CN114380955A - Silicon modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof - Google Patents
Silicon modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof Download PDFInfo
- Publication number
- CN114380955A CN114380955A CN202111656902.7A CN202111656902A CN114380955A CN 114380955 A CN114380955 A CN 114380955A CN 202111656902 A CN202111656902 A CN 202111656902A CN 114380955 A CN114380955 A CN 114380955A
- Authority
- CN
- China
- Prior art keywords
- monomer
- polycarboxylic acid
- reinforcing agent
- modified polycarboxylic
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63424—Polyacrylates; Polymethacrylates
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63428—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid anhydride polymers, e.g. maleic anhydride copolymers
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/6344—Copolymers containing at least three different monomers
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a siliceous modified polycarboxylic acid reinforcing agent for refractory materials and a preparation method thereof, which is characterized in that: the polycarboxylic acid is modified with colloidal silica, lithium silicate or a mixture thereof to obtain a polymeric reinforcing agent containing silicon or silica groups, with excess silicon or silica remaining in the system. The siliceous modified polycarboxylic acid reinforcing agent has good dispersibility, improves the fluidity of the additive in the unshaped refractory material, can improve the mechanical strength of the unshaped refractory material and inhibit the strength reduction of the unshaped refractory material at high temperature.
Description
Technical Field
The invention relates to a refractory material additive, in particular to a reinforcing agent for a refractory material and a preparation method thereof, and especially relates to a siliceous modified polycarboxylic acid reinforcing agent and a preparation method thereof.
Background
Unshaped refractory materials using high alumina cement as a cementing material have wide application in industrial construction. Compared with the sintered refractory material, the unshaped refractory material has the advantages of energy conservation, good integrity, flexible adjustment and composition, high production efficiency, good comprehensive use effect and the like, thereby being developed very rapidly. In the construction and use process, the unshaped refractory material, particularly the refractory castable and the pumping material, is required to have good fluidity and the water consumption is as low as possible, thereby improving the strength of the refractory material. Along with the service time of the high-alumina cement-based refractory material, the high-alumina cement has the tendency of crystal form conversion at high temperature, and the strength of the material subjected to the crystal form conversion is obviously reduced.
In the field of refractory materials, high-alumina cement is mainly used as a bonding agent in unshaped refractory castable to prepare rapid-hardening and high-strength mortar or concrete, shrinkage-free or micro-expansion-free dry-mixed mortar or concrete and sulfate corrosion-resistant mortar or concrete. The main driving force for the development of the existing unshaped refractory material is the superfine powder technology and the water reducing agent, and the superfine powder needs to be uniformly dispersed by the water reducing agent with good dispersion property, so that the water reducing agent plays a vital role in the development of the unshaped refractory material.
The polycarboxylic acid has surface activity in high-alumina cement, and can improve the compactness of the refractory material, thereby improving the mechanical strength of the refractory material. The Chinese invention patent CN103922764A discloses a bonding agent for unshaped refractory material, which comprises the following components in percentage by mass: 30-70% of aluminum oxide, 20-60% of magnesium oxide and 5-20% of an activator, wherein the activator is a mixture of metasilicic acid, polycarboxylic acid and simple substance silicon, the mass fraction of the metasilicic acid in the activator mixture is 40-80%, the mass fraction of the polycarboxylic acid in the activator mixture is 0-40%, and the mass fraction of the simple substance silicon in the activator mixture is 0-50%. The bonding agent is used in aluminate cement-based refractory materials, so that the alumina and the magnesia are controllably and rapidly condensed in aqueous solution to generate bonding strength.
However, the dispersibility and the fluidity of the binding agent in the amorphous refractory material still need to be improved, and meanwhile, although the mixed simple substance silicon has a certain inhibiting effect on the crystal transformation of the high-alumina cement at high temperature, the problems of dispersibility and the like also exist in the simple substance mode mixing.
Disclosure of Invention
The invention aims to provide a siliceous modified polycarboxylic acid reinforcing agent for refractory materials, which is used for improving the dispersibility and the mechanical strength of an amorphous high-alumina cement-based refractory material and inhibiting the strength reduction of high-alumina cement at high temperature.
