CN109111726B - Composite material and preparation method thereof - Google Patents
Composite material and preparation method thereof Download PDFInfo
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- CN109111726B CN109111726B CN201710480464.0A CN201710480464A CN109111726B CN 109111726 B CN109111726 B CN 109111726B CN 201710480464 A CN201710480464 A CN 201710480464A CN 109111726 B CN109111726 B CN 109111726B
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 36
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 31
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 31
- 239000012670 alkaline solution Substances 0.000 claims abstract description 18
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 239000010881 fly ash Substances 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 229920005906 polyester polyol Polymers 0.000 claims description 7
- -1 polymethylene Polymers 0.000 claims description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 239000004111 Potassium silicate Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 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
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 claims description 2
- 239000003818 cinder Substances 0.000 claims 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 claims 1
- 229940066675 ricinoleate Drugs 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- ZAJHMOZTXOGSJO-UHFFFAOYSA-N 4-(dimethylamino)butane-1,2-diol Chemical compound CN(C)CCC(O)CO ZAJHMOZTXOGSJO-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002789 polymer coal Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention relates to the technical field of materials, and discloses a composite material and a preparation method thereof, wherein the composite material comprises a component A, a component B and a component C, and the weight ratio of the component A to the component B to the component C is 1: 0.7-0.95: 0.0001-0.4, wherein the component A contains an alkaline solution and a catalyst, the content of the alkaline solution is 80-99.2 wt% and the content of the catalyst is 0.8-20 wt% based on the weight of the component A; the component B contains polyisocyanate prepolymer and solubilizer, and the content of the polyisocyanate prepolymer is 80-99 wt% and the content of the solubilizer is 1-20 wt% based on the weight of the component B; the component C contains a silicon-aluminum material. The composite material of the present invention has both high compressive strength and low maximum reaction temperature.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a composite material and a preparation method thereof.
Background
The material is commonly used for reinforcing a dam foundation pit, reinforcing coal mine coal and rock mass, preventing seepage and stopping leakage and bearing and filling a road bed at present, and needs to have high compressive strength based on the consideration of safe production; also, considering the safety problem in the material preparation process, it is also required to have a low maximum reaction temperature. However, no composite material is available which combines the characteristics of high compressive strength and low maximum reaction temperature.
US3607794A discloses the reaction of organic polyisocyanates with alkali metal silicate solutions, illustrating the effect of different reaction ratios on the properties of the consolidated bodies. However, the method disclosed in the patent application can obtain a material with a high maximum reaction temperature in the preparation process, and the safety of the preparation process is poor.
CNI068163A discloses a two-component water glass type chemical grouting material, which contains an expandable diluent, wherein the maximum compression strength index of a consolidated body prepared in the specific embodiment is only 89.0kg/cm2(about 8.7MPa) which is far lower than the requirement that the compressive strength index of the safety production standard AQ1089-2011 polymer coal rock mass reinforcer of the people's republic of China is more than or equal to 40 MPa.
Therefore, the composite material which has the characteristics of high compressive strength, low highest reaction temperature and the like is developed, and the composite material has important practical significance and market application value.
Disclosure of Invention
The present invention aims to overcome the above problems of the prior art and to provide a composite material and a method for preparing the same, wherein the composite material has both high compressive strength and low maximum reaction temperature.
In order to achieve the above object, in a first aspect, the present invention provides a composite material comprising an a component, a B component and a C component in a weight ratio of 1: 0.7-0.95: 0.0001-0.4, wherein,
the component A contains alkaline solution and catalyst, wherein the content of the alkaline solution is 80-99.2 wt% and the content of the catalyst is 0.8-20 wt% based on the weight of the component A;
the component B contains polyisocyanate prepolymer and solubilizer, and the content of the polyisocyanate prepolymer is 80-99 wt% and the content of the solubilizer is 1-20 wt% based on the weight of the component B;
the component C contains a silicon-aluminum material.
In a second aspect, the present invention provides a method for preparing the composite material according to the present invention, comprising:
(1) mixing the component A and the component C to form a gel material prepolymer;
(2) and (2) mixing the gel material prepolymer obtained in the step (1) with the component B, and curing.
In a third aspect, the present invention provides a product made from the composite material of the present invention.
Compared with the existing composite material, the composite material has high compressive strength and low maximum reaction temperature.
Wherein, according to a preferred embodiment of the invention, the composite material is prepared according to the method of the invention (firstly, the A component and the C component are mixed to form the gel material prepolymer, then, the gel material prepolymer is mixed with the B component and is solidified), the three components interact according to a specific sequence, and by controlling specific conditions (such as the weight ratio of the A component, the B component and the C component, the type of alkaline solution in the A component or the grain diameter D50 of the silicon-aluminum material), the formed consolidated body is compact, does not foam when meeting water, has better mechanical property, simultaneously has high compressive strength and low highest reaction temperature, can be widely applied to reinforcement treatment of dam foundation pits, coal mine coal and rock body reinforcement, coal mine seepage prevention and leakage stoppage, road subgrade bearing filling and the like, can meet the performance requirements of the industrial standard AQ1089-2011 on the polymer materials for various purposes.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a composite material comprising a component a, a component B and a component C, wherein the weight ratio of the component a, the component B and the component C is 1: 0.7-0.95: 0.0001-0.4, wherein,
the component A contains alkaline solution and catalyst, wherein the content of the alkaline solution is 80-99.2 wt% and the content of the catalyst is 0.8-20 wt% based on the weight of the component A;
the component B contains polyisocyanate prepolymer and solubilizer, and the content of the polyisocyanate prepolymer is 80-99 wt% and the content of the solubilizer is 1-20 wt% based on the weight of the component B;
the component C contains a silicon-aluminum material.
In the present invention, it is preferable that the weight ratio of the component a, the component B and the component C is 1: 0.75-0.85: 0.0001 to 0.25, more preferably 1: 0.75-0.85: 0.01-0.25.
In the present invention, it is preferable that the content of the alkaline solution in the component a is 90 to 99% by weight and the content of the catalyst is 1 to 10% by weight, based on the weight of the component a.
In the present invention, in the component a, the alkaline solution is preferably at least one of a sodium silicate aqueous solution, a potassium silicate aqueous solution, a sodium hydroxide aqueous solution, and a potassium hydroxide aqueous solution, and more preferably, the alkaline solution is a sodium silicate aqueous solution and/or a potassium silicate aqueous solution. The modulus of the sodium silicate aqueous solution and/or the potassium silicate aqueous solution is preferably 1.5 to 4, and more preferably 2 to 3.
Preferably, the concentration (solid content) of the alkaline solution is 30 to 60% by weight, and more preferably 40 to 55% by weight.
In the present invention, it is preferable that the catalyst in the component a is at least one of triethylenediamine, N-dimethylcyclohexylamine, N-dimethylaminoethylethylene glycol, pentamethyldiethylenetriamine, dibutyltin dilaurate, dibutyltin diacetate, potassium isooctanoate, and potassium oleate.
In the present invention, the component a preferably further contains a solubilizer in an amount of 1 to 10% by weight, more preferably 1.5 to 3% by weight, based on the weight of the component a. Wherein, the solubilizer is preferably at least one of castor oil formate, ethylene glycol diacetate, diethylene glycol butyl ether acetate, tributyl citrate and dioctyl phthalate.
In the present invention, it is preferable that the content of the polyisocyanate prepolymer in the component B is 90 to 95% by weight and the content of the solubilizer is 5 to 10% by weight, based on the weight of the component B.
In the present invention, preferably, in the component B, the solubilizer is at least one of castor oil formate, ethylene glycol diacetate, diethylene glycol butyl ether acetate, tributyl citrate, and dioctyl phthalate.
In the present invention, it is preferable that in the component B, the polyisocyanate prepolymer is prepared from polyphenyl polymethylene polyisocyanate and polymer polyol, and the NCO content of the polyisocyanate prepolymer is 20 to 34%.
Preferably, the weight ratio of said polyphenyl polymethylene polyisocyanate to said polymeric polyol is from 4 to 20: 1.
preferably, the polymer polyol is polyether polyol and/or polyester polyol, the functionality of the polyether polyol is 2-4, the number average molecular weight is 100-4000, and the viscosity is 100-1000 mPa.S; the polyester polyol has a functionality of 2-4, a number average molecular weight of 200-3500 and a viscosity of 500-2000 mPa.S.
In the invention, the silicon-aluminum material can be various natural aluminosilicate minerals and various aluminosilicate industrial byproducts or waste residues, and preferably, the silicon-aluminum material is at least one of slag, coal slag, fly ash, volcanic ash and metakaolin.
Preferably, the particle size D50 of the silicon aluminum material is <30 μm, more preferably <20 μm, even more preferably <13 μm.
In the present invention, it should be understood by those skilled in the art that the a component, the B component and the C component are each independently packaged. Before use, the component A, the component B and the component C are mixed in a certain order, so that the composite material is prepared.
In a second aspect, the present invention provides a process for the preparation of the composite material of the present invention, the process comprising:
(1) mixing the component A and the component C to form a gel material prepolymer;
(2) and (2) mixing the gel material prepolymer obtained in the step (1) with the component B, and curing.
In the present invention, preferably, in the step (1), the mixing conditions include: the time is 0.1 to 96 hours, and more preferably 0.5 to 5 hours.
In the present invention, preferably, in the step (2), the mixing conditions include: the time is 0.1-30min, preferably 0.2-3 min.
In another aspect, it will be appreciated by those skilled in the art that the present invention provides products made from the composite material that combine high compressive strength with a low maximum reaction temperature.
Examples
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto. In the following examples and comparative examples, the materials used are all commercially available and the methods used are conventional in the art, unless otherwise specified.
Wherein the used fly ash is purchased from the China's three-river power plant and comprises the following components: 48.2% by weight of SiO232.0% by weight of Al2O37.9% by weight of CaO, 5.65% by weight of Fe2O3The content of other oxides was 6.25% by weight, and the particle diameter D50 was 3 μm, 15 μm or 25 μm.
The used slag is purchased from Shanghai Meishan Steel works Ltd, and comprises the following components: 39.1% by weight of SiO211.5% by weight of Al2O341.0% by weight of CaO, 1.2% by weight of Fe2O3The content of other oxides was 7.2% by weight, and the particle diameter D50 was 5 μm.
The metakaolin used is purchased from Fujian ceramic gold peak new materials Co., Ltd and comprises the following components: 55.0% by weight of SiO243.3% by weight of Al2O30.8% by weight of Fe2O3The content of other oxides was 0.9% by weight, and the particle diameter D50 was 10 μm.
The calcium carbonate used was chemically pure, with a content of 99%, and a particle size D50 of 3 μm.
The talc used was chemically pure, 99% in content, with a particle size D50 of 3 μm.
The polyether polyol was obtained from Daihot chemical Co., Ltd, Shandong, and had a functionality of 2, a number average molecular weight of 2000 and a viscosity of 270-370 mPaS.
The polyester polyol was purchased from Wawter group, Inc., and had a functionality of 2, a number average molecular weight of 2400, and a viscosity of 550-650 mPaS.
Example 1
This example illustrates the composite material of the present invention and the method of making the same.
(1) Preparation of component A
97kg of sodium silicate aqueous solution (47 wt% content, modulus 2.6) was added to the reaction kettle, 3kg of N, N-dimethylaminoethylethylene glycol was added during stirring, and stirred for 30min to obtain a clear and transparent component A.
(2) Preparation of polyisocyanate prepolymer
Adding 80kg of polyphenyl polymethylene polyisocyanate into a reaction kettle, adding 20kg of polyether polyol during stirring, and stirring for 60min to obtain a brown polyisocyanate prepolymer with the NCO content of 23%.
(3) Preparation of component B
And (3) adding 93kg of polyisocyanate prepolymer into the reaction kettle, adding 7kg of diethylene glycol butyl ether acetate during stirring, and stirring for 30min to obtain a brown transparent component B.
(4) Preparation of composite materials
And (3) uniformly mixing 10kg of the component A and 2kg of the component C (the component C is fly ash with the particle size D50 of 3 mu m), stirring for 60min, adding 8kg of the component B, mixing and stirring for 20s, and obtaining the composite material.
Example 2
This example illustrates the composite material of the present invention and the method of making the same.
(1) Preparation of component A
90kg of sodium silicate aqueous solution (with the content of 55 weight percent and the modulus of 2.8) is added into the reaction kettle, 10kg of N, N-dimethylcyclohexylamine is added during stirring, and the mixture is stirred for 30min to obtain a clear and transparent component A.
(2) Preparation of polyisocyanate prepolymer
Adding 80kg of polyphenyl polymethylene polyisocyanate into a reaction kettle, adding 8kg of polyester polyol during stirring, and stirring for 60min to obtain a brown polyisocyanate prepolymer with the NCO content of 27%.
(3) Preparation of component B
Adding 90kg of polyisocyanate prepolymer into a reaction kettle, adding 10kg of castor oil formic ether during stirring, and stirring for 30min to obtain a brown transparent component B.
(4) Preparation of composite materials
10kg of the A component and 2.5kg of the C component (the C component is slag having a particle size D50 of 5 μm) were uniformly mixed, stirred for 1.5 hours, and then 8.5kg of the B component was added, mixed and stirred for 30 seconds to obtain a composite material.
Example 3
This example illustrates the composite material of the present invention and the method of making the same.
(1) Preparation of component A
99kg of potassium silicate aqueous solution (40 wt% in content, 3.0 in modulus) was added to the reaction kettle, and 1kg of dibutyltin dilaurate was added during stirring and stirred for 30min to obtain a clear and transparent component a.
(2) Preparation of polyisocyanate prepolymer
Adding 80kg of polyphenyl polymethylene polyisocyanate into a reaction kettle, adding 4kg of polyester polyol during stirring, and stirring for 60min to obtain a brown polyisocyanate prepolymer with the NCO content of 28%.
(3) Preparation of component B
Adding 95kg of polyisocyanate prepolymer into a reaction kettle, adding 5kg of dioctyl phthalate during stirring, and stirring for 30min to obtain a brown transparent component B.
(4) Preparation of composite materials
10kg of the A component and 0.1kg of the C component (the C component is metakaolin with the particle size D50 of 10 mu m) are uniformly mixed and stirred for 2 hours, and then 7.5kg of the B component is added and mixed and stirred for 45 seconds to obtain the composite material.
Example 4
According to the method of example 1, except that, in the step (4), 10kg of the A component and 4kg of the C component (the C component is fly ash with the particle size D50 of 3 μm) were uniformly mixed, stirred for 60min, and then 7kg of the B component was added, mixed and stirred for 20s, to obtain a composite material.
Example 5
According to the method of example 1, except that, in the step (4), 10kg of the A component and 0.001kg of the C component (the C component is fly ash having a particle size D50 of 3 μm) were uniformly mixed, stirred for 60min, and then 9.5kg of the B component was added, mixed and stirred for 20s, to obtain a composite material.
Example 6
The procedure is as in example 1, except that the C component is replaced by an equivalent amount of fly ash having a particle size D50 of 15 μm.
Example 7
The procedure is as in example 1, except that the C component is replaced by an equivalent amount of fly ash having a particle size D50 of 25 μm.
Example 8
The procedure is as in example 1, except that the C component is replaced by an equivalent amount of fly ash having a particle size D50 of 35 μm.
Example 9
The procedure of example 1 was followed except that, in step (1), 97kg of an aqueous sodium hydroxide solution (content: 47% by weight) was used in place of 97kg of an aqueous sodium silicate solution (content: 47% by weight, modulus: 2.6).
Comparative example 1
The procedure is as in example 1, except that the C component is replaced by an equal amount of calcium carbonate having a particle size D50 of 3 μm.
Comparative example 2
The procedure is as in example 1, except that the C component is replaced by an equivalent amount of talc having a particle size D50 of 3 μm.
Comparative example 3
A part A and a part B were prepared according to the method of example 1, respectively, and then 10kg of the part A and 8kg of the part B were mixed for 30 seconds to obtain a composite material.
Comparative example 4
A component A and a component B were each prepared in the same manner as in example 1, and then 10kg of the component A, 8kg of the component B and 2kg of the component C (the component C being fly ash having a particle size D50 of 3 μm) were mixed and stirred for 20 seconds to obtain a composite material.
Comparative example 5
The component A and the component B were prepared according to the method of example 1, and then 8kg of the component B and 2kg of the component C (the component C is fly ash with a particle size D50 of 3 μm) were uniformly mixed, stirred for 60min, and then 10kg of the component A was added, mixed and stirred for 20s, to obtain a composite material.
Test examples
The compressive strength of each composite material (test piece is a cylinder with the diameter (50 +/-1) mm and the height (100 +/-1) mm) and the highest reaction temperature in the mixing process of each component) are measured according to AQ 1089-. The results are shown in Table 1.
TABLE 1
| Example numbering | Compressive strength (MPa) | Maximum reaction temperature (. degree.C.) |
| Example 1 | 49 | 107 |
| Example 2 | 52 | 110 |
| Example 3 | 41 | 105 |
| Example 4 | 30 | 106 |
| Example 5 | 40 | 112 |
| Example 6 | 44 | 111 |
| Example 7 | 41 | 109 |
| Example 8 | 11 | 110 |
| Example 9 | 12 | 115 |
| Comparative example 1 | 5 | 108 |
| Comparative example 2 | 6 | 104 |
| Comparative example 3 | 49 | 134 |
| Comparative example 4 | 13 | 135 |
| Comparative example 5 | 15 | 132 |
Wherein, the industrial standard AQ 1089-.
From the results in table 1 it can be seen that the composite material of the present invention combines a high compressive strength with a low maximum reaction temperature.
Specifically, as can be seen from a comparison of the results of example 1 and comparative examples 1 to 2 in table 1, the compressive strength of the composite material can be significantly improved by using the silicon-aluminum material as component C when the composite material is prepared.
Comparing the results of example 1 and comparative example 3 in table 1, it can be seen that the maximum reaction temperature of the composite material can be significantly reduced when the sialon material is added to the composite material.
Comparing the results of example 1 and comparative examples 4-5 in Table 1, it can be seen that when preparing the composite material, the A component and the C component are mixed to form a gel material prepolymer; and then the gel material prepolymer and the component B are mixed and cured, so that the compressive strength of the composite material can be obviously improved, and the highest reaction temperature of the composite material can be obviously reduced.
Comparing the results of example 1 and examples 4-5 in Table 1, the weight ratio of component A, component B and component C is 1: 0.75-0.85: 0.01-0.25, the composite material has better compressive strength and higher maximum reaction temperature.
Comparing the results of example 1 and examples 6-8 in table 1, it can be seen that when the particle size D50 of the silicon aluminum material is less than 30 μm, the compressive strength of the composite material can be significantly improved; when the grain diameter D50 of the silicon-aluminum material is less than 16 mu m, the compressive strength of the composite material can be further improved; when the grain diameter D50 of the silicon-aluminum material is less than 13 mu m, the compressive strength of the composite material can be further improved.
Comparing the results of example 1 and example 9 in table 1, it is understood that when the alkaline solution in component a is an aqueous sodium silicate solution and/or an aqueous potassium silicate solution, the compressive strength of the composite material can be significantly improved and the maximum reaction temperature of the composite material can be lowered.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. The composite material is characterized by comprising a component A, a component B and a component C, wherein the weight ratio of the component A to the component B to the component C is 1: 0.7-0.95: 0.0001-0.4, wherein,
the component A contains alkaline solution and catalyst, wherein the content of the alkaline solution is 80-99.2 wt% and the content of the catalyst is 0.8-20 wt% based on the weight of the component A;
the component B contains polyisocyanate prepolymer and solubilizer, and the content of the polyisocyanate prepolymer is 80-99 wt% and the content of the solubilizer is 1-20 wt% based on the weight of the component B;
the component C contains a silicon-aluminum material, the particle size D50 of the silicon-aluminum material is less than 30 mu m,
wherein in the component A, the alkaline solution is a sodium silicate aqueous solution and/or a potassium silicate aqueous solution,
the silicon-aluminum material is at least one of slag, coal cinder, fly ash, volcanic ash and metakaolin,
the preparation method of the composite material comprises the following steps:
(1) mixing the component A and the component C to form a gel material prepolymer;
(2) and (2) mixing the gel material prepolymer obtained in the step (1) with the component B, and curing.
2. The composite material of claim 1, wherein the weight ratio of the a component, the B component, and the C component is 1: 0.75-0.85: 0.01-0.25.
3. The composite material of claim 1, wherein the alkaline solution is present in an amount of 90 to 99 wt% and the catalyst is present in an amount of 1 to 10 wt% based on the weight of the a component.
4. The composite of any of claims 1-3, wherein in component A, the catalyst is at least one of triethylenediamine, N-dimethylcyclohexylamine, N-dimethylaminoethylethylene glycol, pentamethyldiethylenetriamine, dibutyltin dilaurate, dibutyltin diacetate, potassium isooctanoate, and potassium oleate.
5. The composite material according to claim 4, wherein the concentration of the alkaline solution is 30-60 wt%.
6. The composite material of claim 5, wherein the concentration of the alkaline solution is 40-55 wt%.
7. The composite material according to any one of claims 1 to 3, wherein the content of the polyisocyanate prepolymer in the B component is 90 to 95 wt% and the content of the solubilizer is 5 to 10 wt% based on the weight of the B component.
8. The composite material according to any one of claims 1-3, wherein in the B component, the solubilizer is at least one of ricinoleate, ethylene glycol diacetate, diethylene glycol butyl ether acetate, tributyl citrate, and dioctyl phthalate; and/or
In the component B, the polyisocyanate prepolymer is prepared from polyphenyl polymethylene polyisocyanate and polymer polyol, and the NCO content of the polyisocyanate prepolymer is 20-34%.
9. The composite material of claim 8, wherein the weight ratio of the polyphenyl polymethylene polyisocyanate to the polymer polyol is from 4 to 20: 1.
10. the composite material of claim 8, wherein the polymer polyol is a polyether polyol and/or a polyester polyol, the polyether polyol having a functionality of 2-4, a number average molecular weight of 100-4000, and a viscosity of 100-1000 mPa-S; the polyester polyol has a functionality of 2-4, a number average molecular weight of 200-3500 and a viscosity of 500-2000 mPa.S.
11. The composite material according to any one of claims 1-3, wherein the silicon aluminum material has a particle size D50<20 μm.
12. The composite material of claim 11, wherein the silica-alumina material has a particle size D50<13 μ ι η.
13. A method of preparing a composite material according to any one of claims 1 to 12, characterised in that the method comprises:
(1) mixing the component A and the component C to form a gel material prepolymer;
(2) and (2) mixing the gel material prepolymer obtained in the step (1) with the component B, and curing.
14. The method of claim 13, wherein in step (1), the mixing conditions comprise: the time is 0.1 to 96 hours; and/or
In the step (2), the mixing conditions include: the time is 0.1-30 min.
15. The method of claim 14, wherein in step (1), the mixing conditions comprise: the time is 0.5-5 h; and/or
In the step (2), the mixing conditions include: the time is 0.2-3 min.
16. A product made from the composite material according to any one of claims 1 to 12.
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