CN113429537A - Aerogel composite polyurethane and preparation method thereof - Google Patents
Aerogel composite polyurethane and preparation method thereof Download PDFInfo
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- CN113429537A CN113429537A CN202110692737.4A CN202110692737A CN113429537A CN 113429537 A CN113429537 A CN 113429537A CN 202110692737 A CN202110692737 A CN 202110692737A CN 113429537 A CN113429537 A CN 113429537A
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- aerogel
- silane
- polyurethane
- composite polyurethane
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- 239000004964 aerogel Substances 0.000 title claims abstract description 83
- 239000004814 polyurethane Substances 0.000 title claims abstract description 54
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000005187 foaming Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- -1 polysiloxane, dimethyl dichlorosilane Polymers 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- OSNIDQXRNXZEJP-UHFFFAOYSA-N 2-methoxyperoxyethylsilane Chemical compound COOOCC[SiH3] OSNIDQXRNXZEJP-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- CSMYLGXMUPAWOJ-UHFFFAOYSA-N 2-ethoxyperoxyethylsilane Chemical compound C(C)OOOCC[SiH3] CSMYLGXMUPAWOJ-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- HDMXIELEUKTYFR-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC HDMXIELEUKTYFR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 2
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 claims description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- MHWRYTCHHJGQFQ-UHFFFAOYSA-N prop-2-enoic acid hydrate Chemical compound O.OC(=O)C=C MHWRYTCHHJGQFQ-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 239000012774 insulation material Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000004965 Silica aerogel Substances 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of foaming materials, and particularly relates to aerogel composite polyurethane and a preparation method thereof. The method comprises the following steps: 1) modifying an aerogel powder raw material by using a silane treating agent, and coating to form a film to prepare modified coated aerogel particles; 2) mixing the modified coated aerogel particles obtained in the step 1) with a polyurethane preparation material A, and then reacting with a polyurethane preparation material B to prepare the aerogel composite polyurethane. According to the invention, the aerogel powder raw material is modified and coated by the silane treatment agent, so that the aerogel structure is prevented from being damaged by other water phase or oil phase components in the process of preparing the composite polyurethane.
Description
Technical Field
The invention belongs to the technical field of foaming materials, and particularly relates to aerogel composite polyurethane and a preparation method thereof.
Background
At present, the requirements on the heat insulation materials and the performance of people are higher and higher, the research and development of novel heat insulation materials are widely regarded, the market of inorganic heat insulation materials is provided with a plurality of mineral wool, perlite and the like, the inorganic heat insulation materials have the greatest advantages of no combustion, high stability and poor heat insulation effect. The organic heat insulation materials are also in various types, including polyurethane foam, polystyrene boards, phenolic foam and the like, most of which are researched in the early stage, the process is the most mature, the application is the most extensive polyurethane material, and the most important problems of the polyurethane foam material at present are that the use temperature is low, the aging is easy, and the carbonization service life is short. In order to solve the above problems, silica aerogel materials are introduced, which can perfectly solve the above problems.
The silica aerogel has the characteristics of high fire-proof grade, high use temperature and low heat conductivity coefficient, is the best light heat-insulating material recognized at present, is also greatly popularized and used by the nation in recent years, has two hydrophilic and lipophilic silica aerogel materials in the market at present, and is widely applied to various composite materials. However, the application of the silica aerogel is greatly limited due to the defects of brittleness, frangibility and the like. In addition, the polyurethane foaming material is mostly divided into an AB material form, a water phase and an oil phase exist at the same time, and the porous structure of the aerogel is easily damaged, so that the effect of the silicon dioxide aerogel is reduced. In order to solve the problem of compounding of aerogel and polyurethane and simultaneously solve the problems of low heat insulation effect, carbonization problem, aging performance and use temperature of a polyurethane foam material, the aerogel is modified and coated and is added into a polyurethane system in different proportions to prepare the aerogel polyurethane composite material. Mixing SiO2The aerogel nano network framework structure is introduced into a polyurethane matrix, so that the problems are fundamentally solved, the application field of the aerogel is expanded, and the development of the aerogel industry is promoted.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides aerogel composite polyurethane and a preparation method thereof. According to the invention, the polyurethane and the aerogel are compounded, so that the excellent performance of the polyurethane and the heat insulation performance of the aerogel can be reserved, the defects that the aerogel is easy to crack and fall off when being compounded with an inorganic material are overcome, and the development prospect is good.
The technical scheme provided by the invention is as follows:
a preparation method of aerogel composite polyurethane comprises the following steps:
1) modifying an aerogel powder raw material by adopting a silane treating agent, and preparing modified coated aerogel particles by coating a film forming substance;
2) mixing the modified coated aerogel particles obtained in the step 1) with a polyurethane preparation material A, and then reacting with a polyurethane preparation material B to prepare the aerogel composite polyurethane.
Based on the technical scheme, the aerogel powder raw material is subjected to modified coating by the silane treatment agent, so that the aerogel structure is prevented from being damaged by other water phase or oil phase components in the process of preparing the composite polyurethane.
Coating a hydrophilic aerogel powder raw material with a silane treatment agent to obtain hydrophobic aerogel, adding a hydrophilic agent, stirring again, dispersing the hydrophilic aerogel powder raw material with a dispersing agent, an emulsifier, a water-based emulsion, polyvinyl alcohol, polyethylene glycol and polyol into water to form paste, and then spray-drying the paste to obtain the modified coated aerogel particles.
Based on above-mentioned technical scheme, can be applicable to hydrophilic aerogel powder raw materials.
Grinding and modifying a hydrophobic aerogel powder raw material and a hydrophilic agent, then dispersing the modified hydrophobic aerogel powder raw material and a dispersing agent, an emulsifying agent, a water-based emulsion, polyvinyl alcohol, polyethylene glycol and polyhydric alcohol into water to form a paste body, and then carrying out spray drying on the paste body to obtain the modified coated aerogel particles.
Based on above-mentioned technical scheme, can be applicable to hydrophobic aerogel powder raw materials.
Specifically, the step 2) comprises the following specific steps: adding the modified coated aerogel particles obtained in the step 1) into the polyurethane preparation material A, stirring at a high speed until the polyurethane preparation material A is white, adding polyurethane to prepare a material B, stirring, foaming, and curing at room temperature to obtain the aerogel composite polyurethane.
Based on the technical scheme, the existing A, B material method can be combined, and the modified coated aerogel particles are obtained by compounding the modified coated aerogel particles in the process of preparing polyurethane.
Specifically, the silane treatment agent is selected from any one or more of ethyl trioxyethylsilane, diethyl dioxyethylsilane, methyl trioxyethylsilane, polysiloxane, dimethyl dichlorosilane, octyl trimethoxysilane, octyl triethoxysilane, hexamethyldisilazane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, hexadecyl trimethoxysilane, hexadecyl triethoxysilane, dimethylpolysiloxane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, nonafluorohexyl trimethoxysilane, tridecafluorooctyl triethoxysilane, or aminopropyl triethoxysilane.
Specifically, the hydrophilic agent is dimethyl dioxyethyl silane poly diallyl dimethyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
Taking diethyldioxyethylsilane and a hydrophilic aerogel as examples:
after the hydrolysis is completed, ethanol and a silanol group are generated, wherein the silanol group is condensed with self and tetrahydroxy silane in aerogel to obtain a net structure, and the aerogel is not hydrophilic and oleophilic;
and hexadecyl trimethyl ammonium bromide is adopted for treatment, alkyl is combined with the net structure through weak force, hydrophilic ammonium groups are exposed outside, and the modified aerogel becomes a hydrophilic surface. Thus, an external hydrophilic and internal lipophilic structure is formed. This structure can be dispersed in aqueous systems, but water does not destroy the aerogel structure. Then adding emulsion and dispersant to coat the particles, and finally spray drying. At this time, the structure plays a good role in protecting the internal aerogel, and can be used in an oily environment or an aqueous environment. The microstructure of the aerogel is protected to the maximum extent in A, B material mixing of PU.
For hydrophobic aerogels, they can be coated directly with a hydrophilic agent.
Specifically, the dispersing agent is selected from one or more of sodium bis (2-ethylhexyl) succinate sulfonate, branched alkyl dimethyl amine oxide, octyl phenoxy polyethoxy ethanol, TWEEN 100 surfactant, BASF polyoxypropylene surfactant, glycol, alkoxylate polyoxy alkylene fatty ether, polymer surfactant, Renex nonionic surfactant, alcohol ethoxylate, alcohol alkoxylate, ethylene oxide, propylene oxide block copolymer, and polyoxyethylene derivative of sorbitan ester.
Specifically, the emulsifier is selected from PO-10 emulsifier or CA90 emulsifier.
Specifically, the aqueous emulsion is selected from any one or mixture of more of acrylic acid aqueous emulsion, polyurethane aqueous emulsion or fluorine-silicon aqueous emulsion.
Specifically, the particle size of the modified coated aerogel particles is 1-50 microns, and the thermal conductivity is less than 0.020W/(m.K).
The invention also provides the aerogel composite polyurethane prepared by the preparation method.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
the method comprises the steps of stirring and reacting methyl trioxyethylsilane, an ethanol aqueous solution and hydrophilic aerogel at 50 ℃ for 3 hours, drying to obtain hydrophobically modified aerogel powder, and adding a water dispersion of a hydrophilic agent cetyl trimethyl ammonium bromide to perform hydrophilic modification. When hydrophobic modification is carried out, methyl trioxyethylsilane: ethanol aqueous solution (80%): the mass ratio of the hydrophilic aerogel is 10: 50: 5. the mass ratio of the materials in hydrophilic modification is as follows: modified aerogel powder: cetyl trimethylammonium bromide: water 5:2:95
Adding PO-10 emulsifier, 731A dispersant and wetting agent W-1855, SY-3000 aqueous polyurethane emulsion into the dispersion, wherein the dispersion: emulsifier: dispersing agent: wetting agent: the content ratio of the polyurethane emulsion is 75:1:2:2:15, the polyurethane emulsion is dispersed into paste at high speed, and then the paste is sprayed and dried into powder particles with the size of 10 mu m for standby.
1) And A material: polyether 4110, phthalic anhydride polyether polyol, a catalyst, a foam stabilizer, a foaming agent and water;
2) and B material: a benzhydryl diisocyanate;
3) and the step: adding the modified aerogel powder particles into the material A, stirring at a high speed of 2000r/min until the material A is white, then adding the material B, stirring at a high speed, foaming freely, curing at room temperature, cutting into standard samples, and testing.
Composite polyurethanes with 1% to 4% aerogel content were prepared according to the above methods, respectively, and the results are shown in table 1.
Example 2
Hydrophobic aerogel powder of AG-D15 μm was used. Dispersing the powder in water phase treatment liquid containing hydrophilic agents of aminopropyltriethoxysilane and polyvinyl alcohol, dispersing and stirring uniformly at a high speed to perform hydrophilic modification, wherein the weight ratio of aerogel, aminopropyltriethoxysilane and polyvinyl alcohol: the mass ratio of water is 6:10:5: 90. Adding a waterborne polyurethane emulsion containing CA90 emulsifier, 1120 dispersant and wetting agent W-1855, SY-3000 into the dispersion, and dispersing at high speed to obtain paste, wherein the dispersion: emulsifier: dispersing agent: wetting agent: polyurethane emulsion: the mass ratio is 80:1:2:3:20, and the paste is sprayed and dried into powder particles with the size of 5 mu m for later use.
The method of adding the polyurethane is the same as above: the data are as described in Table 2 below
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The preparation method of the aerogel composite polyurethane is characterized by comprising the following steps of:
1) modifying an aerogel powder raw material by using a silane treating agent, and coating to form a film to prepare modified coated aerogel particles;
2) mixing the modified coated aerogel particles obtained in the step 1) with a polyurethane preparation material A, and then reacting with a polyurethane preparation material B to prepare the aerogel composite polyurethane.
2. The method for preparing aerogel composite polyurethane according to claim 1, wherein the step 1) comprises the following specific steps: coating a hydrophilic aerogel powder raw material with a silane treatment agent to obtain hydrophobic aerogel, adding a hydrophilic agent, stirring again, dispersing the hydrophilic aerogel powder raw material with a dispersing agent, an emulsifier, a water-based emulsion, polyvinyl alcohol, polyethylene glycol and polyol into water to form paste, and then spray-drying the paste to obtain the modified coated aerogel particles.
3. The method for preparing aerogel composite polyurethane according to claim 1, wherein the step 1) comprises the following specific steps: grinding and modifying a hydrophobic aerogel powder raw material and a hydrophilic agent, then dispersing the modified hydrophobic aerogel powder raw material and a dispersing agent, an emulsifying agent, a water-based emulsion, polyvinyl alcohol, polyethylene glycol and polyhydric alcohol into water to form a paste body, and then carrying out spray drying on the paste body to obtain the modified coated aerogel particles.
4. The method for preparing aerogel composite polyurethane according to claim 1, wherein the step 2) comprises the following specific steps: adding the modified coated aerogel particles obtained in the step 1) into the polyurethane preparation material A, stirring at a high speed until the polyurethane preparation material A is white, adding polyurethane to prepare a material B, stirring, foaming, and curing at room temperature to obtain the aerogel composite polyurethane.
5. The method of preparing aerogel composite polyurethane according to claim 2, wherein: the silane treating agent is selected from any one or combination of more of ethyl trioxyethyl silane, diethyl dioxyethyl silane, methyl trioxyethyl silane, polysiloxane, dimethyl dichlorosilane, octyl trimethoxy silane, octyl triethoxy silane, hexamethyldisilazane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxy silane, hexadecyl trimethoxy silane, hexadecyl triethoxy silane, dimethyl polysiloxane, glycidoxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, nonafluorohexyl trimethoxy silane, tridecafluorooctyl triethoxy silane or aminopropyl triethoxy silane.
6. The method of preparing aerogel composite polyurethane according to claim 3, wherein: the hydrophilic agent is dimethyl dioxyethyl silane poly diallyl dimethyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
7. The method for preparing aerogel composite polyurethane according to claim 2 or 3, wherein: the dispersant is selected from one or more of sodium bis (2-ethylhexyl) succinate sulfonate, branched alkyl dimethyl amine oxide, octyl phenoxy polyethoxy ethanol, TWEEN 100 surfactant, BASF polyoxypropylene surfactant, glycol, alkoxylate polyoxy alkylene fatty ether, polymer surfactant, Renex nonionic surfactant, alcohol ethoxylate, alcohol alkoxylate, ethylene oxide, propylene oxide block copolymer and polyoxyethylene derivative of sorbitan ester; the emulsifier is selected from PO-10 emulsifier or CA90 emulsifier; the water-based emulsion is selected from any one or mixture of more of acrylic acid water-based emulsion, polyurethane water-based emulsion or fluorine silicon water-based emulsion.
8. The method for preparing aerogel composite polyurethane according to any one of claims 1 to 6, wherein: the particle size of the modified coated aerogel particles is 1-50 microns, and the heat conductivity coefficient is less than 0.020W/(m.K).
9. An aerogel composite polyurethane prepared according to the preparation method of any one of claims 1 to 7.
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| CN114408895A (en) * | 2022-02-17 | 2022-04-29 | 福州大学 | Multifunctional high-porosity high-thermal-conductivity carbon aerogel based on polymer aerogel and preparation method thereof |
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| CN115197387A (en) * | 2022-07-29 | 2022-10-18 | 孙爱萍 | High-selectivity polyurethane oil absorption sponge and preparation method thereof |
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| CN114956863A (en) * | 2022-06-09 | 2022-08-30 | 安徽瑞联节能科技股份有限公司 | Building external wall heat-insulation composite board and processing technology thereof |
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