Another object of the present invention is to provide a method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory materials.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the main component of the siliceous modified polycarboxylic acid reinforcing agent for the refractory materials is a siliceous modified polycarboxylic acid polymer which has the following structural general formula:
in the formula: m1One or more selected from hydrogen ions, monovalent metal ions and divalent metal ions;
M2one or more selected from hydrogen ions, monovalent metal ions and divalent metal ions;
R1is H or-CH3
R2is-CH3or-C2H5
R3Is H or-CH3
R4is-H2or-COOM1
R5is-C2H5or-C3H7
R6Is H or-CH3
R7Is CONHC (CH)3)2CH2
R8 is H or-CH3
R9 is C2H5O or C3H7O
a is a positive integer, b, c, d, e, n1、n2The molecular weight of the polymer is 5000-20000.
In the technical scheme, the molecule of the siliceous modified polycarboxylic acid polymer contains silicon or silicon oxide groups, and excessive silicon or silicon oxide remains in the reinforcing agent system. The polymer molecules have a comb-like structure.
In order to achieve another object of the present invention, there is provided a method for preparing a siliceous modified polycarboxylic acid reinforcing agent for refractory materials, comprising the steps of:
(1) respectively dissolving a monomer B, C, D containing unsaturated double bonds and a macromolecular active monomer A with carboxyl or anhydride groups, sulfonic groups and ester groups in deionized water, stirring for dissolving, adding an oxidant, dropwise adding an aqueous solution of a molecular weight regulator and a reducing agent, dropwise adding an aqueous solution of a silane monomer E containing alkenyl, carrying out free radical copolymerization at 10-90 ℃, keeping the temperature for half an hour after the dropwise addition is finished, adjusting the pH value to 7.5-9.5 after the constant temperature is finished, dropwise adding a monomer F while stirring, continuously keeping the temperature constant after the dropwise addition is finished within 30 minutes-3 hours, and keeping the system temperature below 40 ℃ after the reaction is finished to prepare a siliceous modified polycarboxylic acid reinforcing agent mother liquor;
wherein the monomer A is selected from isopentenol polyoxyethylene ether (TPEG 2400), isobutenol polyoxyethylene ether (HPEG 2400) and six-carbon polyether (GPEG 3000);
the monomer F is colloidal silicon dioxide, lithium silicate or a mixture thereof;
(2) and (2) carrying out spray drying on the siliceous modified polycarboxylic acid reinforcing agent mother liquor obtained in the step (1) to obtain the siliceous modified polycarboxylic acid reinforcing agent for the refractory material.
In the above technical scheme, sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia or organic amine and their aqueous solutions can be selected for adjusting the pH value.
In the technical scheme, the molar ratio of the monomer A, B, C, D, E is 1 to (1-5.5) to (0.1-0.5) to (1-3) to (0.01-0.03), and the mass of the monomer F is 10-20% of that of the monomer A.
According to a preferred technical scheme, the monomer B is selected from acrylic acid, methacrylic acid, itaconic acid, citric acid and maleic anhydride.
In a preferred technical scheme, the monomer C is selected from sodium allyl sulfonate, sodium methallyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid.
According to a preferred technical scheme, the monomer D is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and itaconic acid glyceride.
In a preferred embodiment, the monomer E is selected from vinyltrimethoxysilane, vinyltriethoxysilane, propenyltrimethoxysilane, propenyltriethoxysilane, silica sol or a mixture thereof.
According to the preferable technical scheme, the monomer F is a mixture of colloidal silica and lithium silicate, and the mass ratio of the colloidal silica to the lithium silicate is = 8-9: 2-1.
