CN116656086A - High-hardness inorganic-organic hybrid resin and preparation process thereof - Google Patents
High-hardness inorganic-organic hybrid resin and preparation process thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000010025 steaming Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000005303 weighing Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 20
- 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 16
- 238000001816 cooling Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 11
- 239000004632 polycaprolactone Substances 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 229940014800 succinic anhydride Drugs 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 10
- VZWMKHUMEIECPK-UHFFFAOYSA-M benzyl-dimethyl-octadecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 VZWMKHUMEIECPK-UHFFFAOYSA-M 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WORCCYVLMMTGFR-UHFFFAOYSA-M loxoprofen sodium Chemical compound [Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 WORCCYVLMMTGFR-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention relates to the technical field of resin preparation technology, and provides a high-hardness inorganic-organic hybrid resin and a preparation technology thereof; and secondly, the modified aluminum oxide and the modified graphene are added into the modified epoxy resin, so that the performance of the resin can be further improved, the aluminum oxide is improved through the silane coupling agent and then added into the modified epoxy resin, the wear resistance and the corrosion resistance of the resin can be improved, the graphene oxide is improved through the silane coupling agent serving as the modifier and then added into the modified epoxy resin, and the corrosion resistance of the resin can be enhanced, so that the high-hardness inorganic-organic hybrid resin prepared by the method has better market application value.
Description
Technical Field
The invention relates to the technical field of resin preparation processes, in particular to a high-hardness inorganic-organic hybrid resin and a preparation process thereof.
Background
Hybrid materials refer to the combination of different types of materials, resulting in new materials that have characteristics between the different types of materials. The physical and chemical property analysis of the material can be divided into an organic material and an inorganic material, an organic polymer is taken as a main body, the material which is hybridized and modified by introducing an inorganic component is called an organic-inorganic hybridized material, and the hybridized material with the characteristics of the organic material and the inorganic material can be obtained when the inorganic material and the organic material are combined to the nanometer level. The inorganic material has the advantages of high strength, strong high and low temperature resistance, stable mechanical property, long service life and the like, but also has the defects of large brittleness coefficient, poor adhesion property, difficult processing and the like, the defects of the two materials are complemented, the nano-size effect is exerted due to the introduction of nano particles in the hybridized organic and inorganic hybrid material, the heat resistance of the composite material is greatly improved, the nano particles also have strong mechanical property, and the thermodynamic property of the modified organic resin material is greatly improved, such as toughness and impact resistance.
At present, resins prepared in a market in an organic-inorganic hybrid mode are various, but most of the resins are prepared by hybridization of a single organic component and a single inorganic component, and the prepared resins have single performance and cannot have the advantages of a plurality of types of performances, so that the technical defect of single performance of the resins can be overcome if different organic components or inorganic components are introduced into the organic-inorganic hybrid resins in a modified grafting mode.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects existing in the prior art, the invention provides the inorganic-organic hybrid resin with high hardness and the preparation process thereof, which can effectively solve the problems of single performance and poor market application value of the inorganic-organic hybrid resin in the prior art.
Technical proposal
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a process for preparing a high hardness inorganic-organic hybrid resin, the process comprising the steps of:
step1, weighing 8-10 parts of diphenylmethane diisocyanate, 25-28 parts of polycaprolactone polyol and 6-7 parts of succinic anhydride according to parts by weight, pouring into a three-neck flask, adding 1-2 parts of di-n-butyltin dilaurate under the condition of stirring, reacting for 20-22 hours under the condition of original stirring speed and normal temperature, adding 11-15 parts of 3-aminopropyl triethoxysilane after the reaction is finished, and continuously stirring and reacting for 3-5 hours to obtain the polyurethane prepolymer;
step2, weighing 50 parts of epoxy resin, 5-8 parts of propylene glycol methyl ether acetate and 15-20 parts of polyurethane prepolymer in Step1 according to parts by weight, pouring the mixture into a reaction kettle, heating to 80 ℃, preserving heat for 1h, heating to 120 ℃ and reacting for 4-5h at a stirring speed of 200-300r/min, cooling, filtering and discharging after the reaction is finished, and obtaining the modified epoxy resin;
step3, weighing 10-12 parts by weight of tetraethoxysilane, 8-10 parts by weight of silane coupling agent KH-560 and 35-38 parts by weight of isopropanol, mixing, adding 1-2 parts by weight of di-n-butyltin dilaurate under stirring, heating to 50-55 ℃, dropwise adding 5-8 parts by weight of hydrochloric acid aqueous solution, reacting for 4-5 hours under the original temperature condition, cooling to 25-28 ℃ after the reaction is finished, adding 10-15 parts of mildew-proof component, stirring for 5-8 minutes under the original stirring speed, and recording as a silica sol component after ultrasonic dispersion;
step4, weighing 50 parts by weight of modified epoxy resin in Step2, adding 5-6 parts by weight of silica sol component in Step3, 2-3 parts by weight of modified alumina and 1-2 parts by weight of modified graphene into a container, uniformly mixing, pouring into a rotary steaming bottle, performing vacuum rotary steaming, and cooling to room temperature after vacuum rotary steaming to obtain the inorganic-organic hybrid resin with high hardness.
