CN108948261B - High-strength heat-resistant fireproof concrete viscosity modifying agent and its preparation method and application - Google Patents
High-strength heat-resistant fireproof concrete viscosity modifying agent and its preparation method and application Download PDFInfo
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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
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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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
- C08F228/00—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 bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B2103/44—Thickening, gelling or viscosity increasing agents
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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
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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Abstract
The invention belongs to concrete admixture field, it is related to a kind of concrete viscosity modifying agent and its preparation.The present invention provides a kind of concrete viscosity modifying agent, and the viscosity modifier includes double bond containing polymer and double bond photochemical catalyst；The double bond containing polymer is prepared by the raw material of following components: 5~50 parts by weight of bisphenol compound, 5~100 parts by weight of carboxyl group-containing monomer, 5~100 parts by weight of monomer containing sulfonic group, 1~50 parts by weight of unsaturated monomer, 1,3- diene monomers, 0.1~10 parts by weight, 10~300 parts by weight of alkali, 100~5000 parts by weight of solvent, 0.1~20 parts by weight of catalyst；Total additional amount of carboxyl group-containing monomer and the monomer containing sulfonic group is not less than 50 parts by weight.Gained concrete viscosity modifying agent has the advantages that dissolvable, easy construction and good cohesiveness；When add it to prepare concrete in the materials such as cement when, gained concrete intensity with higher and anti-aging property.
Description
Technical field
The invention belongs to concrete admixture fields, and in particular to a kind of high-strength heat-resistant fireproof concrete viscosity modifying agent
And preparation method thereof.
Background technique
It is further excellent how under the premise of environmentally protective with Environmental and the pay attention to day by day of construction quality
The comprehensive performance (flexibility of such as constructing, mechanical strength, fire-retardant) for changing, improving concrete has become focus concerned by people.From
Since the late 20th century, people just always search for improving the effective way of concrete comprehensive performance.Concrete is improved at present
The effective way of performance mainly passes through introducing water-reducing agent, improves its partial properties by reducing the dosage of water；However it is a large amount of
It was verified that often the addition of single water-reducing agent can't go out concrete by Coordinated Play well in the actual construction process
Comprehensive excellent properties, the workability of concrete, bleeding and package performance are still bad, so as to cause concrete in work progress
In be also easy to produce more defect, such as: honeycomb, pitted skin, cavity, dew muscle and then seriously affect the comprehensive performance of concrete so that its
It is more difficult to play preferable mechanical strength etc., the final integral strength for influencing building；In addition current concrete building material
Thermal stability and flame retardant property are bad, mostly be extremely easy in decomposition after heated or in the case where having open fire with it is combustion-supporting, after building
So that it has potential risk factor.
To solve the above problems, it is generally necessary to concrete viscosity modifying agent is added, such as xanthan gum, warm human relations glue, polyoxyethylene
The tackifier such as class, cellulose ethers, polyacrylamide and polyvinyl alcohol improve the coherency and stability of concrete, thus
The cohesive strength and water-retaining property for improving concrete achieve the purpose that increase concrete overall work performance.
Summary of the invention
The present invention provides a kind of novel high-strength heat-resistant fireproof concrete viscosity modifying agent and preparation method thereof, and gained is mixed
Solidifying soil viscosity modifier has the advantages that dissolvable, easy construction and good cohesiveness；When adding it in the materials such as cement
When preparing concrete, since there are double bonds in viscosity modifier, in work progress under the action of double bond light-catalyzed reaction auxiliary agent
Middle double bond crosslinks reaction and is capable of forming cross-linked three D network, so that gained concrete intensity with higher and anti-ageing
Change performance.
Technical solution of the present invention:
The invention solves first technical problem be to provide a kind of concrete viscosity modifying agent, the concrete viscosity
Modifying agent includes double bond containing polymer and double bond photochemical catalyst；Wherein, the double bond containing polymer by following components original
Material is prepared:
Summation, which is added, in carboxyl group-containing monomer and monomer containing sulfonic group should be not less than 50 parts by weight.
Further, the double bond photochemical catalyst is that can crosslink under light action with the double bond containing polymer instead
The catalyst answered.In the present invention, as long as the additive amount of double bond photochemical catalyst can make containing double, to build polymer reaction complete.Into one
Step, the additive amount of the double bond photochemical catalyst are 0.01~10 parts by weight.
