certain degree of weak point, and the Molecular Design of researcher focuses mostly on
In realizing diminishing dispersion, anti-mud, flocculation, slow release a certain item performance therein, and seldom by connecing under high price cerium salt inducement system
The method of branch polymeric cationic side chain realizes integrating diminishing-guarantor and collapses-disperse-complex function type of the application performance such as anti-mud
Chemical admixture.Its popularization and application in concrete dispersant field, warp is limited only by simple molecular structure modification
Fact proved that synthesis has the complex function group type molecular structure of multiple action and can significantly improve the application performance merit of polymer
Effect.Therefore, this just requires that the concrete dispersant of synthesis realizes the molecular structure innovation of essence, and diminishing to be possessed is protected
Collapse-compound the service behaviour of anti-mud, the most also can guarantee that technological operation easily, cheap preparation cost, simple and easy to get
Reaction raw materials, 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 a kind of high anti-mud polycarboxylic acids of unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain type to divide
The synthesis technique of powder, carries out free-radical polymerized obtaining carboxylic acid-halogenated hydrocarbons by unsaturated carboxylic acid and unsaturated halogenated hydrocarbons monomer
Copolymer chain, is then polymerized unsaturated cationic quaternary ammonium by high price cerium salt with alcohols composition oxidation-reduction trigger system initiation
Salt monomer obtains terminal hydroxy group cationic side chain, then by terminal hydroxy group cationic side chain, Polyethylene Glycol compounds is terminal-modified obtains
Ftmctionalized sidechains, be finally etherified in carboxylic acid-halogenated hydrocarbons copolymer chain graft-functionalized side chain obtain excellent performance height resist
Polycarboxylate dispersant used by chamotte mould concrete.The present invention is from design theory of molecular structure, adds and with high price cerium salt-ol is
Under redox initiation system polymeric cationic side chain step and successfully realize functionalization and etherificate grafting, by polycarboxylic acids-
Halogenated hydrocarbons main chain and cationic side chain are joined together to form has the novel poly-of the multiple action effect such as high diminishing and the anti-mud of height
Carboxylic dispersants, it is achieved that improved the purpose of its work efficiency by molecular side chain modification, is enriched polymer architecture-performance and grinds
Study carefully the application in concrete chemical admixture field.The concrete using this method synthesis has compound side with polycarboxylate dispersant
Chain structure, is different from the side chain composition of conventional polycarboxylate water-reducer, and its polyether lateral chain can realize excellent by sterically hindered effect
Different diminishing protects effect of collapsing, and its cationic side chain structure can also change electric charge electricity in the concrete system of high clay content simultaneously
Property, preferentially occupy clay interlayer to avoid polyether lateral chain to be adsorbed, the adverse effect that effectively dispersive property is produced by suppression clay,
Give full play to high diminishing and the performance advantage feature of the anti-mud of height.
The invention provides a kind of unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain and prepare the dispersion of high anti-chamotte mould polycarboxylic acids
The method of agent, is polymerized with unsaturation halogenated hydrocarbons copolymerization cationic side chain again by first unsaturated carboxylic acid and functionalization is then etherified and connects
The method of branch synthesizes high anti-chamotte mould polycarboxylate dispersant's material, including following condition and step:
(1) unsaturated carboxylic acid and unsaturated halogenated hydrocarbons copolymerization: be sequentially added in reactor (methyl) acrylic acid or its with
The mixture of unsaturated carboxylic acid, unsaturated halogenated hydrocarbons, initiator, organic solvent, each feeding interval mixing time 5-20 minute,
3-5 the deoxygenation repeatedly of reactor inflated with nitrogen sealed after 10-30 minute, carried out polyreaction, reaction at being warming up to 50-120 DEG C
Adding methanol after 1.5-5 hour, cyclic washing precipitates 3-5 time, at 40-80 DEG C, precipitate is dried under vacuum to constant weight, to obtain final product
Carboxylic acid-halogenated hydrocarbons copolymer；
(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) Side functionalization: Polyethylene Glycol compounds, sodium hydroxide are sequentially added into step (2) products therefrom end hydroxyl
In base cationic side chain aqueous solution, it is warming up to 50-70 DEG C, stirs 5-20 minute, moisture in evacuation removing system, add band water
Agent, reacts at being continuously heating to 85-110 DEG C, is separated by reaction gained water while reaction, after reacting 2-6 hour
Slough water entrainer by evacuation, obtain ftmctionalized sidechains；
(4) etherificate grafting: be sequentially added into step (1) products therefrom carboxylic acid-halogenated hydrocarbons copolymer, step in reactor
(3) products therefrom ftmctionalized sidechains, organic solvent, is warming up to 40-60 DEG C, stirs 20-40 minute, is continuously heating to 70-100
DEG C, adding methanol after reacting 4-10 hour, cyclic washing precipitates 3-5 time, at 40-80 DEG C, precipitate is dried under vacuum to perseverance
Weight, is eventually adding water and dilutes to obtain the unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain type high anti-mud polycarboxylic acids dispersion of desired concn
Agent solution.