Further, the stirring speed in Step1 is 400-500r/min.
Further, the temperature of the filtered discharging of the modified epoxy resin in Step2 is 45-50 ℃.
Further, the stirring speed in Step3 is 500-800r/min, and the volume concentration of the hydrochloric acid aqueous solution in Step3 is 10-20%.
Further, the preparation method of the mildew-proof component in Step3 comprises the following steps: weighing 3-5 parts of tetradecyl trimethyl ammonium chloride, 2-3 parts of tetradecyl trimethyl ammonium bromide, 1-2 parts of dodecyl dimethyl benzyl ammonium bromide and 2-3 parts of octadecyl dimethyl benzyl ammonium bromide according to parts by weight, mixing, and stirring at a stirring speed of 500-600r/min for 10min to obtain the mildew-proof component.
Further, the ultrasonic dispersion frequency in Step3 is 27-28kHz, and the ultrasonic dispersion time is 10min.
Further, the preparation method of the modified alumina in Step4 comprises the following steps: adding 10-15 parts of silane coupling agent KH-550 into 50-60 parts by weight of ethanol solution with the volume concentration of 80%, stirring and mixing at the stirring speed of 500-600r/min, adding a proper amount of acetic acid to adjust the pH value to 4-5, stirring at the original speed for 2 hours at the temperature of 35-38 ℃, adding 8-10 parts by weight of nano alumina, heating to 60 ℃, stirring at the original speed for 4 hours, pumping filtration, flushing with absolute ethanol for 3 times, and vacuum drying at the temperature of 65 ℃ for 6 hours to obtain the modified alumina.
Further, the preparation method of the modified graphene in Step4 comprises the following steps:
s1, adding 3-5 parts by weight of graphene oxide into 25-30 parts by weight of ethanol solution with the volume concentration of 80%, mixing and stirring, and performing ultrasonic dispersion for 10min at the frequency of 26-28kHz to obtain graphene oxide dispersion liquid;
s2, adding 10-12 parts by weight of a silane coupling agent KH-550 into the graphene oxide dispersion liquid in the S1, stirring at a stirring speed of 800-1000r/min for 1h, heating to 60 ℃ by an oil bath, and then keeping the temperature for constant-temperature reaction for 5h;
and S3, filtering the system obtained in the step S2, flushing for 3 times by using absolute ethyl alcohol after filtering, and then drying in a vacuum drying oven at 60 ℃ until the weight is constant, thus obtaining the modified graphene.
Further, the specific operation of spin steaming in Step4 is as follows: steaming at 75deg.C for 30min, heating to 90deg.C, and steaming for 40min.
A high hardness inorganic-organic hybrid resin comprising the following components: diphenylmethane diisocyanate, polycaprolactone polyol, succinic anhydride, di-n-butyltin dilaurate, 3-aminopropyl triethoxysilane, epoxy resin, propylene glycol methyl ether acetate, ethyl orthosilicate, silane coupling agent KH-560, isopropanol, aqueous hydrochloric acid solution, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide, silane coupling agent KH-550, acetic acid, nano alumina, graphene oxide and 80% ethanol solution.