Further, the double bond photochemical catalyst selection: 1- benzoylcyclohexanol (PI-184), 4,4 '-(2- hydroxypropyl acyls
Base) diphenyl-methane (PI-127), 2- hydroxypropyl phenyl ketone (PI-1173), 2- hydroxypropyl -2- hydroxyethoxyphenyl ketone
(PI-2959), carbomethoxvphenvl ketone (PI-184), bis- (2,4,6- trimethylbenzoyl) phosphono benzene (PI-819),
2,4,6- trimethylbenzoy-dipheny phosphine oxides (PI-TPO), 4- benzoyl -4'- methyl-diphenyl sulfide (PI-
BMS), benzoin dimethylether (PI-BDK), (dimethylamino)-ethyl benzoate (PI-EDB), 4,4'- bis- (lignocaine) hexichol
Ketone (PI-EAB), 2- ethyl hydrazine (PI-EAQ), 2- isopropyl thioxanthone (PI-ITX), 2- methyl-1-[4- methylthio phenyl
Base] -2- morpholinyl -1- acetone (PI-907), 2,4- diethyl thioxanthone (PI-DETX) or 2- benzyl -2- dimethylamino -
At least one of 1- (4- morpholinyl phenyl) butanone (PI-369).
Further, described mixed containing double polymer built and the double bond photochemical catalyst in above-mentioned concrete viscosity modifying agent
Conjunction is uniformly placed spare；Or: it is described to be placed respectively containing double polymer built and the double bond photochemical catalyst, when concrete batching again
The two is uniformly mixed.
Further, the double bond containing polymer is prepared using following methods: by 5~100 parts by weight of carboxyl group-containing monomer, being contained
5~100 parts by weight of sulfonic group monomer, 10~300 parts by weight of alkali, 100~5000 parts by weight of solvent are added in reaction kettle, Yu Wendu
5~20min is reacted at 0~80 DEG C；Add 5~50 parts by weight of bisphenol compound, 1~50 parts by weight of unsaturated monomer, catalysis
0.1~20 parts by weight of agent obtain faint yellow thick solution after reacting 10~120min at 10~80 DEG C of temperature；Then it is added 1,
0.1~10 parts by weight of 3- diene monomers are stirred to react 10~120min at 20~85 DEG C of temperature, filter insoluble matter residue, collect
Filtrate obtains double bond containing polymer.
Further, the bisphenol compound is hydroquinone (HQ), resorcinol (HP), bisphenol-A, bisphenol S, Bisphenol F, connection
Bis- (4- the hydroxy phenyl) -1- diphenylphosphino ethanes (BHPPE) of benzenediol (BP), 4,4 '-dihydroxy diphenyl ethers (DHBE), 2,2-, 2,2-
Bis- (2,6- diformazan oxyphenyl)-propane (BDMPP), 4,4 '-dihydroxy diphenyl sulfides (DHBT), 4,4 '-dimercapto diphenyl sulfides
Ether (DTBT) to diphenyl disulfide phenol (DTB), 4,4 '-dimercapto diphenyl sulphone (DPS)s (FSH), 4,4 '-dimercapto benzophenone (TSH) or contains
At least one of phospho hetero phenanthrene oxide bis-phenol (DOPO-HQ).
Further, the carboxyl group-containing monomer is acrylic acid, methacrylic acid, 2- ethylacrylic acid, butene dioic acid, clothing health
Acid, 2- methyl -4- penetenoic acid, 4- penetenoic acid, 2- methyl -2- penetenoic acid, 2- heptenoic acid, 3- heptenoic acid, 2- octenoic acid or 3,7-
At least one of dimethyl -6- octenoic acid.
Further, the monomer containing sulfonic group is vinyl sulfonic acid, propene sulfonic acid, methacrylic sulfonic acid, styrene sulfonic acid, 2-
Acrylamide-2-methyl propane sulfonic, alpha-olefin sulfonic acid (C12-C16), allyl glycidyl ether sulfonic acid or 2- hydroxyl -3- fourth
At least one of alkene -1- p-methyl benzenesulfonic acid.
Further, the unsaturated monomer is acrylamide, Methacrylamide, N,N-DMAA, N- hydroxyl
Ethyl acrylamide, N hydroxymethyl acrylamide, N- ethyl acrylamide, N, N- diethyl -2- acrylamide, N- (2- amino
Ethyl) acrylamide, N- (2- dimethylaminoethyl) acrylamide, methyl allyl polyoxyethylene ether, N, N '-di-2-ethylhexylphosphine oxide third
Acrylamide or N, any one of N '-methylenebismethacrylamide.