In the technical scheme, the molecular weight regulator is selected from thioglycolic acid, mercaptopropionic acid, mercaptoethanol, sodium bisulfite and sodium methallyl sulfonate, and the molecular weight regulator accounts for 0.1-0.5 percent of the mass of the monomer A; the oxidant is ammonium persulfate, potassium persulfate, sodium persulfate or a mixture thereof, and the oxidant accounts for 0.3-0.8% of the mass of the monomer A; the reducing agent is vitamin C, sodium bisulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate or a mixture thereof, and the reducing agent accounts for 0.05-0.2% of the mass of the monomer A.
The reinforcing agent of the present invention can be used in refractory materials together with known dispersants, retarders, air-entraining agents, early strength agents, defoamers.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. compared with the prior art, the silicon modified polycarboxylic acid reinforcing agent has the advantages that the silane group is introduced into the side chain of the silicon modified polycarboxylic acid reinforcing agent, the steric hindrance effect is achieved, the molecular weight of the additive is controlled by the molecular weight regulator, the polymer with proper molecular weight and uniform molecular weight distribution is obtained, the silicon modified polycarboxylic acid reinforcing agent is more suitable for unshaped refractory materials, and the dispersibility is better.
2. The siliceous modified polycarboxylic acid reinforcing agent synthesized by the invention improves the fluidity of the additive in unshaped refractory materials.
3. The invention utilizes silicon or silicon-oxygen polymer to carry out physical and chemical modification on the high molecular polymer, improves the high-temperature performance of the unshaped refractory material and improves the high-temperature strength.
Detailed Description
The invention is further described below with reference to the following examples:
example 1:
weighing 230g (0.1mol) of isoamylene polyoxyethylene ether, 24.5g (0.5 mol) of maleic anhydride, 1.58g (0.01 mol) of sodium methallyl sulfonate, 23.2g (0.2 mol) of hydroxyethyl acrylate and 230g of deionized water, stirring and dissolving the mixture in a four-neck flask, dropwise adding 1.38g of sodium persulfate as an oxidant, 0.296g (0.002 mol) of vinyltrimethoxysilane and 50g of deionized water solution into a reactor, simultaneously dropwise adding 0.92g of thioglycolic acid and 20g of deionized water solution into the reactor, controlling the temperature to be between 75 and 80 ℃, completing dropwise adding within 3 hours, keeping the temperature for half an hour, regulating the pH to be 8.5 by using sodium hydroxide, dropwise adding 61.3g of colloidal silica with the concentration of 30 percent and 4.6g of lithium silicate mixture (the mass ratio of the silica to the lithium silicate is 8: 2) while stirring, continuing to cool to below 40 ℃ for half an hour, the sample solution was spray dried at high temperature to give a dark yellow powder.
The main composition of the amorphous silica-free refractory tested for net slurry fluidity is shown in the following table.
| Material | Dosage per gram |
| Micro powder (corundum, alumina) | 115 |
| High alumina cement | 17 |
| Water (W) | 25 |
| Siliceous modified polycarboxylic acid reinforcing agent | 0.36 |
Example 2:
230g (0.1mol) of isobutylene polyoxyethylene ether, 34.4g (0.4 mol) of methacrylic acid, 2.88g (0.02 mol) of sodium allylsulfonate, 19.5g (0.15 mol) of hydroxypropyl acrylate and 230g of deionized water are weighed into a four-neck flask and stirred to be dissolved, 1.15g of ammonium persulfate as an oxidant, 0.285g (0.002 mol) of vinyl triethoxysilane and 50g of deionized water solution are added dropwise into a reactor, simultaneously dripping 0.46g of mercaptopropionic acid, 0.184g of vitamin C and 20g of deionized water solution into the reactor, controlling the temperature between 50 and 55 ℃, finishing the dripping within 2.5 hours, keeping the temperature for half an hour, adjusting pH to 8 with calcium hydroxide, dropwise adding 61.3g of a mixture of 30% colloidal silica and 4.6g of lithium silicate (mass ratio of silica to lithium silicate is 8: 2) while stirring, keeping constant temperature for half an hour after dropwise adding, and cooling to below 40 deg.C. The sample solution was spray dried at high temperature to give a pale yellow powder.