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)；Unsaturated halogen described in step (1)
Be allyl chloride, allyl bromide, bromoallylene, methylallyl chloride, the bromo-1-butylene of 4-, chloroisoamylene or vinyl benzyl chloride for hydrocarbon, consumption with
(methyl) acrylic acid described in step (1) or its mol ratio with the mixture of unsaturated carboxylic acid are 0.15-0.5:1；Step (1)
Described in initiator be azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide, consumption and step (1) add
(methyl) acrylic acid or its mixture with unsaturated carboxylic acid and step (1) in the total mole number of unsaturated halogenated hydrocarbons that adds
Ratio be 0.01-0.05:1；Organic solvent described in step (1) is dimethyl sulfoxide, 1,4-dioxane or dimethyl methyl
(methyl) acrylic acid added in amide, consumption and step (1) or its addition middle with the mixture of unsaturated carboxylic acid and step (1)
The ratio of unsaturated halogenated hydrocarbons quality sum be 4-10:1；Methanol usage described in step (1) and (first of addition in step (1)
Base) the unsaturated halogenated hydrocarbons quality that adds in acrylic acid or its mixture with unsaturated carboxylic acid and step (1) and ratio be 5-
10:1.
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, the mol ratio of the unsaturated halogenated hydrocarbons described in consumption and step (1) is 0.2-
0.5:1；High price cerium salt described in step (2) is ammonium ceric nitrate or Cericammoniumsulfate, consumption and the rudimentary fat described in step (2)
The mol ratio of fat alcohol is 0.03-1:1.
Polyethylene Glycol compounds described in above-mentioned steps (3) is Polyethylene Glycol or methoxy poly (ethylene glycol), consumption with
The mol ratio of the unsaturated halogenated hydrocarbons described in step (1) is 0.5-0.8:1；Sodium hydroxide concentration described in step (3) with
The ratio of the lower aliphatic alcohols described in step (2) and the Polyethylene Glycol compounds total mole number described in step (3) is 0.8-
1.5:1；Water entrainer described in step (3) is hexamethylene, benzene or toluene, and consumption is products therefrom terminal hydroxy group sun in step (2)
The 8-30% of the Polyethylene Glycol compounds gross mass added in ionic side chains and step (3).
Organic solvent described in above-mentioned steps (4) is dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane or dimethylformamide, uses
Amount and products therefrom ftmctionalized sidechains's mass in products therefrom carboxylic acid-halogenated hydrocarbons copolymer and step (3) in step (1) and ratio
For 1-5:1；Methanol usage described in step (4) and products therefrom carboxylic acid-halogenated hydrocarbons copolymer and step (3) in step (1)
The ratio of middle products therefrom ftmctionalized sidechains's mass sum is 5-10:1.
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 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, system is pure, and side reaction is few, and can be substantially reduced the activation energy in polymerization process, application
Have a extensive future, provide a kind of new method causing polymerization for concrete with polycarboxylate dispersant.