Further, 1, the 3- diene monomers are 1,3-butadiene, 2- methyl-1,3- butadiene, 2- ethyl -1,3- fourth two
Alkene, 1,3- pentadiene, 2- methyl-1,3-pentylene, 2- ethyl -1,3- pentadiene, 2- ethyl -1,3- cyclopentadiene, 1,3- are pungent
Any one of diene, pyrroles or 1,3- cyclo-octadiene.
Further, the alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, lithium carbonate, carbon
Appointing in sour sodium, potassium carbonate, calcium carbonate, magnesium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus, calcium bicarbonate or magnesium bicarbonate
It is a kind of.
Further, the solvent is the mixture of water, ethyl alcohol or both.
Further, the catalyst are as follows: azodiisobutyronitrile, dibenzoyl peroxide, ammonium persulfate, potassium peroxydisulfate, mistake
Sodium sulphate, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, protochloride
Copper, frerrous chloride, ferrous sulfate, urea, vitamin C, iron chloride, aluminium chloride, zinc chloride, boron trifluoride, stannic chloride, chlorination
In titanium, trifluoromethanesulfonic acid sodium, trifluoromethanesulfonic acid potassium, trifluoromethanesulfonic acid calcium, magnesium triflate or trifluoromethanesulfonic acid zinc at least
It is a kind of.
The invention solves second technical problem be to provide the preparation method of above-mentioned concrete viscosity modifying agent, it is described
Preparation method includes the following steps:
1) preparation containing double polymer built: by 5~100 parts of carboxyl group-containing monomer, 5~100 parts of monomer containing sulfonic group, alkali 10~
300 parts, in 100~5000 parts of addition reaction kettles of solvent, 5~20min is reacted at 0~80 DEG C of Yu Wendu；Add bis-phenol chemical combination
5~50 parts of object, 1~50 part of unsaturated monomer, 0.1~20 part of catalyst at 10~80 DEG C of temperature react 10~120min after
Faint yellow thick solution；Then be added 0.1~10 part of 1,3- diene monomers be stirred to react 10 at 20~85 DEG C of temperature~
120min filters insoluble matter residue, collects filtrate and double bond containing polymer is made；In the present invention, it is necessary to first by alkali and carboxyl, sulphur
After acid-base reaction is complete, bis-phenol is added, otherwise the hydroxyl in bis-phenol can also react with alkali, so that its active hydrogen is reacted
Fall, and influences its subsequent reacting with double bond；
2) 0.01~10 part of double bond photochemical catalyst is added into double bond containing polymer filtrate made from step 1), by its point
Up to concrete viscosity modifying agent after dissipating uniformly.
The invention solves third technical problem be to provide the application of above-mentioned concrete viscosity modifying agent, the coagulation
The additive amount of native viscosity modifier is 0.5wt%~3wt% of polycarboxylate water-reducer quality.
The invention solves the 4th technical problem be to provide a kind of double bond containing polymer, the double bond containing polymerization
Object is prepared by the raw material of following components:
Summation, which is added, in carboxyl group-containing monomer and monomer containing sulfonic group should be not less than 50 parts by weight.
The invention solves the 5th technical problem be to provide the preparation method of above-mentioned double bond containing polymer, the system
Preparation Method are as follows: by 5~100 parts by weight of carboxyl group-containing monomer, 5~100 parts by weight of monomer containing sulfonic group, 10~300 parts by weight of alkali, molten
100~5000 parts by weight of agent are added in reaction kettle, and 5~20min is reacted at 0~80 DEG C of Yu Wendu；Add bisphenol compound 5~
50 parts by weight, 1~50 parts by weight of unsaturated monomer, 0.1~20 parts by weight of catalyst react 10 at 10~80 DEG C of temperature~
Faint yellow thick solution is obtained after 120min；Then 1,3- diene monomers, 0.1~10 parts by weight are added at 20~85 DEG C of temperature
It is stirred to react 10~120min, filters insoluble matter residue, collects filtrate.
The invention solves the 6th technical problem to be to provide above-mentioned double bond containing polymer modified in concrete viscosity
Application in agent, specifically: above-mentioned double bond containing polymer is uniformly mixed with double bond photochemical catalyst.