Example 3:
weighing 300g (0.1mol) of novel water reducing agent polyether monomer (GPEG), 25.2g (0.35 mol) of acrylic acid, 3.1g (0.015 mol) of 2-acrylamide-2-methylpropanesulfonic acid, 13g (0.10 mol) of hydroxyethyl methacrylate and 230g of deionized water into a four-neck flask, stirring and dissolving, dropwise adding 4.8g of oxydol with the concentration of 50% and 0.486g (0.003 mol) of propenyl trimethoxy silane and 50g of deionized water into a reactor, simultaneously dropwise adding 0.9g of mercaptopropionic acid, 0.3g of sodium formaldehyde sulfoxylate and 20g of deionized water into the reactor, controlling the temperature to be between 35 and 40 ℃, completing dropwise adding within 1.5 hours, keeping the temperature for half an hour, regulating the pH to 8.5 by using organic amine, dropwise adding 80g of a mixture of 30% colloidal silicon dioxide and 6g of lithium silicate (the mass ratio of silicon dioxide to lithium silicate is 8: 2) while stirring, and after half an hour of dropwise addition, keeping the temperature for half an hour, and performing high-temperature spray drying on the sample solution to obtain light yellow powder.
Example 4:
weighing 150g (0.05mol) of novel water reducing agent polyether monomer (GPEG), 115g (0.05mol) of isobutylene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methylpropanesulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water, stirring and dissolving the components in a four-neck flask, dropwise adding 0.93g of ammonium persulfate, 1.86g of 50% concentration hydrogen peroxide, 0.204g (0.003 mol) of allyl triethoxysilane and 50g of deionized water solution into a reactor, dropwise adding 0.66g of mercaptoethanol, 0.3g of sodium formaldehyde sulfoxylate, 0.3g of sodium thiosulfate and 20g of deionized water solution into the reactor, naturally heating, completing dropwise adding within 2 hours, keeping the temperature for half an hour, adjusting the pH to 7.5 by using potassium hydroxide, dropwise adding 61.3g of a mixture of 30% colloidal silica and 4.6g of lithium silicate (the mass ratio of silica: 2) while stirring, and after half an hour of dropwise addition, keeping the temperature for half an hour, and performing high-temperature spray drying on the sample solution to obtain light yellow powder.
Comparative example 1:
weighing 230g (0.1mol) of isoamylene polyoxyethylene ether, 24.5g (0.5 mol) of maleic anhydride, 1.58g (0.01 mol) of sodium methallyl sulfonate, 23.2g (0.2 mol) of hydroxyethyl acrylate and 230g of deionized water, stirring and dissolving the mixture in a four-neck flask, dropwise adding 1.38g of sodium persulfate as an oxidant, 0.296g (0.002 mol) of vinyltrimethoxysilane and 50g of deionized water solution into a reactor, simultaneously dropwise adding 0.92g of thioglycolic acid and 20g of deionized water solution into the reactor, controlling the temperature to be between 75 and 80 ℃, completing dropwise adding within 3 hours, keeping the temperature for half an hour, adjusting the pH to be 8.5 by using sodium hydroxide, cooling to be below 40 ℃, and carrying out high-temperature spray drying on the sample solution to obtain dark yellow powder.
Comparative example 2:
weighing 230g (0.1mol) of isobutylene polyoxyethylene ether, 34.4g (0.4 mol) of methacrylic acid, 2.88g (0.02 mol) of sodium allylsulfonate, 19.5g (0.15 mol) of hydroxypropyl acrylate and 230g of deionized water into a four-neck flask, stirring and dissolving, dropwise adding 1.15g of ammonium persulfate oxidant, 0.285g (0.002 mol) of vinyltriethoxysilane and 50g of deionized water solution into a reactor, simultaneously dropwise adding 0.46g of mercaptopropionic acid, 0.184g of vitamin C and 20g of deionized water solution into the reactor, controlling the temperature to be between 50 and 55 ℃, completing dropwise adding within 2.5 hours, keeping the temperature for half an hour, adjusting the pH to be 8 by using calcium hydroxide, and cooling to be below 40 ℃. The sample solution was spray dried at high temperature to give a pale yellow powder.
