CN112390927A - Retarder for refractory material - Google Patents
Retarder for refractory material Download PDFInfo
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- CN112390927A CN112390927A CN202011189984.4A CN202011189984A CN112390927A CN 112390927 A CN112390927 A CN 112390927A CN 202011189984 A CN202011189984 A CN 202011189984A CN 112390927 A CN112390927 A CN 112390927A
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- Prior art keywords
- retarder
- diisocyanate
- refractory materials
- silsesquioxane
- refractory
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- 239000011819 refractory material Substances 0.000 title claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 10
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000000269 nucleophilic effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940049964 oleate Drugs 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000562 Poly(ethylene adipate) Polymers 0.000 claims description 2
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 claims description 2
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 claims description 2
- GPCIDUIBGGUBJG-UHFFFAOYSA-N hexanedioic acid;hexane-1,1-diol Chemical compound CCCCCC(O)O.OC(=O)CCCCC(O)=O GPCIDUIBGGUBJG-UHFFFAOYSA-N 0.000 claims description 2
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 10
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000002028 premature Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 description 10
- 239000004568 cement Substances 0.000 description 9
- 230000036571 hydration Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- -1 polytrimethylene adipate Polymers 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- 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
-
- 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
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a retarder used in refractory materials, which is prepared by the following steps: weighing polyester polyol, silsesquioxane and diisocyanate according to a ratio, adding the polyester polyol, the silsesquioxane and a solvent N-methylpyrrolidone into a reaction vessel, fully stirring, heating, then adding the diisocyanate, adding a catalyst, keeping the temperature and continuously stirring after adding, and then heating and keeping the temperature to prepare a prepolymer with an end group of-NCO; and (3) after cooling, adding sodium bisulfite into the reaction vessel, continuously stirring and preserving heat, finally adding water into the reaction vessel, and continuously stirring to obtain the retarder for the refractory material. The retarder can adjust the setting time of the refractory castable, avoids the premature setting of the castable, has good operability, and can reduce the construction energy consumption to a greater extent. Meanwhile, the refractory castable can be used as a dispersant to improve the fluidity and reduce the consistency of the refractory castable.
Description
Technical Field
The invention provides a retarder, particularly relates to an additive for adjusting the setting time of a refractory castable in a refractory material and preventing the castable from being prematurely set, and belongs to the technical field of refractory material additives.
Background
In general, refractory castable materials containing high fine silica powder are relatively difficult to disperse, mainly because of the following reasons: the silicon oxide micro powder has very fine granularity, shows very high specific surface area and is very easy to agglomerate; the chemical composition is unstable and the content of basic oxide impurities, such as sodium oxide, potassium oxide, etc., is usually high. The presence of higher surface area and higher alkaline impurities can easily lead to shorter construction time (initial setting time) of the castable, and particularly, the castable is more prominent in summer or under higher construction temperature conditions, thereby leading to frequent construction problems of the castable containing higher silica fume systems.
The Set Retarder is an additive for reducing the hydration speed and the hydration heat of cement or gypsum and prolonging the setting time. The retarder is added into commercial concrete for prolonging the hydration hardening time of cement, so that the fresh concrete can keep plasticity for a long time, thereby adjusting the setting time of the fresh concrete. The traditional retarder used in the refractory castable often causes that the construction time of the castable is not enough at a high temperature, so that the construction fails. Finally, the high-temperature performance of the castable containing silica fume is damaged to different degrees, so that the retarder with better performance needs to be provided in the field.
Disclosure of Invention
The retarder can adjust the setting time of the refractory castable, avoid the premature setting of the castable, has good operability and can reduce the construction energy consumption to a greater extent. Meanwhile, the refractory castable can be used as a dispersant to improve the fluidity and reduce the consistency of the refractory castable.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
a retarder for use in a refractory material, the retarder being prepared by:
(1) weighing polyester polyol, silsesquioxane and diisocyanate according to the molar ratio of (1.5-2.5) to (3-5) to 1, adding the polyester polyol, the silsesquioxane and a solvent N-methylpyrrolidone into a reaction container, fully stirring, heating to 45-55 ℃, then adding the diisocyanate, then adding a catalyst accounting for 2-5% of the total mass of reactants, keeping the temperature and continuously stirring after adding, heating to 65-75 ℃, and keeping the temperature to prepare a prepolymer with an end group of-NCO;
(2) and cooling to 45-55 ℃, then adding sodium bisulfite into the reaction vessel, wherein the molar ratio of the added sodium bisulfite to the terminal-NCO group in the prepolymer is (1.5-2.5): 1, continuing stirring and preserving heat, finally adding water into the reaction vessel, and continuing stirring to obtain the retarder for the refractory material.
The polyester polyol is one or a mixture of more than two of neopentyl glycol adipate, ethylene glycol adipate, propylene glycol adipate, butanediol adipate and hexanediol adipate, and the molecular weight of the polyester polyol is 1000-3000.
The silsesquioxane particles are a mixture of cage type silsesquioxane with a vinyl content of 0.15-0.2% and trapezoid type silsesquioxane with a vinyl content of 0.15-0.2% in a mass ratio of 2: 1.
The diisocyanate is any one or a mixture of any two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate.
The catalyst is an organic metal salt catalyst or a nucleophilic tertiary amine catalyst.
The organic metal salt catalyst is more than one of dibutyltin dilaurate, stannous octoate and stannous oleate.
The nucleophilic tertiary amine catalyst is more than one of triethylamine, triethylene diamine and N-methylmorpholine.
The retarder for the refractory material provided by the application has the following action principle: the molecular structure of the complex contains complex forming groups such as-OH, -COOH and SO3-Etc. Ca2+Is a divalent positive ion with a coordination number of 4, is a weak bond, and can form an unstable complex in an alkaline environment. Hydroxyl radicals with free Ca in alkaline medium of cement hydration products2+Forming unstable complex, and controlling Ca in liquid phase at early stage of hydration2+The concentration of (b) produces a retarding effect. As the hydration process proceeds, the unstable complex compound will decompose automatically, and the hydration will continue to proceed normally without affecting the later hydration of cement. And secondly, the hydroxyl and the carboxyl are easy to associate with water molecules through hydrogen bonds, and the hydrogen bonds between the water molecules are associated, so that a stable water solvating film is formed on the surface of the cement particles, the direct contact between the cement particles is prevented, and the hydration is hindered. Ca which is easily liberated from compounds having carboxyl groups or carboxylate groups2+Insoluble calcium salt is generated and precipitated on the surface of cement particles, thereby retarding the hydration speed of cement.
This application has introduced the side chain in molecular structure, and the primary action provides the steric hindrance effect, and when the cement granule that has polyurethane retarder macromolecule to adsorb is close to, the side chain of polyurethane is longer more, and the macromolecule adsorbed layer is just thicker, and the steric hindrance is big more, and the system tends to stability more, and the dispersibility is also better. And silsesquioxane is introduced, so that the dispersion retention is good due to weak steric hindrance effect of the section. The system formed by the synthetic product after the silsesquioxane is added is stable, is not greatly influenced by external factors, and the storage time is correspondingly prolonged.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the scope of the present invention is not limited to the examples.
Example 1:
10g (0.01mol) of neopentyl glycol polyadipate adipate (molecular weight: 1000), 10mL of N-methylpyrrolidone and 2.54g (0.005mol) of methylsilsesquioxane were weighed into a three-necked flask equipped with a reflux condenser. Stirring at a constant speed by using a stirrer, and heating to 50 ℃; after the temperature of the solution in the reaction vessel had reached 50 ℃ 4.45g (0.02mol) of isophorone diisocyanate were added. Then adding a catalyst dibutyltin dilaurate (the dosage accounts for 2 percent of the total mass of the reaction system), preserving the heat for 1 hour after the addition is finished, then heating to 70 ℃, and preserving the heat for 4 hours. Adding 1.04g (0.01mol) of sodium bisulfite, stirring intensively, continuing to stir for 1h, adding water into the reaction kettle, and stirring for 30min to obtain the retarder used in the refractory material, which is named as HN-1.
Example 2:
15g (0.01mol) of polytrimethylene adipate (molecular weight: 1500), 15mL of N-methylpyrrolidone, and 2.54g (0.005mol) of methylsilsesquioxane were weighed and charged into a three-necked flask equipped with a reflux condenser. Stirring at a constant speed by using a stirrer, and heating to 50 ℃; after the temperature of the solution in the reaction vessel had reached 50 ℃ 3.5g (0.02mol) of toluene diisocyanate were added. Then adding catalyst stannous octoate (the dosage accounts for 3 percent of the total mass of the reaction system), preserving heat for 1 hour after adding, then heating to 70 ℃, and preserving heat for 4 hours. Adding 1.04g of sodium bisulfite, stirring intensively, continuing stirring for 1h, adding water into the reaction kettle, and stirring for 30min to obtain the retarder used in the refractory material, which is named as HN-2.
Example 3:
20g (0.01mol) of polybutylene adipate (molecular weight: 2000), 20mL of N-methylpyrrolidone, and 2.54g (0.005mol) of methylsilsesquioxane were weighed out and charged into a three-necked flask equipped with a reflux condenser. Stirring at a constant speed by using a stirrer, and heating to 50 ℃; after the temperature of the solution in the reaction vessel had reached 50 ℃ 3.4g (0.02mol) of hexamethylene diisocyanate were added. Then adding catalyst stannous oleate (the dosage accounts for 4% of the total mass of the reaction system), preserving heat for 1h after adding, then heating to 70 ℃, and preserving heat for 4 h. Adding 1.04g of sodium bisulfite, stirring intensively, continuing stirring for 1h, adding water into the reaction kettle, and stirring for 30min to obtain the retarder used in the refractory material, which is named as HN-3.
Example 4:
30g (0.01mol) of polyhexamethylene adipate (molecular weight 3000), 30mL of N-methylpyrrolidone and 2.54g (0.005mol) of methylsilsesquioxane were weighed out and charged into a three-necked flask equipped with a reflux condenser. Stirring at a constant speed by using a stirrer, and heating to 50 ℃; after the temperature of the solution in the reaction vessel had reached 50 ℃ 5g (0.02mol) of diphenylmethane diisocyanate were added. And then adding catalyst triethylamine (the dosage accounts for 5 percent of the total mass of the reaction system), preserving heat for 1 hour after adding, then raising the temperature to 70 ℃, and preserving heat for 4 hours. Adding 1.04g of sodium bisulfite, stirring intensively, continuing stirring for 1h, adding water into the reaction kettle, and stirring for 30min to obtain the retarder used in the refractory material, which is named as HN-4.
Example 5
In this embodiment, the retarder prepared in the above examples 1 to 4 is compared with a commercially available conventional retarder through experiments, and specific experimental schemes and test results are shown in the following table:
as can be seen from the above table, when other retarders (control group 1 and control group 2) on the market are used, the castable has higher water addition amount and shorter construction time: under the condition of higher temperature of 35 ℃, the retarder prepared by the invention is used as a castable raw material, the construction time of the castable reaches 100 minutes, the water adding amount is obviously lower than that of other two retarders on the market, and the comprehensive construction performance reaches a good effect.
Example 6
In this example, the retarder prepared in the above example 1 is added to the castable refractory according to different addition amounts for experimental comparison, and the specific experimental scheme and the test result are shown in the following table:
as can be seen from the above table, even when the addition amount of the retarder prepared in example 1 of the present application is reduced to 0.1% in the refractory castable, a good use effect can be achieved. Meanwhile, the retarder purchased from the market is easy to cause the problems of bleeding phenomenon, uneven air hole distribution and the like, the retarder in the embodiment is used for eliminating the bleeding phenomenon, and the air holes in the matrix are uniformly distributed after the casting material is poured and maintained.
Claims (7)
1. A retarder for use in refractory materials, characterized in that the retarder is prepared by the steps of:
(1) weighing polyester polyol, silsesquioxane and diisocyanate according to the molar ratio of (1.5-2.5) to (3-5) to 1, adding the polyester polyol, the silsesquioxane and a solvent N-methylpyrrolidone into a reaction container, fully stirring, heating to 45-55 ℃, then adding the diisocyanate, then adding a catalyst accounting for 2-5% of the total mass of reactants, keeping the temperature and continuously stirring after adding, heating to 65-75 ℃, and keeping the temperature to prepare a prepolymer with an end group of-NCO;
(2) and cooling to 45-55 ℃, then adding sodium bisulfite into the reaction vessel, wherein the molar ratio of the added sodium bisulfite to the terminal-NCO group in the prepolymer is (1.5-2.5): 1, continuing stirring and preserving heat, finally adding water into the reaction vessel, and continuing stirring to obtain the retarder for the refractory material.
2. The set retarder for use in refractory materials according to claim 1, wherein: the polyester polyol is one or a mixture of more than two of neopentyl glycol adipate, ethylene glycol adipate, propylene glycol adipate, butanediol adipate and hexanediol adipate, and the molecular weight of the polyester polyol is 1000-3000.
3. The set retarder for use in refractory materials according to claim 1, wherein: the silsesquioxane particles are a mixture of cage type silsesquioxane with a vinyl content of 0.15-0.2% and trapezoid type silsesquioxane with a vinyl content of 0.15-0.2% in a mass ratio of 2: 1.
4. The set retarder for use in refractory materials according to claim 1, wherein: the diisocyanate is any one or a mixture of any two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate.
5. The set retarder for use in refractory materials according to claim 1, wherein: the catalyst is an organic metal salt catalyst or a nucleophilic tertiary amine catalyst.
6. The retarder for use in refractory materials according to claim 5, wherein: the organic metal salt catalyst is more than one of dibutyltin dilaurate, stannous octoate and stannous oleate.
7. The retarder for use in refractory materials according to claim 5, wherein: the nucleophilic tertiary amine catalyst is more than one of triethylamine, triethylene diamine and N-methylmorpholine.
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