2., based on design theory of molecular structure, the present invention obtains with unsaturated carboxylic acid and unsaturated halogenated hydrocarbons for monomer copolymerizable
To polycarboxylic acids-halogenated hydrocarbons main chain, meanwhile, with unsaturated cationic quaternary ammonium salt monomer as reactant, form with alcohol at high price cerium salt
Oxidation-reduction trigger system under radical polymerization obtain cationic side chain, will after Side functionalization with main chain etherificate be grafted
To final dispersant product, this is that the single side chain for tradition comb shape molecule is combined side-chain structure to diversification, multifunction
The innovative design of development, its novel special structure is possible not only to the change realizing dispersant in terms of application performance, Er Qieyou
It is beneficial to expand the intension of theory of Polymer supported catalyst-structure-performance, divides for other new varieties polycarboxylic acids of follow-up further exploitation
Powder has widened research direction and mentality of designing.
3. be different from other inventive method only a small amount of cationic structural of copolymerization in molecular backbone, the inventive method
The high anti-mud polycarboxylate dispersant of the unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain type of synthesis has substantial amounts of cationic quaternary ammonium
Salt polymer lateral chain, it is possible to produce electrostatic adsorption with interlayer and the surface of electronegative clay particle, be conducive to absorption to exist
Clay interlayer, meanwhile, the interlamination region volume of clay is not infinitely-great, after having adsorbed substantial amounts of cationic side chain, permissible
Avoid that there is diminishing to protect the side chain entrance clay interlayer of effect of collapsing and lose effect, show the effect effect of high diminishing, high anti-mud
Really.Additionally, this dispersant can with diversification ground expanded application in the field such as fine chemistry industry and surfactant, its peculiar advantage and
Distinguishing feature shows good application prospect and the market competitiveness.
4. have than commercially available polycarboxylate water-reducer more according to the height anti-chamotte mould polycarboxylate 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 dispersant Product Status is stable, high concentration
After lower standing not stratified, do not crystallize and performance is the most unaffected after storage under low temperature.This synthetic method simple the most simultaneously,
Products obtained therefrom still has the property indices of excellence, beneficially industrial application, therefore has the most economic effect
Benefit and social benefit.
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, polymerization used and grafting step are also normal operations technique, it is not necessary to special operational or expensive auxiliary agent, enrich synthesis
The preparation method of concrete chemical admixture, has feature the most easily, it is easy to accomplish industrialized production.This conjunction
One-tenth 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 has
Molecule can the advantages such as designed capacity is strong, narrow molecular weight distribution, the degree of polymerization high, molecular weight is controlled, have good promotion potential and
Using value.
6. this building-up process energy consumption is low, mild condition, safety and environmental protection, and water entrainer used also may be used after separatory-standing-separation
Continue cycling through use, greatly reduce wastage of material, saved production cost.The condensing reflux of water entrainer can also keep reaction
The temperature plateau of system, reduces the viscosity of reaction system simultaneously, makes stirring mixing more uniformly fully, thus improves whole process
Reaction rate.Additionally, the monomers such as the unsaturated carboxylic acid used, unsaturated halogenated hydrocarbons, unsaturated cation quaternary ammonium salt is applicable
The variation of molecular weight ranges width, beneficially product popularization and application, increase the market share of high anti-chamotte mould polycarboxylate dispersant
Occupancy volume.