Advantageous effects
The invention provides a high-hardness inorganic-organic hybrid resin and a preparation process thereof, and compared with the prior art, the invention has the following beneficial effects:
according to the invention, diphenylmethane diisocyanate, polycaprolactone polyol and succinic anhydride are used as raw materials, di-n-butyltin dilaurate is used as a catalyst to prepare the polyurethane prepolymer, and the polyurethane prepolymer is connected to the molecular chain of the epoxy resin in a functional group reaction mode through the ring-opening reaction of the epoxy resin, so that the epoxy resin can be toughened and modified, and the hardness of the epoxy resin is improved to a certain extent.
According to the invention, the silica sol component is added into the modified epoxy resin for organic-inorganic hybridization, so that the mechanical property, heat resistance and ablation resistance of the resin prepared by the invention can be improved, and the mildew-proof component with antibacterial property is introduced into the silica sol component, so that the mildew probability of the resin prepared by the invention in the use process can be reduced to a certain extent; and secondly, the modified aluminum oxide and the modified graphene are added into the modified epoxy resin, so that the performance of the resin can be further improved, the aluminum oxide is improved through the silane coupling agent and then added into the modified epoxy resin, the wear resistance and the corrosion resistance of the resin can be improved, the graphene oxide is improved through the silane coupling agent serving as the modifier and then added into the modified epoxy resin, and the corrosion resistance of the resin can be enhanced, so that the high-hardness inorganic-organic hybrid resin prepared by the method has better market application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further described below with reference to examples.
Example 1
The preparation process of the inorganic-organic hybrid resin with high hardness comprises the following steps:
step1, weighing 8 parts of diphenylmethane diisocyanate, 25 parts of polycaprolactone polyol and 6 parts of succinic anhydride according to parts by weight, pouring into a three-neck flask, adding 1 part of di-n-butyltin dilaurate under the condition of stirring, reacting for 20 hours under the condition of original stirring speed and normal temperature, adding 11 parts of 3-aminopropyl triethoxysilane after the reaction is finished, and continuously stirring and reacting for 3 hours to obtain the polyurethane prepolymer;
step2, weighing 50 parts of epoxy resin, 5 parts of propylene glycol methyl ether acetate and 15 parts of polyurethane prepolymer in Step1 according to parts by weight, pouring the materials into a reaction kettle, heating to 80 ℃, preserving heat for 1h, heating to 120 ℃ and reacting for 4h at a stirring speed of 200r/min, cooling, filtering and discharging after the reaction is finished, and obtaining the modified epoxy resin;
step3, weighing 10 parts by weight of tetraethoxysilane, 8 parts by weight of silane coupling agent KH-560 and 35 parts by weight of isopropanol, mixing, adding 1 part by weight of di-n-butyltin dilaurate under stirring, heating to 50 ℃, dropwise adding 5 parts by weight of hydrochloric acid aqueous solution, reacting for 4 hours under the original temperature condition, cooling to 25 ℃ after the reaction is finished, adding 10 parts of mildew-proof component, stirring for 5 minutes under the original stirring speed, and recording as a silica sol component after ultrasonic dispersion;
step4, weighing 50 parts by weight of modified epoxy resin in Step2, adding into a container, adding 5 parts by weight of silica sol component, 2 parts of modified alumina and 1 part of modified graphene in Step3, uniformly mixing, pouring into a rotary steaming bottle, carrying out vacuum rotary steaming, and cooling to room temperature after vacuum rotary steaming to obtain the inorganic-organic hybrid resin with high hardness.
The stirring speed in Step1 was 400r/min.
The temperature of the filtration discharge of the modified epoxy resin in Step2 was 45 ℃.
The stirring speed in Step3 was 500r/min, and the volume concentration of the aqueous hydrochloric acid solution in Step3 was 10%.
The preparation method of the mildew-proof component in Step3 comprises the following steps: weighing 3 parts of tetradecyl trimethyl ammonium chloride, 2 parts of tetradecyl trimethyl ammonium bromide, 1 part of dodecyl dimethyl benzyl ammonium bromide and 2 parts of octadecyl dimethyl benzyl ammonium bromide according to parts by weight, mixing, and stirring at a stirring speed of 500r/min for 10min to obtain the mildew-proof component.