Comparative example 3:
weighing 300g (0.1mol) of novel water reducing agent polyether monomer (GPEG), 25.2g (0.35 mol) of acrylic acid, 3.1g (0.015 mol) of 2-acrylamide-2-methylpropanesulfonic acid, 13g (0.10 mol) of hydroxyethyl methacrylate and 230g of deionized water into a four-neck flask, stirring and dissolving, dropwise adding 4.8g of oxydol with the concentration of 50% and 0.486g (0.003 mol) of propenyl trimethoxy silane and 50g of deionized water solution into a reactor, simultaneously dropwise adding 0.9g of mercaptopropionic acid, 0.3g of sodium formaldehyde sulfoxylate and 20g of deionized water solution into the reactor, controlling the temperature to be between 35 and 40 ℃, completing dropwise adding within 1.5 hours, keeping the temperature for half an hour, regulating the pH to 8.5 by using organic amine, and carrying out high-temperature spray drying on a sample solution to obtain pale yellow powder.
Comparative example 4:
weighing 150g (0.05mol) of novel water reducing agent polyether monomer (GPEG), 115g (0.05mol) of isobutylene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methylpropanesulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water, stirring and dissolving the mixture in a four-neck flask, dropwise adding 0.93g of ammonium persulfate, 1.86g of 50% concentration hydrogen peroxide, 0.204g (0.003 mol) of allyl triethoxysilane and 50g of deionized water solution into a reactor, dropwise adding 0.66g of mercaptoethanol, 0.3g of sodium formaldehyde sulfoxylate, 0.3g of sodium thiosulfate and 20g of deionized water solution into the reactor, naturally heating, completing dropwise adding within 2 hours, keeping the temperature for half an hour, adjusting the pH to 7.5 by using potassium hydroxide, and carrying out high-temperature spray drying on the sample solution to obtain light yellow powder.
Comparative example 5:
weighing 150g (0.05mol) of novel water reducing agent polyether monomer (GPEG), 115g (0.05mol) of isobutylene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methylpropanesulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water, stirring and dissolving the mixture in a four-neck flask, dropwise adding 0.93g of ammonium persulfate, 1.86g of 50% concentration hydrogen peroxide, 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water solution into a reactor, dropwise adding 0.66g of mercaptoethanol, 0.3g of sodium formaldehyde sulfoxylate, 0.3g of sodium thiosulfate and 20g of deionized water solution into the reactor, naturally heating, completing dropwise adding within 2 hours, keeping the temperature for half an hour, adjusting the pH to 7.5 by using potassium hydroxide, dropwise adding 88.3g of 30% concentration colloidal silica solution while stirring, finishing dropwise adding, continuing to dry the mixture at the constant temperature for half an hour, and spraying the sample at high temperature, a pale yellow powder was obtained.
Comparative example 6:
weighing 150g (0.05mol) of novel water reducing agent polyether monomer (GPEG), 115g (0.05mol) of isobutylene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methylpropanesulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water, stirring and dissolving the mixture in a four-neck flask, dropwise adding 0.93g of ammonium persulfate, 1.86g of 50% concentration hydrogen peroxide, 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water solution into a reactor, dropwise adding 0.66g of mercaptoethanol, 0.3g of sodium formaldehyde sulfoxylate, 0.3g of sodium thiosulfate and 20g of deionized water solution into the reactor, naturally heating, finishing dropwise adding within 2 hours, keeping the temperature for half an hour, regulating the pH to 7.5 by using potassium hydroxide, dropwise adding 26.5g of lithium silicate solution while stirring, continuing to keep the dropwise adding for half an hour, and drying the sample solution by high-temperature spray, a pale yellow powder was obtained.