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 will be sequentially added in reactor 7.82g methacrylic acid, 1.06g fumaric acid, 1.91g allyl chloride,
0.61g dibenzoyl peroxide, 86.36g dimethyl sulfoxide, each feeding interval mixing time 18 minutes, reactor inflated with nitrogen
3 deoxygenations sealed after 30 minutes repeatedly, were warming up at 90 DEG C carry out polyreaction, added 91.76g methanol, instead after reacting 3 hours
After backwashing washs precipitation 4 times, at 60 DEG C, precipitate is dried under vacuum to constant weight, obtains carboxylic acid-chlorohydrocarbon copolymer；By 48.5g bis-
Methyl diallyl ammonium chloride and 0.45g isopropanol add in another reactor, add 562.94g water and are configured to mass concentration
Being the aqueous solution of 8%, 4 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 20 minutes, added 0.89g Cericammoniumsulfate, stirred 20 points
Its mix homogeneously treated by clock, is continuously heating at 40 DEG C carry out polyreaction, reacts 10 hours, obtains terminal hydroxy group cationic side chain water
Solution；35g methoxy poly (ethylene glycol) (molecular weight=2000), 12g sodium hydroxide are sequentially added into gained terminal hydroxy group cation side
In chain aqueous solution, it is warming up to 60 DEG C, stirs 12 minutes, moisture in evacuation removing system, add 12.59g benzene, be continuously heating to
React at 100 DEG C, while reaction, reaction gained water is separated, after reacting 4 hours, slough benzene by evacuation,
To ftmctionalized sidechains；Gained carboxylic acid-chlorohydrocarbon copolymer, gained ftmctionalized sidechains, 320.25g bis-it is sequentially added in reactor
Methyl sulfoxide, is warming up to 45 DEG C, stirs 25 minutes, is continuously heating to 90 DEG C, adds 640.5g methanol, repeatedly after reacting 7 hours
Washing precipitation 4 times, is dried under vacuum to constant weight by precipitate at 65 DEG C, is eventually adding 162.38g water and i.e. obtains mass fraction and is
The polycarboxylate dispersant's solution prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain of 40%.
Embodiment 2
After the polycarboxylate dispersant's solution that concentration is 40% embodiment 1 obtained deposits 30 days at 6 DEG C, measure in fact
Execute effect.
Embodiment 3
First 7.17g methacrylic acid, 1.63g maleic anhydride, 2.03g4-bromo-1-fourth will be sequentially added in reactor
Alkene, 0.76g azodiisobutyronitrile, 108.34g dimethyl sulfoxide, each feeding interval mixing time 5 minutes, reactor inflated with nitrogen
3 deoxygenations sealed after 25 minutes repeatedly, were warming up at 110 DEG C carry out polyreaction, added 102.92g methanol after reacting 2 hours,
Cyclic washing precipitates 3 times, at 80 DEG C, precipitate is dried under vacuum to constant weight, obtains carboxylic acid-bromo-hydrocarbons copolymer；By 8.83g
Methylacryoyloxyethyl dimethylbutyl ammonium bromide and 0.36g normal propyl alcohol add in another reactor, add 450.14g water
Being configured to the aqueous solution that mass concentration is 2%, 4 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 10 minutes, added 0.33g nitric acid
Cerium ammonium, stirs and treats its mix homogeneously in 10 minutes, is continuously heating at 45 DEG C carry out polyreaction, reacts 9 hours, obtains terminal hydroxy group
Cationic side chain aqueous solution；10.8g Polyethylene Glycol (molecular weight=1200), 4.8g sodium hydroxide are sequentially added into gained terminal hydroxy group
In cationic side chain aqueous solution, it is warming up to 65 DEG C, stirs 10 minutes, moisture in evacuation removing system, add 6g benzene, continue to rise
Temperature is reacted at 85 DEG C, is separated by reaction gained water, sloughed by evacuation after reacting 6 hours while reaction
Benzene, obtains ftmctionalized sidechains；Be sequentially added in reactor gained carboxylic acid-bromo-hydrocarbons copolymer, gained ftmctionalized sidechains,
178.11g dimethyl sulfoxide, is warming up to 60 DEG C, stirs 35 minutes, is continuously heating to 75 DEG C, adds 356.21g after reacting 9 hours
Methanol, cyclic washing precipitates 5 times, at 80 DEG C, precipitate is dried under vacuum to constant weight, is eventually adding 85.65g water and i.e. obtains quality
Mark is the polycarboxylate dispersant's solution prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain of 30%.
Embodiment 4
After the polycarboxylate dispersant's solution that concentration is 30% embodiment 3 obtained deposits 40 days at 5 DEG C, measure in fact
Execute effect.
Embodiment 5
First 1.2g acrylic acid, 10.84g itaconic acid, 2.42g allyl bromide, bromoallylene, 0.89g will be sequentially added in reactor occasionally
The different heptonitrile of nitrogen two, 86.77g1,4-dioxane, each feeding interval mixing time 25 minutes, reactor inflated with nitrogen 4 times repeatedly
Deoxygenation sealed after 20 minutes, was warming up at 80 DEG C carry out polyreaction, added 94g methanol after reacting 3.5 hours, and cyclic washing sinks
Form sediment 4 times, precipitate is dried under vacuum to constant weight at 50 DEG C, obtain carboxylic acid-bromo-hydrocarbons copolymer；By 31.16g methacryl
Oxy-ethyl-trimethyl salmiac and 0.37g n-butyl alcohol add in another reactor, add 598.99g water and are configured to mass concentration
Being the aqueous solution of 5%, 3 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 30 minutes, added 0.89g Cericammoniumsulfate, stirred 25 points
Its mix homogeneously treated by clock, is continuously heating at 30 DEG C carry out polyreaction, reacts 12 hours, obtains terminal hydroxy group cationic side chain water
Solution；36g methoxy poly (ethylene glycol) (molecular weight=2400), 8g sodium hydroxide are sequentially added into gained terminal hydroxy group cationic side chain
In aqueous solution, it is warming up to 50 DEG C, stirs 15 minutes, moisture in evacuation removing system, add 13.51g toluene, be continuously heating to
React at 95 DEG C, while reaction, reaction gained water is separated, after reacting 4.5 hours, slough first by evacuation
Benzene, obtains ftmctionalized sidechains；Be sequentially added in reactor gained carboxylic acid-bromo-hydrocarbons copolymer, gained ftmctionalized sidechains,
314.96g1,4-dioxane, is warming up to 55 DEG C, stirs 30 minutes, is continuously heating to 80 DEG C, adds after reacting 8 hours
719.91g methanol, cyclic washing precipitates 3 times, at 60 DEG C, precipitate is dried under vacuum to constant weight, is eventually adding 214.15g water
Obtain the polycarboxylate dispersant's solution prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain that mass fraction is 30%.
Embodiment 6
After the polycarboxylate dispersant's solution that mass fraction is 30% embodiment 5 obtained deposits 20 days at 5 DEG C, measure it
Implementation result.
Embodiment 7
First 8.61g methacrylic acid, 5.23g chloroisoamylene, 0.37g azo two will be sequentially added in reactor different
Heptonitrile, 124.54g dimethylformamide, each feeding interval mixing time 9 minutes, 5 deoxygenations 20 repeatedly of reactor inflated with nitrogen
Sealing after minute, be warming up at 120 DEG C carry out polyreaction, add 69.19g methanol after reacting 1.5 hours, cyclic washing precipitates
5 times, precipitate is dried under vacuum to constant weight at 65 DEG C, obtains carboxylic acid-chlorohydrocarbon copolymer；By 43.58g acrylyl oxy-ethyl
Trimethyl ammonium chloride and 2.5g Hexalin add in another reactor, and adding 721.92g water and being configured to mass concentration is 6%
Aqueous solution, 3 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 25 minutes, added 0.41g ammonium ceric nitrate, stirred and within 30 minutes, treat that it mixes
Close uniformly, be continuously heating at 10 DEG C carry out polyreaction, react 16 hours, obtain terminal hydroxy group cationic side chain aqueous solution；Will
12.5g Polyethylene Glycol (molecular weight=500), 28g sodium hydroxide are sequentially added in gained terminal hydroxy group cationic side chain aqueous solution, rise
Temperature, to 68 DEG C, stirs 9 minutes, moisture in evacuation removing system, adds 14.65g hexamethylene, is continuously heating at 90 DEG C carry out
Reaction, separates reaction gained water while reaction, sloughs hexamethylene by evacuation, obtain official after reacting 4.5 hours
Side chain can be changed；Gained carboxylic acid-chlorohydrocarbon copolymer, gained ftmctionalized sidechains, 401.7g dimethyl it is sequentially added in reactor
Methanamide, is warming up to 58 DEG C, stirs 32 minutes, is continuously heating to 100 DEG C, adds 702.97g methanol, repeatedly after reacting 4 hours
Washing precipitation 4 times, is dried under vacuum to constant weight by precipitate at 55 DEG C, is eventually adding 151.81g water and i.e. obtains mass fraction and is
The polycarboxylate dispersant's solution prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain of 40%.
Embodiment 8
After the polycarboxylate dispersant's solution that mass fraction is 40% embodiment 7 obtained deposits 30 days at 6 DEG C, measure it
Implementation result.
Embodiment 9
First 2.15g methacrylic acid, 3.25g itaconic acid, 2.9g maleic acid, 2.9g richness will be sequentially added in reactor
Horse acid, 2.72g methylallyl chloride, 0.79g dibenzoyl peroxide, 97.48g dimethylformamide, each feeding interval stirs
12 minutes time, 5 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 10 minutes, were warming up at 60 DEG C carry out polyreaction, reaction
Adding 104.44g methanol after 4.5 hours, cyclic washing precipitates 4 times, at 40 DEG C, precipitate is dried under vacuum to constant weight, to obtain final product
Carboxylic acid-chlorohydrocarbon copolymer；71.21g trimethylallylammonium chloride and 0.93g n-amyl alcohol are added in another reactor, then
Adding 729.38g water and be configured to the aqueous solution that mass concentration is 9%, 5 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 15 minutes,
Adding 0.29g ammonium ceric nitrate, stir and treat its mix homogeneously in 15 minutes, be continuously heating at 50 DEG C carry out polyreaction, reaction 8 is little
Time, obtain terminal hydroxy group cationic side chain aqueous solution；By 35.1g Polyethylene Glycol (molecular weight=1800), 15.6g sodium hydroxide successively
Add in gained terminal hydroxy group cationic side chain aqueous solution, be warming up to 70 DEG C, stir 5 minutes, moisture in evacuation removing system, add
Enter 10.72g hexamethylene, be continuously heating at 105 DEG C react, while reaction, reaction gained water separated, reaction
Slough hexamethylene by evacuation after 3.5 hours, obtain ftmctionalized sidechains；Gained carboxylic acid-chloro it is sequentially added in reactor
Hydrocarbon copolymer, gained ftmctionalized sidechains, 273.53g dimethylformamide, be warming up to 50 DEG C, stirs 20 minutes, is continuously heating to
95 DEG C, adding 752.21g methanol after reacting 6 hours, cyclic washing precipitates 5 times, at 70 DEG C, precipitate is dried under vacuum to perseverance
Weight, being eventually adding 137.84g water and i.e. obtaining mass fraction is 50% prepare with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain
Polycarboxylate dispersant's solution.
Embodiment 10
After the polycarboxylate dispersant's solution that mass fraction is 50% embodiment 9 obtained deposits 40 days at 7 DEG C, measure it
Implementation result.
Embodiment 11
First will be sequentially added in reactor 7.21g acrylic acid, 6.1g vinyl benzyl chloride, 1.15g azodiisobutyronitrile,
53.24g1,4-dioxane, each feeding interval mixing time 20 minutes, after 4 deoxygenations 15 minutes repeatedly of reactor inflated with nitrogen
Sealing, be warming up at 50 DEG C carry out polyreaction, add 133.11g methanol after reacting 5 hours, cyclic washing precipitates 5 times, will be heavy
Shallow lake thing is dried under vacuum to constant weight at 70 DEG C, obtains carboxylic acid-chlorohydrocarbon copolymer；By 17.66g methacryl oxypropyl trimethyl
Ammonium chloride and 0.59g isobutanol add in another reactor, add 769.89g water be configured to mass concentration be 4% water-soluble
Liquid, 5 deoxygenations repeatedly of reactor inflated with nitrogen sealed after 25 minutes, added 4.77g Cericammoniumsulfate, stirred and within 18 minutes, treat its mixing all
Even, it is continuously heating at 60 DEG C carry out polyreaction, reacts 6 hours, obtain terminal hydroxy group cationic side chain aqueous solution；By 96g first
Epoxide Polyethylene Glycol (molecular weight=3000), 24g sodium hydroxide are sequentially added in gained terminal hydroxy group cationic side chain aqueous solution, rise
Temperature, to 55 DEG C, stirs 20 minutes, moisture in evacuation removing system, adds 9.14g toluene, is continuously heating at 110 DEG C carry out
Reaction, separates reaction gained water while reaction, sloughs toluene by evacuation, obtain functionalization after reacting 2 hours
Side chain；Be sequentially added in reactor gained carboxylic acid-chlorohydrocarbon copolymer, gained ftmctionalized sidechains, 151.57g1,4-dioxy oneself
Ring, is warming up to 40 DEG C, stirs 40 minutes, is continuously heating to 70 DEG C, adds 757.85g methanol, cyclic washing after reacting 10 hours
Precipitating 3 times, at 40 DEG C, precipitate is dried under vacuum to constant weight, being eventually adding 157.49g water and i.e. obtaining mass fraction is 50%
The polycarboxylate dispersant's solution prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain.
Embodiment 12
After the polycarboxylate dispersant's solution that concentration is 50% embodiment 11 obtained deposits 20 days at 6 DEG C, measure it
Implementation result.
Implementation result:
1. flowing degree of net paste of cement
For investigating the height anti-chamotte mould polycarboxylic acids dispersion that the present invention is prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain
The agent solution mobility action effect to cement, reference cement is starched stream by test determination each embodiment under identical volume only
Dynamic degree.Test is carried out by GB/T8077-2012 " Methods for testing uniformity of concrete admixture ", W/C=0.29, and volume is solid for folding
Volume.Selecting existing commercially available traditional comb shape poly carboxylic acid series water reducer (comparative example) as a comparison sample, result of the test is shown in Table 1.
Table 1 pulp flowage results of property
From table 1 it follows that the height that the inventive method is prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain resists
Chamotte mould polycarboxylate dispersant's solution, the ratio of mud and the folding of 0.35% 0.29 are consolidated under volume, all can show the dispersion of excellence
Ability and cement adaptability.
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 height that the inventive method is prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain resists
Chamotte mould polycarboxylate dispersant's solution 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 height that the inventive method is prepared with unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain resists
Chamotte mould polycarboxylate dispersant's solution all can show preferable divergence and the slump and holding under the clay additive of 1.8%
Ability.
Claims (3)
1. the method that unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain prepares high anti-chamotte mould polycarboxylate dispersant, its feature
Being, step is as follows:
(1) unsaturated carboxylic acid and unsaturated halogenated hydrocarbons copolymerization: be sequentially added into (methyl) acrylic acid or itself and insatiable hunger in reactor
With the mixture of carboxylic acid, unsaturated halogenated hydrocarbons, initiator, organic solvent, each feeding interval mixing time 5-20 minute, reaction
3-5 the deoxygenation repeatedly of device inflated with nitrogen sealed after 10-30 minute, carried out polyreaction at being warming up to 50-120 DEG C, and 1.5-5 is little in reaction
Adding methanol time after, cyclic washing precipitates 3-5 time, precipitate is dried under vacuum at 40-80 DEG C constant weight, obtains carboxylic acid-halogen
For hydrocarbon copolymer；
(2) 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；
(3) Side functionalization: Polyethylene Glycol compounds, sodium hydroxide are sequentially added into step (2) products therefrom terminal hydroxy group sun
In ionic side chains aqueous solution, it is warming up to 50-70 DEG C, stirs 5-20 minute, moisture in evacuation removing system, add water entrainer,
React at being continuously heating to 85-110 DEG C, while reaction, reaction gained water is separated, pass through after reacting 2-6 hour
Evacuation sloughs water entrainer, obtains ftmctionalized sidechains；
(4) etherificate grafting: be sequentially added into step (1) products therefrom carboxylic acid-halogenated hydrocarbons copolymer, step (3) institute in reactor
Obtain product ftmctionalized sidechains, organic solvent, be warming up to 40-60 DEG C, stir 20-40 minute, be continuously heating to 70-100 DEG C, reaction
Adding methanol after 4-10 hour, cyclic washing precipitates 3-5 time, at 40-80 DEG C, precipitate is dried under vacuum to constant weight, finally adds
Enter water and dilute to obtain the high anti-mud polycarboxylate dispersant's solution of unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain type of desired concn；
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；Unsaturated halogenated hydrocarbons described in step (1) is allyl chloride, allyl bromide, bromoallylene, methylallyl chloride, 4-bromo-1-fourth
Alkene, chloroisoamylene or vinyl benzyl chloride, consumption and (methyl) acrylic acid described in step (1) or its mixed with unsaturated carboxylic acid
The mol ratio of compound is 0.15-0.5:1；Initiator described in step (1) is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or mistake
Aoxidize (methyl) acrylic acid or itself and the mixture of unsaturated carboxylic acid and step added in dibenzoyl, consumption and step (1)
(1) ratio of the total mole number of the unsaturated halogenated hydrocarbons added in is 0.01-0.05:1；Organic solvent described in step (1) is
Dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane or dimethylformamide, (methyl) acrylic acid added in consumption and step (1) or its with
The ratio of the unsaturated halogenated hydrocarbons quality sum added in the mixture of unsaturated carboxylic acid and step (1) is 4-10:1；Institute in step (1)
In (methyl) acrylic acid that adds in the methanol usage stated and step (1) or its mixture with unsaturated carboxylic acid and step (1)
The ratio of the unsaturated halogenated hydrocarbons quality sum added is 5-10:1；
Unsaturated cation quaternary ammonium salt described in step (2) 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 (2)；Low described in step (2)
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 (2) is ammonium ceric nitrate or Cericammoniumsulfate, consumption and step
(2) mol ratio of the lower aliphatic alcohols described in is 0.03-1:1；
Polyethylene Glycol compounds described in step (3) is Polyethylene Glycol or methoxy poly (ethylene glycol)；Described in step (3)
Sodium hydroxide concentration always rubs with the lower aliphatic alcohols described in step (2) and the Polyethylene Glycol compounds described in step (3)
Your ratio of number is 0.8-1.5:1；Water entrainer described in step (3) is hexamethylene, benzene or toluene, and consumption is institute in step (2)
Obtain the 8-30% of the Polyethylene Glycol compounds gross mass added in product end hydroxyl cationic side chain and step (3)；
Organic solvent described in step (4) is dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane or dimethylformamide, consumption and step
(1) in, in products therefrom carboxylic acid-halogenated hydrocarbons copolymer and step (3), the ratio of products therefrom ftmctionalized sidechains's mass sum is 1-5:1；
Methanol usage described in step (4) is produced with gained in products therefrom carboxylic acid-halogenated hydrocarbons copolymer in step (1) and step (3)
The ratio of thing ftmctionalized sidechains's mass sum is 5-10:1.
A kind of unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain the most according to claim 1 prepares high anti-chamotte mould polycarboxylic acids
The method of dispersant, it is characterised in that the lower aliphatic alcohols described in step (2) and the unsaturated halogenated hydrocarbons described in step (1)
Mol ratio be 0.2-0.5:1.
A kind of unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain the most according to claim 1 prepares high anti-chamotte mould polycarboxylic acids
The method of dispersant, it is characterised in that the Polyethylene Glycol compounds described in step (3) and the unsaturation described in step (1)
The mol ratio of halogenated hydrocarbons is 0.5-0.8:1.
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| CN114605073A (en) * | 2022-04-12 | 2022-06-10 | 广州市纳能环保技术开发有限公司 | Preparation method and application of functional ceramic glaze powder |
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