The ultrasonic dispersion frequency in Step3 was 27kHz and the ultrasonic dispersion time was 10 minutes.
The preparation method of the modified alumina in Step4 comprises the following steps: adding 10 parts of silane coupling agent KH-550 into 50 parts by weight of ethanol solution with the volume concentration of 80%, stirring and mixing at the stirring speed of 500r/min, adding a proper amount of acetic acid to adjust the pH value to 4, stirring at the original speed for 2 hours at the temperature of 35 ℃, adding 8 parts by weight of nano-alumina, heating to 60 ℃, stirring at the original speed for 4 hours, flushing 3 times by using absolute ethanol after suction filtration, and vacuum drying at the temperature of 65 ℃ for 6 hours to obtain the modified alumina.
The preparation method of the modified graphene in Step4 comprises the following steps:
s1, adding 3 parts by weight of graphene oxide into 25 parts by weight of ethanol solution with the volume concentration of 80%, mixing and stirring, and performing ultrasonic dispersion for 10min at the frequency of 26kHz to obtain graphene oxide dispersion liquid;
s2, adding 10 parts by weight of a silane coupling agent KH-550 into the graphene oxide dispersion liquid in the S1, stirring at a stirring speed of 800r/min for 1h, heating to 60 ℃ by an oil bath, and then keeping the temperature for constant-temperature reaction for 5h;
and S3, filtering the system obtained in the step S2, flushing for 3 times by using absolute ethyl alcohol after filtering, and then drying in a vacuum drying oven at 60 ℃ until the weight is constant, thus obtaining the modified graphene.
The specific operation of spin steaming in Step4 is: steaming at 75deg.C for 30min, heating to 90deg.C, and steaming for 40min.
A high-hardness inorganic-organic hybrid resin, comprising the following components: diphenylmethane diisocyanate, polycaprolactone polyol, succinic anhydride, di-n-butyltin dilaurate, 3-aminopropyl triethoxysilane, epoxy resin, propylene glycol methyl ether acetate, ethyl orthosilicate, silane coupling agent KH-560, isopropanol, aqueous hydrochloric acid solution, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide, silane coupling agent KH-550, acetic acid, nano alumina, graphene oxide and 80% ethanol solution.
Example 2
The preparation process of the inorganic-organic hybrid resin with high hardness comprises the following steps:
step1, weighing 10 parts of diphenylmethane diisocyanate, 28 parts of polycaprolactone polyol and 7 parts of succinic anhydride according to parts by weight, pouring the materials into a three-neck flask, adding 2 parts of di-n-butyltin dilaurate under the condition of stirring, reacting for 22 hours under the condition of original stirring speed and normal temperature, adding 15 parts of 3-aminopropyl triethoxysilane after the reaction is finished, and continuously stirring and reacting for 5 hours to obtain the polyurethane prepolymer;
step2, weighing 50 parts of epoxy resin, 8 parts of propylene glycol methyl ether acetate and 20 parts of polyurethane prepolymer in Step1 according to parts by weight, pouring the materials into a reaction kettle, heating to 80 ℃, preserving heat for 1h, heating to 120 ℃ and reacting for 5h at a stirring speed of 300r/min, cooling, filtering and discharging after the reaction is finished, and obtaining the modified epoxy resin;
step3, weighing 12 parts by weight of tetraethoxysilane, 10 parts by weight of silane coupling agent KH-560 and 38 parts by weight of isopropanol, mixing, adding 2 parts by weight of di-n-butyltin dilaurate under stirring, heating to 55 ℃, dropwise adding 8 parts by weight of aqueous hydrochloric acid solution, reacting for 5 hours under the original temperature condition, cooling to 28 ℃ after the reaction is finished, adding 15 parts of mildew-proof component, stirring for 8 minutes under the original stirring speed, and recording as a silica sol component after ultrasonic dispersion;
step4, weighing 50 parts by weight of modified epoxy resin in Step2, adding into a container, adding 6 parts by weight of silica sol component, 3 parts of modified alumina and 2 parts of modified graphene in Step3, uniformly mixing, pouring into a rotary steaming bottle, carrying out vacuum rotary steaming, and cooling to room temperature after vacuum rotary steaming to obtain the inorganic-organic hybrid resin with high hardness.
The stirring speed in Step1 was 500r/min.
The temperature of the filtration discharge of the modified epoxy resin in Step2 was 50 ℃.
The stirring speed in Step3 was 800r/min, and the volume concentration of the aqueous hydrochloric acid solution in Step3 was 20%.
The preparation method of the mildew-proof component in Step3 comprises the following steps: weighing 5 parts of tetradecyl trimethyl ammonium chloride, 3 parts of tetradecyl trimethyl ammonium bromide, 2 parts of dodecyl dimethyl benzyl ammonium bromide and 3 parts of octadecyl dimethyl benzyl ammonium bromide according to parts by weight, mixing, and stirring at a stirring speed of 600r/min for 10min to obtain the mildew-proof component.
The ultrasonic dispersion frequency in Step3 was 28kHz and the ultrasonic dispersion time was 10 minutes.
The preparation method of the modified alumina in Step4 comprises the following steps: adding 15 parts of silane coupling agent KH-550 into 60 parts by weight of ethanol solution with the volume concentration of 80%, stirring and mixing at the stirring speed of 600r/min, adding a proper amount of acetic acid to adjust the pH value to 5, stirring at the original speed for 2 hours at the temperature of 38 ℃, adding 10 parts by weight of nano-alumina, heating to 60 ℃, stirring at the original speed for 4 hours, flushing with absolute ethanol for 3 times after suction filtration, and vacuum drying at the temperature of 65 ℃ for 6 hours to obtain the modified alumina.
The preparation method of the modified graphene in Step4 comprises the following steps:
s1, adding 5 parts by weight of graphene oxide into 30 parts by weight of ethanol solution with the volume concentration of 80%, mixing and stirring, and performing ultrasonic dispersion for 10min at the frequency of 28kHz to obtain graphene oxide dispersion liquid;
s2, adding 12 parts by weight of a silane coupling agent KH-550 into the graphene oxide dispersion liquid in the S1, stirring at a stirring speed of 1000r/min for 1h, heating to 60 ℃ by an oil bath, and then keeping the temperature for constant-temperature reaction for 5h;
and S3, filtering the system obtained in the step S2, flushing for 3 times by using absolute ethyl alcohol after filtering, and then drying in a vacuum drying oven at 60 ℃ until the weight is constant, thus obtaining the modified graphene.
The specific operation of spin steaming in Step4 is: steaming at 75deg.C for 30min, heating to 90deg.C, and steaming for 40min.
A high-hardness inorganic-organic hybrid resin, comprising the following components: diphenylmethane diisocyanate, polycaprolactone polyol, succinic anhydride, di-n-butyltin dilaurate, 3-aminopropyl triethoxysilane, epoxy resin, propylene glycol methyl ether acetate, ethyl orthosilicate, silane coupling agent KH-560, isopropanol, aqueous hydrochloric acid solution, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide, silane coupling agent KH-550, acetic acid, nano alumina, graphene oxide and 80% ethanol solution.
Example 3
The preparation process of the inorganic-organic hybrid resin with high hardness comprises the following steps:
step1, weighing 9 parts of diphenylmethane diisocyanate, 27 parts of polycaprolactone polyol and 7 parts of succinic anhydride according to parts by weight, pouring the materials into a three-neck flask, adding 2 parts of di-n-butyltin dilaurate under the condition of stirring, reacting for 21 hours under the condition of original stirring speed and normal temperature, adding 14 parts of 3-aminopropyl triethoxysilane after the reaction is finished, and continuously stirring and reacting for 4 hours to obtain the polyurethane prepolymer;
step2, weighing 50 parts of epoxy resin, 7 parts of propylene glycol methyl ether acetate and 18 parts of polyurethane prepolymer in Step1 according to parts by weight, pouring the mixture into a reaction kettle, heating to 80 ℃, preserving heat for 1h, heating to 120 ℃ and reacting for 4h at a stirring speed of 300r/min, cooling, filtering and discharging after the reaction is finished, and obtaining the modified epoxy resin;
step3, weighing 11 parts by weight of tetraethoxysilane, 9 parts by weight of silane coupling agent KH-560 and 37 parts by weight of isopropanol, mixing, adding 2 parts by weight of di-n-butyltin dilaurate under stirring, heating to 53 ℃, dropwise adding 7 parts by weight of hydrochloric acid aqueous solution, reacting for 4 hours under the original temperature condition, cooling to 26 ℃ after the reaction is finished, adding 13 parts of mildew-proof component, stirring for 7 minutes under the original stirring speed, and recording as a silica sol component after ultrasonic dispersion;
step4, weighing 50 parts by weight of modified epoxy resin in Step2, adding 5 parts by weight of silica sol component in Step3, 3 parts of modified alumina and 2 parts of modified graphene into a container, uniformly mixing, pouring into a rotary steaming bottle, performing vacuum rotary steaming, and cooling to room temperature after vacuum rotary steaming to obtain the inorganic-organic hybrid resin with high hardness.
The stirring speed in Step1 was 400r/min.
The temperature of the filtration output of the modified epoxy resin in Step2 was 48 ℃.
The stirring speed in Step3 was 700r/min, and the volume concentration of the aqueous hydrochloric acid solution in Step3 was 15%.
The preparation method of the mildew-proof component in Step3 comprises the following steps: weighing 4 parts of tetradecyl trimethyl ammonium chloride, 2 parts of tetradecyl trimethyl ammonium bromide, 1 part of dodecyl dimethyl benzyl ammonium bromide and 3 parts of octadecyl dimethyl benzyl ammonium bromide according to parts by weight, mixing, and stirring at a stirring speed of 600r/min for 10min to obtain the mildew-proof component.
The ultrasonic dispersion frequency in Step3 was 28kHz and the ultrasonic dispersion time was 10 minutes.
The preparation method of the modified alumina in Step4 comprises the following steps: adding 12 parts of a silane coupling agent KH-550 into 55 parts by weight of an ethanol solution with the volume concentration of 80%, stirring and mixing at the stirring speed of 500r/min, adding a proper amount of acetic acid to adjust the pH value to 5, stirring at the original speed for 2 hours at the temperature of 37 ℃, adding 9 parts by weight of nano-alumina, heating to 60 ℃, stirring at the original speed for 4 hours, flushing with absolute ethyl alcohol for 3 times after suction filtration, and vacuum drying at the temperature of 65 ℃ for 6 hours to obtain the modified alumina.
The preparation method of the modified graphene in Step4 comprises the following steps:
s1, adding 4 parts by weight of graphene oxide into 28 parts by weight of ethanol solution with the volume concentration of 80%, mixing and stirring, and performing ultrasonic dispersion for 10min at the frequency of 27kHz to obtain graphene oxide dispersion liquid;
s2, adding 11 parts by weight of a silane coupling agent KH-550 into the graphene oxide dispersion liquid in the S1, stirring at a stirring speed of 900r/min for 1h, heating to 60 ℃ by an oil bath, and then keeping the temperature for constant-temperature reaction for 5h;
and S3, filtering the system obtained in the step S2, flushing for 3 times by using absolute ethyl alcohol after filtering, and then drying in a vacuum drying oven at 60 ℃ until the weight is constant, thus obtaining the modified graphene.
The specific operation of spin steaming in Step4 is: steaming at 75deg.C for 30min, heating to 90deg.C, and steaming for 40min.
A high-hardness inorganic-organic hybrid resin, comprising the following components: diphenylmethane diisocyanate, polycaprolactone polyol, succinic anhydride, di-n-butyltin dilaurate, 3-aminopropyl triethoxysilane, epoxy resin, propylene glycol methyl ether acetate, ethyl orthosilicate, silane coupling agent KH-560, isopropanol, aqueous hydrochloric acid solution, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide, silane coupling agent KH-550, acetic acid, nano alumina, graphene oxide and 80% ethanol solution.
Comparative example 1:
the inorganic-organic hybrid resin provided in this comparative example and the preparation method thereof are substantially the same as in example 1, with the main differences that: comparative example 1 the modified epoxy resin in example 1 was replaced with an unmodified epoxy resin.
Comparative example 2:
the inorganic-organic hybrid resin provided in this comparative example and the preparation method thereof are substantially the same as in example 2, with the main differences that: the modified alumina of example 2 was not added to the feedstock of comparative example 2.
Comparative example 3:
the inorganic-organic hybrid resin provided in this comparative example and the preparation method thereof are substantially the same as in example 3, with the main differences that: the modified graphene in example 3 was not added to the raw material of comparative example 3.
Performance testing
The inorganic-organic hybrid resins of high hardness prepared in examples 1 to 3 were labeled as example 1, example 2 and example 3, respectively, the inorganic-organic hybrid resins prepared in comparative examples 1 to 3 were labeled as comparative example 1, comparative example 2 and comparative example 3, respectively, and then the properties of examples 1 to 3 and comparative examples 1 to 3 were examined by the following specific examination methods:
1. the resins of examples 1-3 and comparative examples 1-3 were tested for Shore hardness using an LX-A/D Shore durometer;
2. the resins of examples 1 to 3 and comparative examples 1 to 3 were tested for shear strength at 100℃with reference to the standard of GB 7124-2008;
3. the method for detecting the ablation resistance comprises the following steps: weighing the resins in the examples 1-3 and the comparative examples 1-3 with the same weight, drying to obtain six detection sample blocks, respectively burning the six detection sample blocks at 600 ℃ for 20min, recording the mass and the volume before and after burning, and calculating to obtain the mass residual rate and the volume residual rate;
the above detection results are recorded in table 1:
TABLE 1
As can be seen from the data shown in table 1, the high-hardness inorganic-organic hybrid resin prepared in examples 1 to 3 has better performance than that of comparative examples 1 to 3, the high-hardness inorganic-organic hybrid resin prepared in examples 1 to 3 has higher hardness as shown by the data of shore hardness, the high-hardness inorganic-organic hybrid resin prepared in examples 1 to 3 has better mechanical properties as shown by the data of shear strength, and finally the high-hardness inorganic-organic hybrid resin prepared in examples 1 to 3 has better ablation resistance as shown by the data of mass and volume residual ratio.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A process for preparing a high-hardness inorganic-organic hybrid resin, which is characterized by comprising the following steps:
step1, weighing 8-10 parts of diphenylmethane diisocyanate, 25-28 parts of polycaprolactone polyol and 6-7 parts of succinic anhydride according to parts by weight, pouring into a three-neck flask, adding 1-2 parts of di-n-butyltin dilaurate under the condition of stirring, reacting for 20-22 hours under the condition of original stirring speed and normal temperature, adding 11-15 parts of 3-aminopropyl triethoxysilane after the reaction is finished, and continuously stirring and reacting for 3-5 hours to obtain the polyurethane prepolymer;
step2, weighing 50 parts of epoxy resin, 5-8 parts of propylene glycol methyl ether acetate and 15-20 parts of polyurethane prepolymer in Step1 according to parts by weight, pouring the mixture into a reaction kettle, heating to 80 ℃, preserving heat for 1h, heating to 120 ℃ and reacting for 4-5h at a stirring speed of 200-300r/min, cooling, filtering and discharging after the reaction is finished, and obtaining the modified epoxy resin;
step3, weighing 10-12 parts by weight of tetraethoxysilane, 8-10 parts by weight of silane coupling agent KH-560 and 35-38 parts by weight of isopropanol, mixing, adding 1-2 parts by weight of di-n-butyltin dilaurate under stirring, heating to 50-55 ℃, dropwise adding 5-8 parts by weight of hydrochloric acid aqueous solution, reacting for 4-5 hours under the original temperature condition, cooling to 25-28 ℃ after the reaction is finished, adding 10-15 parts of mildew-proof component, stirring for 5-8 minutes under the original stirring speed, and recording as a silica sol component after ultrasonic dispersion;
step4, weighing 50 parts by weight of modified epoxy resin in Step2, adding 5-6 parts by weight of silica sol component in Step3, 2-3 parts by weight of modified alumina and 1-2 parts by weight of modified graphene into a container, uniformly mixing, pouring into a rotary steaming bottle, performing vacuum rotary steaming, and cooling to room temperature after vacuum rotary steaming to obtain the inorganic-organic hybrid resin with high hardness.
2. The process for preparing a high-hardness inorganic-organic hybrid resin according to claim 1, wherein the stirring speed in Step1 is 400-500r/min.
3. The process for preparing a high-hardness inorganic-organic hybrid resin according to claim 1, wherein the temperature of the filtration discharge of the modified epoxy resin in Step2 is 45-50 ℃.
4. The process for preparing a high-hardness inorganic-organic hybrid resin according to claim 1, wherein the stirring speed in Step3 is 500-800r/min, and the volume concentration of the aqueous hydrochloric acid solution in Step3 is 10-20%.
5. The process for preparing the high-hardness inorganic-organic hybrid resin according to claim 1, wherein the preparation method of the mildew-proof component in Step3 is as follows: weighing 3-5 parts of tetradecyl trimethyl ammonium chloride, 2-3 parts of tetradecyl trimethyl ammonium bromide, 1-2 parts of dodecyl dimethyl benzyl ammonium bromide and 2-3 parts of octadecyl dimethyl benzyl ammonium bromide according to parts by weight, mixing, and stirring at a stirring speed of 500-600r/min for 10min to obtain the mildew-proof component.
6. The process for preparing a high-hardness inorganic-organic hybrid resin according to claim 1, wherein the ultrasonic dispersion frequency in Step3 is 27-28kHz, and the ultrasonic dispersion time is 10min.
7. The process for preparing the high-hardness inorganic-organic hybrid resin according to claim 1, wherein the preparation method of the modified alumina in Step4 is as follows: adding 10-15 parts of silane coupling agent KH-550 into 50-60 parts by weight of ethanol solution with the volume concentration of 80%, stirring and mixing at the stirring speed of 500-600r/min, adding a proper amount of acetic acid to adjust the pH value to 4-5, stirring at the original speed for 2 hours at the temperature of 35-38 ℃, adding 8-10 parts by weight of nano alumina, heating to 60 ℃, stirring at the original speed for 4 hours, pumping filtration, flushing with absolute ethanol for 3 times, and vacuum drying at the temperature of 65 ℃ for 6 hours to obtain the modified alumina.
8. The preparation process of the high-hardness inorganic-organic hybrid resin according to claim 1, wherein the preparation method of the modified graphene in Step4 comprises the following steps:
s1, adding 3-5 parts by weight of graphene oxide into 25-30 parts by weight of ethanol solution with the volume concentration of 80%, mixing and stirring, and performing ultrasonic dispersion for 10min at the frequency of 26-28kHz to obtain graphene oxide dispersion liquid;
s2, adding 10-12 parts by weight of a silane coupling agent KH-550 into the graphene oxide dispersion liquid in the S1, stirring at a stirring speed of 800-1000r/min for 1h, heating to 60 ℃ by an oil bath, and then keeping the temperature for constant-temperature reaction for 5h;
and S3, filtering the system obtained in the step S2, flushing for 3 times by using absolute ethyl alcohol after filtering, and then drying in a vacuum drying oven at 60 ℃ until the weight is constant, thus obtaining the modified graphene.
9. The process for preparing the high-hardness inorganic-organic hybrid resin according to claim 1, wherein the specific operation of spin-steaming in Step4 is as follows: steaming at 75deg.C for 30min, heating to 90deg.C, and steaming for 40min.
10. The high-hardness inorganic-organic hybrid resin prepared by the preparation process of the high-hardness inorganic-organic hybrid resin according to any one of claims 1 to 9, wherein the high-hardness inorganic-organic hybrid resin comprises the following components: diphenylmethane diisocyanate, polycaprolactone polyol, succinic anhydride, di-n-butyltin dilaurate, 3-aminopropyl triethoxysilane, epoxy resin, propylene glycol methyl ether acetate, ethyl orthosilicate, silane coupling agent KH-560, isopropanol, aqueous hydrochloric acid solution, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide, silane coupling agent KH-550, acetic acid, nano alumina, graphene oxide and 80% ethanol solution.
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