Comparative example 7:
weighing 150g (0.05mol) of novel water reducing agent polyether monomer (GPEG), 115g (0.05mol) of isobutylene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methylpropanesulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water, stirring and dissolving the materials in a four-neck flask, dropwise adding 0.93g of ammonium persulfate, 1.86g of 50% concentration hydrogen peroxide, 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water solution into a reactor, dropwise adding 0.66g of mercaptoethanol, 0.3g of sodium formaldehyde sulfoxylate, 0.3g of sodium thiosulfate and 20g of deionized water solution into the reactor, naturally heating, completing dropwise adding within 2 hours, keeping the temperature for half an hour, and adding potassium silicate into the obtained product in an ultrasonic dispersion state to enable the pH of the system to be 10. The sample solution was spray dried at high temperature to give a pale yellow powder.
The unshaped refractory composition in example 1 was compounded, and the net slurry fluidity of the refractory fine powder system and the compressive strength after firing at 1400 ℃ for 5 hours were measured. The results are shown in the following table:
as shown in the table, the addition of the mixture of silica and lithium silicate in examples 1 to 4 did not change the net slurry fluidity much compared to comparative examples 1 to 4, but the addition of the mixture of silica and lithium silicate significantly improved the high temperature strength of the refractory, while the addition of comparative examples 5 to 7, which added a single colloidal silica or lithium silicate and potassium silicate in the formulation of comparative example 4, improved the high temperature strength compared to comparative example 4, but still did not exceed the high temperature strength of example 4.
Claims (10)
1. A siliceous modified polycarboxylic acid reinforcing agent for refractory materials, characterized in that the main component is a siliceous modified polycarboxylic acid polymer having the following general structural formula:
in the formula: m1One or more selected from hydrogen ions, monovalent metal ions and divalent metal ions;
M2one or more selected from hydrogen ions, monovalent metal ions and divalent metal ions;
R1is H or-CH3
R2is-CH3or-C2H5
R3Is H or-CH3
R4is-H2or-COOM1
R5is-C2H5or-C3H7
R6Is H or-CH3
R7Is CONHC (CH)3)2CH2
R8 is H or-CH3
R9 is C2H5O or C3H7O
a is a positive integer, b, c, d, e, n1、n2The molecular weight of the polymer is 5000-20000.
2. The siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the silicon modified polycarboxylic acid polymer contains silicon or silicon oxide groups in the molecule, and excessive silicon or silicon oxide is remained in the reinforcing agent system.
3. A process for producing a siliceous modified polycarboxylic acid reinforcing agent for refractories according to claim 1, comprising the steps of:
(1) respectively dissolving a monomer B, C, D containing unsaturated double bonds and a macromolecular active monomer A with carboxyl or anhydride groups, sulfonic groups and ester groups in deionized water, stirring for dissolving, adding an oxidant, dropwise adding an aqueous solution of a molecular weight regulator and a reducing agent, dropwise adding an aqueous solution of a silane monomer E containing alkenyl, carrying out free radical copolymerization at 10-90 ℃, keeping the temperature for half an hour after the dropwise addition is finished, adjusting the pH value to 7.5-9.5 after the constant temperature is finished, dropwise adding a monomer F while stirring, continuously keeping the temperature constant after the dropwise addition is finished within 30 minutes-3 hours, and keeping the system temperature below 40 ℃ after the reaction is finished to prepare a siliceous modified polycarboxylic acid reinforcing agent mother liquor;
wherein the monomer A is selected from isoamylol polyoxyethylene ether, isobutenol polyoxyethylene ether and six-carbon polyether;
the monomer F is colloidal silicon dioxide, lithium silicate or a mixture thereof;
(2) and (2) carrying out spray drying on the siliceous modified polycarboxylic acid reinforcing agent mother liquor obtained in the step (1) to obtain the siliceous modified polycarboxylic acid reinforcing agent for the refractory material.
4. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 3, wherein: the molar ratio of the monomer A, B, C, D, E is 1 to (1-5.5) to (0.1-0.5) to (1-3) to (0.01-0.03), and the mass of the monomer F is 10-20% of that of the monomer A.
5. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 3, wherein: the monomer B is selected from acrylic acid, methacrylic acid, itaconic acid, citric acid and maleic anhydride.
6. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 3, wherein: the monomer C is selected from sodium allyl sulfonate, sodium methallyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid.
7. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 3, wherein: the monomer D is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and itaconic acid glyceride.
8. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 3, wherein: the monomer E is selected from vinyl trimethoxy silane, vinyl triethoxy silane, propenyl trimethoxy silane, propenyl triethoxy silane, silica sol or a mixture thereof.
9. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 3, wherein: the monomer F is a mixture of colloidal silicon dioxide and lithium silicate, and the mass ratio of the colloidal silicon dioxide to the lithium silicate is = 8-9: 2-1.
10. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 3, wherein: the molecular weight regulator is selected from thioglycolic acid, mercaptopropionic acid, mercaptoethanol, sodium bisulfite and sodium methallyl sulfonate, and the molecular weight regulator accounts for 0.1 to 0.5 percent of the mass of the monomer A; the oxidant is ammonium persulfate, potassium persulfate, sodium persulfate or a mixture thereof, and the oxidant accounts for 0.3-0.8% of the mass of the monomer A; the reducing agent is vitamin C, sodium bisulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate or a mixture thereof, and the reducing agent accounts for 0.05-0.2% of the mass of the monomer A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111656902.7A CN114380955B (en) | 2021-12-31 | 2021-12-31 | Siliceous modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111656902.7A CN114380955B (en) | 2021-12-31 | 2021-12-31 | Siliceous modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114380955A true CN114380955A (en) | 2022-04-22 |
| CN114380955B CN114380955B (en) | 2023-08-22 |
Family
ID=81199050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111656902.7A Active CN114380955B (en) | 2021-12-31 | 2021-12-31 | Siliceous modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114380955B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475659A (en) * | 2009-01-08 | 2009-07-08 | 同济大学 | Preparation of special plasticizer for unshaped refractory containing silica fume |
| CN102037023A (en) * | 2008-05-21 | 2011-04-27 | 巴斯夫欧洲公司 | Graft copolymer, method for the production thereof, and use thereof |
| US20120142844A1 (en) * | 2010-11-26 | 2012-06-07 | Wacker Chemie Ag | Aqueous hybrid binder for jointing mortars |
| CN103011680A (en) * | 2012-12-13 | 2013-04-03 | 中国矿业大学(北京) | Sulfate-resistant organosilicone modified polycarboxylic superplasticizer and preparation method thereof |
| CN104725573A (en) * | 2014-10-11 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Superplasticizer for facilitating cement hydration, preparation method thereof and application |
| CN105384379A (en) * | 2015-12-10 | 2016-03-09 | 西安建筑科技大学 | White carbon black modified polycarboxylic acid water reducer and preparation method thereof |
| CN108129611A (en) * | 2017-12-26 | 2018-06-08 | 中科院广州化学有限公司 | A kind of organic-silicon-modified polycarboxylate water-reducer and preparation method thereof |
| CN108373523A (en) * | 2018-02-12 | 2018-08-07 | 中交二航武汉港湾新材料有限公司 | Polycarboxylate water-reducer of organic inorganic hybridization and preparation method thereof |
| CN111808244A (en) * | 2020-08-21 | 2020-10-23 | 湖南加美乐素新材料股份有限公司 | Polycarboxylate superplasticizer with high water reduction and high adaptability and preparation method thereof |
-
2021
- 2021-12-31 CN CN202111656902.7A patent/CN114380955B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037023A (en) * | 2008-05-21 | 2011-04-27 | 巴斯夫欧洲公司 | Graft copolymer, method for the production thereof, and use thereof |
| CN101475659A (en) * | 2009-01-08 | 2009-07-08 | 同济大学 | Preparation of special plasticizer for unshaped refractory containing silica fume |
| US20120142844A1 (en) * | 2010-11-26 | 2012-06-07 | Wacker Chemie Ag | Aqueous hybrid binder for jointing mortars |
| CN102584106A (en) * | 2010-11-26 | 2012-07-18 | 瓦克化学股份公司 | Aqueous hybrid binder for jointing mortars |