Further, the double bond photochemical catalyst is that can crosslink under light action with the double bond containing polymer instead
The catalyst answered.The double bond photochemical catalyst selection: 1- benzoylcyclohexanol (PI-184), 4,4 '-(2- hydroxy propionyl groups) two
Phenylmethane (PI-127), 2- hydroxypropyl phenyl ketone (PI-1173), 2- hydroxypropyl -2- hydroxyethoxyphenyl ketone (PI-
2959), carbomethoxvphenvl ketone (PI-184), bis- (2,4,6- trimethylbenzoyl) phosphono benzene (PI-819), 2,4,
6- trimethylbenzoy-dipheny phosphine oxide (PI-TPO), 4- benzoyl -4'- methyl-diphenyl sulfide (PI-BMS), peace
Breath fragrant double methyl ether (PI-BDK), (dimethylamino)-ethyl benzoate (PI-EDB), (lignocaine) benzophenone of 4,4'- bis- (PI-
EAB), 2- ethyl hydrazine (PI-EAQ), 2- isopropyl thioxanthone (PI-ITX), 2- methyl-1-[4- methyl mercapto phenyl]-2-
Quinoline base -1- acetone (PI-907), 2,4- diethyl thioxanthone (PI-DETX) or 2- benzyl -2- dimethylamino -1- (4-
At least one of quinoline phenyl) butanone (PI-369).
Further, as long as the additive amount of double bond photochemical catalyst can make containing double, to build polymer reaction complete.The double bond
The additive amount of photochemical catalyst is 0.01~10 parts by weight.
Heretofore described raw material parts is parts by weight unless otherwise specified.
Beneficial effects of the present invention:
1. 3- diene monomers bring it about Diels-Alder reaction (D-A by controlling polymerizing condition present invention introduces 1
Reaction), i.e., polymer containing double bonds is generated by 1,3- diene monomers and carboxyl group-containing monomer, monomer polymerization containing sulfonic group；Again
The polymer containing double bonds is uniformly mixed with double bond photochemical catalyst up to concrete viscosity modifying agent, since gained viscosity changes
There are double bonds in property agent, and there are evenly dispersed double bond photochemical catalysts, so that the viscosity modifier concrete batching
When crosslink reaction in the construction process, and then form cross-linked three D network structure；Change so that both having maintained viscosity
Property agent use before can dissolve, easily construction and good cohesiveness；Simultaneously after construction since the presence of cross-linked three D network makes
Obtain finally obtained concrete intensity with higher and anti-aging property.
2. the present invention using contain thioether, phosphorous or oxygen containing high density layer of charcoal promotor diphenol as reacting bottom on a small quantity
Object, not only increases the intensity and hot property of final concrete, while imparting its preferable inhibition burning and flame retardant property.
3. apparent viscosity of the gained concrete modifying agent of the invention at 30.0 ± 0.1 DEG C of temperature is 200~1000Pas.
4. the present invention has, polymerization technology is simple, fixed equipment less investment, low energy consumption, safety is good, it is repeated it is strong,
The advantages that stability is good, and product yield is high, pollution is small.
5. gained concrete viscosity modifying agent of the invention is added to the bridging in concrete mix by polymer molecule
And recombination function, equably it is isolated in a manner of being similar to space matrix, is distributed cement slurry, so that reaching improves concrete
Workability, bleeding, the slump and application property, adjust concrete setting time, reduce the heat of hydration, improve concrete early stage or
Each age strength.
6. the workability easily occurred in the construction process the present invention overcomes concrete, cohesiveness are poor, bleeding isolates and mixed
Coagulate the defects of soil material hot property is bad, inflammable；And preparation method have high income, operation simple, fixed equipment less investment,
Low energy consumption and environmentally protective advantage.
Specific embodiment
In the present invention, bis-phenol structure is introduced in viscosity modifier molecular structure, so that obtained viscosity modifier has
Compression strength while preferable anti-flammability with preferable hot property (due to the introducing of bis-phenol aromatic ring structure) and after solidifying；Draw
Enter the monomer of strong anion containing sulfonic group, so that it can be complexed in concrete mixing process with formation such as calcium ion, magnesium ions
Effect, so that concrete is not easy cementing, isolation during mixing and stirring, greatly improve concrete can application property；1 is introduced,
3- diene monomers are brought it about Diels-Alder reaction (D-A reaction) by controlling polymerizing condition, namely pass through 1,3- bis-
Alkene monomer and carboxyl group-containing monomer, monomer polymerization containing sulfonic group generate compound containing double bonds, the double bond generated finally by this
Cross-linking reaction is carried out in construction with double bond photochemical catalyst, to form cross-linked three D network structure, both maintains viscosity modifier
Can dissolve before agent use, can application property, while further improving the intensity and anti-aging property for making concrete obtained by user.
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for
Invention is further explained, should not be understood as the limitation to the present invention including range, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made according to the content of aforementioned present invention.
Embodiment 1
Acrylic acid 50g, propene sulfonic acid 50g, sodium hydroxide 20g, water 2000g are added in reaction kettle, at 20 DEG C of Yu Wendu
10min is reacted, bisphenol S 28g, acrylamide 20g, azodiisobutyronitrile+FeCl are added3(1+1) g is anti-under temperature 50 C
Faint yellow thick solution is obtained after answering 120min；It adds 1,3-butadiene monomer 1g and is stirred to react 60min, filtering pole in 60 DEG C
A small amount of insoluble matter residue, collects filtrate；Double bond photochemical catalyst (PI-184+PI-127:0.1g+0.05g) is added into filtrate again,
The high-strength heat-resistant fireproof concrete viscosity modifying agent of finished product is obtained after being uniformly dispersed.
Rotational viscometer is used at 30.0 ± 0.1 DEG C of temperature, measuring its apparent viscosity is 750Pas, pure resin pole
Limited oxygen index (LOI) is 39, excellent fireproof performance.Each component raw material is than as shown in table 1.By gained viscosity modifier and polycarboxylic acids
For water-reducing agent with the use of being added in concrete, the performance of concrete is as shown in table 2.
Embodiment 2
Reaction is added in methacrylic acid 70g, methacrylic sulfonic acid 50g, lithium hydroxide 25g, water+ethyl alcohol (4000+10) g
In kettle, 20min is reacted at 25 DEG C of Yu Wendu；Add BP+DTBT (5+20) g, Methacrylamide 20g, ammonium persulfate+thio
Potassium sulfate (0.2+0.1) g obtains faint yellow thick solution after reacting 120min under temperature 50 C；Add 1,3- octadiene list
Body 5g is stirred to react 80min in 50 DEG C；Minute quantity insoluble matter residue is filtered, filtrate is collected, then double bond light is added into filtrate and urges
Agent (PI-BDK:0.01g) obtains the high-strength heat-resistant fireproof concrete viscosity modifying agent of finished product after being uniformly dispersed.
Rotational viscometer is used at 30.0 ± 0.1 DEG C of temperature, measuring its apparent viscosity is 780Pas, pure resin pole
Limited oxygen index (LOI) is 39, excellent fireproof performance.Each component raw material is than as shown in table 1.By gained viscosity modifier and polycarboxylic acids
With the use of being added in concrete, the performance of concrete is shown in Table 2 water-reducing agent.
Embodiment 3
By acrylic acid+itaconic acid (40+20) g, methacrylic sulfonic acid+styrene sulfonic acid (40+5) g, potassium hydroxide 30g, water
5000g is added in reaction kettle, reacts 15min at 10 DEG C of Yu Wendu；Add BHPPE+DOPO-HQ (10+15) g, acrylamide
50g, potassium peroxydisulfate+vitamin C (1+0.7) g obtain faint yellow thick solution after reacting 100min at 35 DEG C of temperature；It adds
1,3-pentadiene monomer 3g reacts 100min in temperature 45 C；Minute quantity insoluble matter residue is filtered, collects filtrate, then into filtrate
It is added double bond photochemical catalyst (PI-TPO:0.05g), the high-strength heat-resistant fireproof concrete of finished product is obtained after being uniformly dispersed and is glued
Spend modifying agent.
Rotational viscometer is used at 30.0 ± 0.1 DEG C of temperature, measuring its apparent viscosity is 820Pas, pure resin pole
Limited oxygen index (LOI) is 40, excellent fireproof performance.Each component raw material is than as shown in table 1.By gained viscosity modifier and polycarboxylic acids
With the use of being added in concrete, the performance of concrete is shown in Table 2 water-reducing agent.
Embodiment 4
By acrylic acid+3,7 dimethyl 6 octenoic acid (30+20) g, methacrylic sulfonic acid+2- acrylamide -2- methyl-prop
Sulfonic acid (10+35) g, sodium carbonate 100g, water 3500g are added in reaction kettle, react 15min at 5 DEG C of Yu Wendu；Add HQ
15g, N hydroxymethyl acrylamide 15g, dibenzoyl peroxide+titanium chloride (1.1+0.5) g react 60min at 75 DEG C of temperature
Afterwards faint yellow thick solution, add 2- methyl-1,3- divinylic monomer 3g is in 65 DEG C of reaction 30min of temperature；Filter pole
A small amount of insoluble matter residue, collects filtrate；Double bond photochemical catalyst (PI-369:0.1g) is added into filtrate again, is uniformly dispersed
After obtain the high-strength heat-resistant fireproof concrete viscosity modifying agent of finished product.
Rotational viscometer is used at 30.0 ± 0.1 DEG C of temperature, measuring its apparent viscosity is 900Pas, pure resin pole
Limited oxygen index (LOI) is 36, excellent fireproof performance.Each component raw material is than as shown in table 1.By gained viscosity modifier and polycarboxylic acids
With the use of being added in concrete, the performance of concrete is shown in Table 2 water-reducing agent.
Embodiment 5
Acrylic acid 70g, methacrylic sulfonic acid 90g, sodium hydroxide 70g, water 4500g are added in reaction kettle, Yu Wendu 56
10min is reacted at DEG C, adds HP 5g, methyl allyl polyoxyethylene ether 50g, sodium peroxydisulfate+urea (5+1.2) g in temperature
Faint yellow thick solution is obtained after reacting 90min at 65 DEG C, adds 2- ethyl -1,3- cyclopentadiene monomers 10g in temperature 70
DEG C reaction 45min；Filter minute quantity insoluble matter residue, collect filtrate, then into filtrate be added double bond photochemical catalyst (PI-DETX:
2g), the high-strength heat-resistant fireproof concrete viscosity modifying agent of finished product is obtained after being uniformly dispersed.
Rotational viscometer is used at 30.0 ± 0.1 DEG C of temperature, measuring its apparent viscosity is 660Pas, pure resin pole
Limited oxygen index (LOI) is 38, excellent fireproof performance.Each component raw material is than as shown in table 1.By gained viscosity modifier and polycarboxylic acids
With the use of being added in concrete, the performance of concrete is shown in Table 2 water-reducing agent.
The viscosity modifier for being BASF RHEOPLUS 420 by viscosity modifier obtained by embodiment 1-5 and the addition trade mark
Agent (comparative example 1) is applied to concrete, and tests the test that gained concrete carries out bleeding rate, mechanical property, is also tested for
It is not added with the correlated performance of the blank sample of viscosity modifier；Test method is carried out according to GB/T8077 and GB/T50080-2016,
Test result is as shown in table 2.The compositing formula of tested concrete is as follows: cement 260kg/m3, flyash 110kg/m3, poly- carboxylic
Sour water-reducing agent 3.7kg/m3, viscosity modifier 0.0629kg/m3, coarse aggregate 1160kg/m3, sand 710kg/m3。
The raw material components of 1 embodiment of table-embodiment 5
The performance comparison of table 2 addition Examples 1 to 5 and the obtained concrete of 1 viscosity modifier of comparative example and blank sample
Claims (12)
1. a kind of concrete viscosity modifying agent, which is characterized in that the concrete viscosity modifying agent includes double bond containing polymer
With double bond photochemical catalyst；Wherein, the double bond photochemical catalyst is that can crosslink under light action with double bond containing polymer
The catalyst of reaction；The double bond containing polymer is prepared by the raw material of following components:
Total additional amount of carboxyl group-containing monomer and the monomer containing sulfonic group is not less than 50 parts by weight；
Also, the double bond containing polymer is prepared using following methods: by carboxyl group-containing monomer, monomer containing sulfonic group, alkali and molten
Agent is added in reaction kettle, and 5~20min is reacted at 0~80 DEG C；Add bisphenol compound, unsaturated monomer and catalyst in
Faint yellow thick solution is obtained after reacting 10~120min at 10~80 DEG C；Then 1,3- diene monomers are added at 20~85 DEG C
It is stirred to react 10~120min, filters insoluble matter residue, collects filtrate；
The unsaturated monomer is acrylamide, Methacrylamide, N, N- dimethylacrylamide, N- hydroxylethyl acyl
Amine, N hydroxymethyl acrylamide, N- ethyl acrylamide, N, N- diethyl -2- acrylamide, N- (2- amino-ethyl) acryloyl
Amine, N- (2- dimethylaminoethyl) acrylamide, methyl allyl polyoxyethylene ether, N, N '-methylene-bisacrylamide or N,
Any one of N '-methylenebismethacrylamide.
2. concrete viscosity modifying agent according to claim 1, which is characterized in that the double bond photochemical catalyst selection: 1-
Benzoylcyclohexanol, 4,4 '-(2- hydroxy propionyl group) diphenyl-methanes, 2- hydroxypropyl phenyl ketone, 2- hydroxypropyl -2- '-hydroxyethoxy
Base phenyl ketone, carbomethoxvphenvl ketone, bis- (2,4,6- trimethylbenzoyl) phosphono benzene, 2,4,6- trimethylbenzene first
Acyl group-diphenyl phosphine oxide, 4- benzoyl -4'- methyl-diphenyl sulfide, benzoin dimethylether, p-(dimethylamino)-benzoic acid second
Ester, 4,4'- bis- (lignocaine) benzophenone, 2- ethyl hydrazine, 2- isopropyl thioxanthone, 2- methyl-1-[4- methylthio phenyl
Base] -2- morpholinyl -1- acetone, 2,4- diethyl thioxanthone or 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) fourth
At least one of ketone.
3. concrete viscosity modifying agent according to claim 2, which is characterized in that the additive amount of the double bond photochemical catalyst
For 0.01~10 parts by weight.
4. concrete viscosity modifying agent according to claim 1, which is characterized in that
The bisphenol compound is hydroquinone, resorcinol, bisphenol-A, bisphenol S, Bisphenol F, '-biphenyl diphenol, 4,4 '-dihydroxy
Bis- (4- the hydroxy phenyl) -1- diphenylphosphino ethanes of diphenyl ether, 2,2-, 2,2- bis- (2,6- diformazan oxyphenyl)-propane, 4,4 '-dihydroxies
Base diphenyl sulfide, 4,4 '-dimercapto diphenyl sulfides, to diphenyl disulfide phenol, 4,4 '-dimercapto diphenyl sulphone (DPS)s, 4,4 '-dimercapto hexichol first
At least one of ketone or the bis-phenol of oxide containing phospho hetero phenanthrene；Or:
The carboxyl group-containing monomer is acrylic acid, methacrylic acid, 2- ethylacrylic acid, butene dioic acid, itaconic acid, 2- methyl -4-
Penetenoic acid, 4- penetenoic acid, 2- methyl -2- penetenoic acid, 2- heptenoic acid, 3- heptenoic acid, 2- octenoic acid or 3,7- dimethyl -6- octene
At least one of acid；Or:
The monomer containing sulfonic group is methacrylic sulfonic acid, styrene sulfonic acid, 2- acrylamide-2-methyl propane sulfonic, alpha-olefin
At least one of sulfonic acid, allyl glycidyl ether sulfonic acid or 2- hydroxyl-3- butene-1-p-methyl benzenesulfonic acid；Or:
1, the 3- diene monomers are 1,3-butadiene, 2- methyl-1,3- butadiene, 2- ethyl -1,3-butadiene, 1,3- penta 2
Alkene, 2- methyl-1,3-pentylene, 2- ethyl -1,3- pentadiene, 2- ethyl -1,3- cyclopentadiene, 1,3- octadiene, Bi Kahuo
Any one of 1,3- cyclo-octadiene；Or:
The alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, lithium carbonate, sodium carbonate, carbonic acid
Any one of potassium, calcium carbonate, magnesium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus, calcium bicarbonate or magnesium bicarbonate；Or:
The solvent is the mixture of water, ethyl alcohol or both；Or:
The catalyst is azodiisobutyronitrile, dibenzoyl peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sulfurous acid
Sodium, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, stannous chloride, frerrous chloride, sulphur
Sour ferrous iron, urea, vitamin C, iron chloride, aluminium chloride, zinc chloride, boron trifluoride, stannic chloride, titanium chloride, trifluoromethanesulfonic acid sodium,
At least one of trifluoromethanesulfonic acid potassium, trifluoromethanesulfonic acid calcium, magnesium triflate or trifluoromethanesulfonic acid zinc.
5. concrete viscosity modifying agent according to any one of claims 1 to 4, which is characterized in that the concrete viscosity
In modifying agent, it is spare that the double bond containing polymer is uniformly mixed placement with the double bond photochemical catalyst；Or: it is described double bond containing
Polymer is placed respectively with the double bond photochemical catalyst, and the two is uniformly mixed by when concrete batching again.
6. the preparation method of any one of Claims 1 to 5 concrete viscosity modifying agent, which is characterized in that the preparation side
Method includes the following steps:
1) it prepares double bond containing polymer: carboxyl group-containing monomer, monomer containing sulfonic group, alkali and solvent is added in reaction kettle, in 0~
5~20min is reacted at 80 DEG C；Add bisphenol compound, unsaturated monomer and catalyst react 10 at 10~80 DEG C~
Faint yellow thick solution is obtained after 120min；Then be added 1,3- diene monomers be stirred to react 10 at 20~85 DEG C~
120min filters insoluble matter residue, collects filtrate and double bond containing polymer is made；
2) 0.01~10 part of double bond photochemical catalyst is added into double bond containing polymer filtrate made from step 1), is dispersed
Obtained concrete viscosity modifying agent after even.
7. concrete viscosity modifying agent is used to prepare concrete, which is characterized in that the concrete viscosity changes when preparing concrete
Property agent additive amount be polycarboxylate water-reducer quality 0.5wt%~3wt%；Wherein, the concrete viscosity modifying agent is power
Benefit requires 1~5 described in any item viscosity modifiers, or is made for preparation method as claimed in claim 6.
8. a kind of double bond containing polymer, which is characterized in that the double bond containing polymer by following components raw material preparation and
At:
Total additional amount of carboxyl group-containing monomer and the monomer containing sulfonic group is not less than 50 parts by weight；
Also, the double bond containing polymer is prepared using following methods: by carboxyl group-containing monomer, monomer containing sulfonic group, alkali and molten
Agent is added in reaction kettle, and 5~20min is reacted at 0~80 DEG C；Add bisphenol compound, unsaturated monomer and catalyst in
Faint yellow thick solution is obtained after reacting 10~120min at 10~80 DEG C；Then 1,3- diene monomers are added at 20~85 DEG C
It is stirred to react 10~120min, filters insoluble matter residue, collects filtrate；
Wherein, the unsaturated monomer is acrylamide, Methacrylamide, N,N-DMAA, N- ethoxy third
Acrylamide, N hydroxymethyl acrylamide, N- ethyl acrylamide, N, N- diethyl -2- acrylamide, N- (2- amino-ethyl) third
Acrylamide, N- (2- dimethylaminoethyl) acrylamide, methyl allyl polyoxyethylene ether, N, N '-methylene-bisacrylamide
Or any one of N, N '-methylenebismethacrylamide.
9. the preparation method of double bond containing polymer described in claim 8, which is characterized in that the preparation method is that: carboxylic will be contained
Base monomer, monomer containing sulfonic group, alkali and solvent are added in reaction kettle, and 5~20min is reacted at 0~80 DEG C；It adds bisphenol
It closes after object, unsaturated monomer and catalyst react 10~120min at 10~80 DEG C and obtains faint yellow thick solution；Then plus
Enter 1,3- diene monomers and be stirred to react 10~120min at 20~85 DEG C, filter insoluble matter residue, collection filtrate contains double to obtain the final product
The polymer of key.
10. application of the double bond containing polymer in concrete viscosity modifying agent, which is characterized in that by the double bond containing polymerization
Object is uniformly mixed up to concrete viscosity modifying agent with double bond photochemical catalyst；Wherein, the double bond containing polymer is wanted for right
Double bond containing polymer described in asking 8, or for using polymer made from preparation method as claimed in claim 9.
11. application of the double bond containing polymer according to claim 10 in concrete viscosity modifying agent, feature exist
In the double bond photochemical catalyst is the catalyst that cross-linking reaction can occur under light action with double bond containing polymer.
12. application of the double bond containing polymer in concrete viscosity modifying agent described in 0 or 11 according to claim 1, special
Sign is that the additive amount of the double bond photochemical catalyst is 0.01~10 parts by weight.
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| CN110396159B (en) * | 2019-09-11 | 2022-04-19 | 江苏博思通新材料有限公司 | Preparation method of polycarboxylic acid water reducer containing claw-type short side chains |
| CN111620609A (en) * | 2020-06-24 | 2020-09-04 | 广西南宁嘉泰水泥制品有限公司 | Ultra-low electric flux concrete and preparation method thereof |
| CN114163581A (en) * | 2021-12-28 | 2022-03-11 | 安徽海螺新材料科技有限公司 | Concrete tackifier and preparation method thereof |
| CN114437280A (en) * | 2022-01-25 | 2022-05-06 | 安徽科瑞艾迪新材料科技有限公司 | Cement grinding aid synergist containing disulfide bond polymer and preparation method and application thereof |
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