| CN103011680A (en) * | 2012-12-13 | 2013-04-03 | 中国矿业大学(北京) | Sulfate-resistant organosilicone modified polycarboxylic superplasticizer and preparation method thereof |
| CN104725573A (en) * | 2014-10-11 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Superplasticizer for facilitating cement hydration, preparation method thereof and application |
| CN105384379A (en) * | 2015-12-10 | 2016-03-09 | 西安建筑科技大学 | White carbon black modified polycarboxylic acid water reducer and preparation method thereof |
| CN108129611A (en) * | 2017-12-26 | 2018-06-08 | 中科院广州化学有限公司 | A kind of organic-silicon-modified polycarboxylate water-reducer and preparation method thereof |
| CN108373523A (en) * | 2018-02-12 | 2018-08-07 | 中交二航武汉港湾新材料有限公司 | Polycarboxylate water-reducer of organic inorganic hybridization and preparation method thereof |
| CN111808244A (en) * | 2020-08-21 | 2020-10-23 | 湖南加美乐素新材料股份有限公司 | Polycarboxylate superplasticizer with high water reduction and high adaptability and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHIYANG BAI: "Preparation and pH-responsive performance of silane-modified poly(methylacrylic acid)", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 131, no. 12, pages 40403 * |
| 任春蓉;侯莉;李军;卢忠远;牛云辉;: "纳米二氧化硅改性聚羧酸减水剂及其对水泥净浆流变性能的影响", 西南科技大学学报, no. 02, pages 72 - 78 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114380955B (en) | 2023-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109400821B (en) | Concrete bleeding-resistant inhibitor with water reducing function and preparation method thereof | |
| CN105837763B (en) | Silane polycarboxylic acid water reducing agent and preparation method thereof | |
| CN109575198B (en) | Enhanced polycarboxylate superplasticizer and preparation method thereof | |
| CN108948288B (en) | Preparation method of crosslinking type polycarboxylate superplasticizer by adopting carboxyl functional monomer | |
| CN105924592B (en) | Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| WO2003031365A1 (en) | Superplasticizer for concrete and self-leveling compounds | |
| CN110746136B (en) | Shrinkage-reducing thickening type alkali-free liquid accelerator and preparation method and application thereof | |
| CN102765899B (en) | Low air leading reducing type polycarboxylic acid concrete water reducer and preparation method thereof | |
| CN111548459A (en) | Preparation method of high slump loss resistant polycarboxylate superplasticizer | |
| CN111100253A (en) | Concrete anti-sensitive polycarboxylate superplasticizer and preparation method thereof | |
| CN112745464A (en) | Phosphate-containing high-adaptability early-strength polycarboxylate superplasticizer and preparation method and application thereof | |
| CN113929837B (en) | Shrinkage-reducing polycarboxylic acid water reducing agent, and preparation method and application thereof | |
| CN114656600A (en) | Preparation method of high-solid-content early-strength polycarboxylate superplasticizer | |
| CN113444210B (en) | Low-sensitivity water-reducing slump-retaining polycarboxylic acid water reducer and preparation method thereof | |
| CN114671982A (en) | Shrinkage-reducing polycarboxylic acid water reducing agent and preparation method thereof | |
| CN108192010B (en) | Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof | |
| CN112979214B (en) | Polyether water-retaining agent, preparation method thereof and cement-based building material | |
| CN110627972A (en) | Novel mud-resistant polyether polycarboxylic acid water reducer and normal-temperature synthesis process thereof | |
| CN114230726A (en) | Polycarboxylate superplasticizer with strong adsorption and fast dispersion and preparation method thereof | |
| CN117126346A (en) | Nuclear early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN109734847B (en) | Viscosity reduction type polycarboxylate superplasticizer containing three viscosity reduction functional groups, and preparation method and application thereof | |
| CN114380955B (en) | Siliceous modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof | |
| CN110668758A (en) | Grouting material for connecting reinforcing steel bar sleeve | |
| CN114478939B (en) | Slow-release polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |