CN114752316A - Degradable adhesive and preparation method thereof - Google Patents
Degradable adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN114752316A CN114752316A CN202210607037.5A CN202210607037A CN114752316A CN 114752316 A CN114752316 A CN 114752316A CN 202210607037 A CN202210607037 A CN 202210607037A CN 114752316 A CN114752316 A CN 114752316A
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- CN
- China
- Prior art keywords
- aerogel
- adhesive
- degradable adhesive
- degradable
- hydrogen bond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000853 adhesive Substances 0.000 title claims abstract description 194
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 193
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004964 aerogel Substances 0.000 claims abstract description 148
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000009413 insulation Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 22
- 229920000858 Cyclodextrin Polymers 0.000 claims description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002689 soil Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001116 FEMA 4028 Substances 0.000 claims description 8
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 8
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 8
- 229960004853 betadex Drugs 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 6
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 6
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- AAWZDTNXLSGCEK-LNVDRNJUSA-N (3r,5r)-1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid Chemical compound O[C@@H]1CC(O)(C(O)=O)C[C@@H](O)C1O AAWZDTNXLSGCEK-LNVDRNJUSA-N 0.000 claims description 3
- AAWZDTNXLSGCEK-UHFFFAOYSA-N Cordycepinsaeure Natural products OC1CC(O)(C(O)=O)CC(O)C1O AAWZDTNXLSGCEK-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- AAWZDTNXLSGCEK-ZHQZDSKASA-N Quinic acid Natural products O[C@H]1CC(O)(C(O)=O)C[C@H](O)C1O AAWZDTNXLSGCEK-ZHQZDSKASA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229920005596 polymer binder Polymers 0.000 abstract 1
- 239000002491 polymer binding agent Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 34
- 239000012790 adhesive layer Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 26
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical group O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2405/00—Presence of polysaccharides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a degradable adhesive and a preparation method thereof, comprising the following steps: mixing the hydrogen bond acceptor, the aerogel and a solvent, and reacting to obtain a compound; and mixing the compound with a hydrogen bond donor, and removing the solvent after reaction to obtain the degradable adhesive. Compared with the traditional aqueous polymer binder, the degradable binder containing aerogel has good biodegradability, heat insulation property and adhesion property, not only effectively solves the problem that the aerogel is easy to fall off, but also avoids the problem that the binder is difficult to remove. The heat conductivity coefficient of the degradable adhesive containing aerogel is less than 0.019W/(m.K), and the adhesive strength is up to 7.6 MPa. The preparation method of the degradable adhesive is simple, environment-friendly, low in production cost and beneficial to industrial popularization.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a degradable adhesive and a preparation method thereof.
Background
The aerogel is a solid material with excellent heat insulation performance and has a special microstructure of high specific surface area, nanoscale pores, low density and the like. The aerogel has low mechanical strength and large brittleness, is difficult to be used as a heat insulation material independently, and needs to be compounded with a reinforcement to form an aerogel heat insulation composite material with good mechanical strength and excellent heat insulation performance.
Although the composite process improves the strength, flexibility and formability of the aerogel product, the aerogel particles filled in the gaps of the reinforcement are easy to fall out in the use process due to the action of segmentation or external force, so that the performance of the aerogel material is reduced, and the use effect and the service life of the aerogel material are influenced. In the market, a layer of packing material is often wrapped on the surface of the aerogel composite material by using an adhesive to solve the problem of powder falling. On one hand, the inorganic adhesive used in the market has no heat insulation property but has stronger heat conductivity, so that the overall heat insulation property of the aerogel composite material is reduced; on the other hand, although the heat insulating performance of the organic adhesive used in the market is superior to that of the inorganic adhesive, the heat insulating performance of the entire aerogel composite is still lowered below that of the aerogel composite itself. In addition, most of the organic adhesives used in the market are not biodegradable, are difficult to clean and remove, and even contain toxic components.
Patent application CN111234733A discloses an environment-friendly adhesive, which is obtained by mixing, heating and stirring a hydrogen bond donor and a hydrogen bond acceptor. The hydrogen bond donor is one of citric acid, malic acid and tartaric acid, and the hydrogen bond acceptor is cyclodextrin; the cyclodextrin is one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin. The environment-friendly adhesive disclosed by the patent is not added with any heat insulating material, so that the environment-friendly adhesive is not heat insulating. In addition, the environment-friendly adhesive has high viscosity, and the aerogel is difficult to disperse in the adhesive. This application patent is through letting aerogel thermal insulation material get into the hydrogen bond acceptor who contains macroporous structure earlier, and the adhesive in the interact formation of rethread hydrogen bond acceptor and hydrogen bond donor has improved the dissolubility and the dispersibility of aerogel in the adhesive, has given the good heat-proof quality of adhesive.
Disclosure of Invention
The invention aims to solve the problems of difficult biodegradation and difficult cleaning removal of the existing adhesive, and provides a degradable adhesive which is prepared by filling a hydrogen bond acceptor or a hydrogen bond donor with a pore structure and strong adhesiveness into an aerogel and synthesizing the aerogel-containing adhesive in situ by using the action of the hydrogen bond.
The existing adhesive is difficult to be directly combined with aerogel due to high viscosity. The invention realizes the combination of the hydrogen bond donor and the hydrogen bond donor by embedding the aerogel into the pores of the hydrogen bond acceptor before the hydrogen bond donor and the hydrogen bond donor react to form the adhesive. In order to ensure the combination effect, the reaction temperature in the step (2) is 90-150 ℃, the reaction time is 3-8 hours, otherwise, a stable adhesive cannot be formed between the hydrogen bond acceptor and the hydrogen bond donor, solid precipitation occurs in the system, and the bonding effect strength is greatly reduced.
The aerogel has heat insulation performance, and the heat insulation performance is improved after the aerogel is compounded with the adhesive; meanwhile, the dispersion state of the aerogel is changed, and the problem of powder falling of the aerogel can be avoided. However, aerogel has certain rigidity and can cause adverse effect on the bonding effect, therefore, aerogel powder material with the particle size of 1-50 nm is preferably reacted with a hydrogen bond acceptor, and a hydrogen bond acceptor containing macropores is preferably used, and the aperture of the hydrogen bond acceptor is preferably 100-500 nm.
The degradable adhesive of the present invention has degradability, and it can be degraded by itself in natural environment, for example, in soil. The degradation means that the adhesive can be gradually degraded into fragments and particles and is compatible with the natural environment.
The specific scheme is as follows:
a preparation method of a degradable adhesive is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the hydrogen bond acceptor, the aerogel and a solvent, and reacting to obtain a compound;
(2) and mixing the compound with a hydrogen bond donor, and removing the solvent after reaction to obtain the degradable adhesive.
Further, the hydrogen bond acceptor has a pore cavity with the size of 100-500nm, and the compound is a hydrogen bond acceptor with the pore cavity filled with aerogel.
Furthermore, the hydrogen bond acceptor is one or a mixture of a plurality of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
Further, the hydrogen bond donor is one or more of oxalic acid, tartaric acid, citric acid, succinic acid, quinic acid, malic acid and ascorbic acid;
optionally, the solvent is methanol, ethanol, propanol or butanol.
Further, the aerogel is SiO2Aerogel, Al2O3One or more of aerogel, cellulose aerogel, graphene aerogel, melamine-formaldehyde aerogel and resorcinol-formaldehyde aerogel.
Further, in the step (1), the hydrogen bond acceptor and the aerogel are mixed according to a molar ratio of 1: 0.1-1: 10;
optionally, the molar ratio of the hydrogen bond acceptor in the compound in the step (2) to the hydrogen bond donor is 1: 0.1-1: 20.
Further, the reaction temperature in the step (1) and/or the step (2) is 0-180 ℃, and the reaction time is 1-10 hours; preferably, the temperature in the step (2) is 90-150 ℃, and the time is 3-8 h.
The invention also protects the degradable adhesive prepared by the preparation method of the degradable adhesive, and the time for the degradable adhesive to be completely degraded in soil is 15-120 days.
Further, the adhesive strength of the degradable adhesive is 6-8 MPa; the degradable adhesive has heat insulation performance, and the heat conductivity coefficient is less than 0.019W/(m.K); the degradable adhesive is easy to remove, and can be removed by cleaning the degradable adhesive with water or an organic solvent.
The invention also protects the application of the degradable adhesive in the field of object bonding.
Has the advantages that: 1. the degradable adhesive containing aerogel provided by the invention has good heat insulation property, and the heat conductivity coefficient of the degradable adhesive is less than 0.019W/(m.K).
2. The degradable adhesive containing aerogel provided by the invention does not contain toxic substances, is nonvolatile and biodegradable.
3. The degradable adhesive containing aerogel provided by the invention is coated on the surfaces of materials such as metal, fiber, glass and plastic, has strong adhesion, the adhesion strength is up to 7.6MPa, an adhesive layer can be cleaned and removed by water, and the use safety is high.
4. The preparation method of the degradable adhesive containing aerogel provided by the invention is simple, has low cost and is beneficial to industrial popularization.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Those skilled in the art will recognize that the specific techniques or conditions, not specified in the examples, are according to the techniques or conditions described in the literature of the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The cyclodextrin used in the examples was macroporous cyclodextrin, with a pore size of 150 nm. The grain diameter of the aerogel powder is 50 nm.
Preparation of degradable adhesive containing aerogel
Example 1:
19.46g of alpha-cyclodextrin were mixed with 30g of SiO2And respectively adding the aerogel into 50mL of propanol, and stirring at 80 ℃ for 2h to obtain the hydrogen bond acceptor with the pore space filled with the aerogel. And adding 6.79g of oxalic acid into the system, stirring for 4 hours at 90 ℃, after the reaction is finished, rotationally steaming for 4 hours at 100 ℃ to remove the propanol solvent to obtain the milky degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.026W/(m.K), and the time for complete degradation in soil is 30 days. SiO in this example2The thermal conductivity of the aerogel is 0.018W/(mK).
Example 2:
19.46g of alpha-cyclodextrin was mixed with 20g of Al2O3And respectively adding the aerogel into 50mL of propanol, and stirring for 1h at 20 ℃ to obtain the hydrogen bond acceptor with the pore space filled with the aerogel. Adding 13.59g tartaric acid into the system, stirring at 95 deg.C for 8 hr, and reacting at 100 deg.CAnd (3) rotatably evaporating for 1h to remove the propanol solvent to obtain the wine red degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the degradable adhesive is 0.038W/(m.K), and the complete degradation time in soil is 45 days. Al in this example2O3The thermal conductivity of the aerogel is 0.021W/(m.K).
Example 3:
respectively adding 22.68g of beta-cyclodextrin and 50g of cellulose aerogel into 50mL of butanol, and stirring at 90 ℃ for 10h to obtain a hydrogen bond acceptor with pore cavities filled with the aerogel. And adding 18.52g of citric acid into the system, stirring for 7h at 115 ℃, after the reaction is finished, rotationally evaporating for 10h at 120 ℃ to remove the propanol solvent to obtain the orange degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the degradable adhesive is 0.046W/(m.K), and the time for complete degradation in soil is 60 days. The thermal conductivity of the cellulose aerogel in this example was 0.025W/(m.K).
Example 4:
respectively adding 22.68g of beta-cyclodextrin and 60g of melamine-formaldehyde aerogel into 50mL of butanol, and stirring at 100 ℃ for 4h to obtain a hydrogen bond acceptor with pore cavities filled with the aerogel. Adding 8.52g of succinic acid into the system, stirring for 8h at 130 ℃, after the reaction is finished, rotationally evaporating for 8h at 120 ℃ to remove the butanol solvent to obtain the brownish yellow degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.037W/(m.K), and the time for complete degradation in soil is 75 days. The thermal conductivity of the melamine-formaldehyde aerogel in this example was 0.019W/(m.K).
Example 5:
25.94g of gamma-cyclodextrin and 10g of resorcinol-formaldehyde aerogel are respectively added into 50mL of butanol, and stirred at 100 ℃ for 6h to obtain a hydrogen bond acceptor with pore cavities filled with the aerogel. And adding 14.83g of quinic acid into the system, stirring for 3 hours at 105 ℃, after the reaction is finished, rotationally steaming for 6 hours at 110 ℃ to remove the butanol solvent to obtain the black brown degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.022W/(m.K), and the time for complete degradation in soil is 105 days. The thermal conductivity of the resorcinol-formaldehyde aerogel in the present example was 0.014W/(m.K).
Example 6:
25.94g of gamma-cyclodextrin were mixed with 45g of SiO2And respectively adding the aerogel into 50mL of propanol, and stirring for 4h at 60 ℃ to obtain the hydrogen bond acceptor with the pore cavities filled with the aerogel. And adding 9.15g of malic acid into the system, stirring the mixture for 9 hours at 95 ℃, after the reaction is finished, carrying out rotary evaporation for 2 hours at 80 ℃ to remove the propanol solvent to obtain the milky degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.042W/(m.K), and the time for complete degradation in soil is 120 days. SiO in this example2The thermal conductivity of the aerogel is 0.018W/(m.K).
Example 7:
22.68g of alpha-cyclodextrin were mixed with 50g of SiO2And respectively adding the aerogel into 50mL of butanol, and stirring at 70 ℃ for 7h to obtain the hydrogen bond acceptor with the pore cavities filled with the aerogel. Adding 18.29g of oxalic acid into the system, stirring for 3h at 105 ℃, after the reaction is finished, rotationally steaming for 4h at 140 ℃ to remove the butanol solvent to obtain the milky degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.019W/(m.K), and the time for complete degradation in soil is 15 days. SiO in this example2The thermal conductivity of the aerogel is 0.018W/(m.K).
Example 8:
22.68g of beta-cyclodextrin was mixed with 25g of Al2O3And respectively adding the aerogel into 50mL of butanol, and stirring for 5h at 100 ℃ to obtain the hydrogen bond acceptor with the pore cavities filled with the aerogel. And adding 4.79g of tartaric acid into the system, stirring for 5 hours at 100 ℃, after the reaction is finished, rotationally steaming for 5 hours at 120 ℃ to remove the butanol solvent to obtain the wine-red degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.033W/(m.K), and the time for complete degradation in soil is 60 days. Al in this example2O3The thermal conductivity of the aerogel is 0.021W/(m.K).
Example 9:
adding 25.94g of beta-cyclodextrin and 15g of cellulose aerogel into 50mL of propanol respectively, and stirring at 50 ℃ for 9h to obtain the hydrogen bond acceptor with the pore cavities filled with the aerogel. And adding 24.84g of citric acid into the system, stirring for 2h at 95 ℃, after the reaction is finished, carrying out rotary evaporation for 3h at 90 ℃ to remove the ethanol solvent, thus obtaining the orange degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the degradable adhesive is 0.047W/(m.K), and the complete degradation time in soil is 45 days. The thermal conductivity of the cellulose aerogel in this example was 0.025W/(m.K).
Example 10:
respectively adding 25.94g of alpha-cyclodextrin and 35g of melamine-formaldehyde aerogel into 50mL of propanol, and stirring at 90 ℃ for 3.5h to obtain a hydrogen bond acceptor with a pore cavity filled with the aerogel. And adding 7.73g of malic acid into the system, stirring for 1h at 95 ℃, after the reaction is finished, rotationally evaporating for 7h at 70 ℃ to remove the propanol solvent to obtain the black brown degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.032W/(m.K), and the time for complete degradation in soil is 75 days. The thermal conductivity of the melamine-formaldehyde aerogel in this example was 0.019W/(m.K).
Example 11:
adding 25.94g of gamma-cyclodextrin and 55g of resorcinol-formaldehyde aerogel into 50mL of butanol respectively, and stirring at 110 ℃ for 6.5h to obtain a hydrogen bond acceptor with pore cavities filled with the aerogel. And adding 9.48g of ascorbic acid into the system, stirring for 3.5h at 100 ℃, after the reaction is finished, rotationally steaming for 6h at 120 ℃ to remove the ethanol solvent to obtain the gray degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.035W/(m.K), and the time for complete degradation in soil is 90 days. The thermal conductivity of the resorcinol-formaldehyde aerogel in this example was 0.014W/(m · K).
Example 12:
25.94g of beta-cyclodextrin was mixed with 45g of Al2O3Adding the aerogel into 50mL of propanol respectively, and stirring at 40 ℃ for 5.5h to obtain a hydrogen bond acceptor with a pore cavity filled with the aerogel. And adding 20.38g of succinic acid into the system, stirring for 4.5h at 90 ℃, after the reaction is finished, carrying out rotary evaporation for 3h at 80 ℃ to remove a propanol solvent, thus obtaining the black brown degradable adhesive containing aerogel, wherein the thermal conductivity coefficient of the adhesive is 0.055W/(m.K), and the time for complete degradation in soil is 120 days. Al in this example2O3The thermal conductivity of the aerogel is 0.021W/(m.K).
Example 13:
referring to example 12, except that the adhesive used a commercially available one-component epoxy glue (model JL-6103), the procedure was as follows: 45g of Al2O3Adding the aerogel into 46.32g of single-component epoxy resin adhesive, stirring for 4.5 hours at 90 ℃, and obtaining the conventional organic adhesive containing the aerogel after the reaction is finished, wherein the thermal conductivity coefficient of the conventional organic adhesive is 0.14W/(m.K), and the aerogel can not be uniformly dispersed in the single-component epoxy resin adhesive and is obviously agglomerated. The shape of the soil is not changed after 120 days, and the degradation is not obvious.
Example 14:
referring to example 2, except for the different reaction conditions, the process is as follows: 19.46g of alpha-cyclodextrin was mixed with 20g of Al2O3And respectively adding the aerogel into 50mL of propanol, and stirring for 1h at 20 ℃ to obtain the hydrogen bond acceptor with the pore space filled with the aerogel. 13.59g tartaric acid was added to the system, and the mixture was stirred at 80 ℃ for 2 hours, and after the reaction was completed, the propanol solvent was removed by rotary evaporation at 80 ℃ for 1 hour, and it was found that the product did not form a stable adhesive agent, and that an insoluble solid precipitated in the system and did not have a stable appearance.
Secondly, testing the adhesion performance of the material surface coated with the degradable adhesive containing aerogel
Example 13:
2g of the aerogel-containing degradable adhesive of example 1 was uniformly applied to a metal surface of 10cm × 10cm to form an adhesive layer of 1mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was washed with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in table 1.
Example 14:
1g of the aerogel-containing degradable adhesive of example 2 was uniformly coated on a fiber surface of 10cm × 10cm to form an adhesive layer of 0.5mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was cleaned with 50mL of methylene chloride for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in table 1.
Example 15:
5g of the aerogel-containing degradable adhesive of example 3 was uniformly applied to a 10cm × 10cm glass surface to form an adhesive layer of 3mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was cleaned with 50mL of acetone for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in Table 1.
Example 16:
8g of the aerogel-containing degradable adhesive of example 4 was uniformly applied to a plastic surface of 10cm × 10cm to form an adhesive layer of 5mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was cleaned with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in Table 1.
Example 17:
10g of the aerogel-containing degradable adhesive of example 5 was uniformly applied to a plastic surface of 10cm × 10cm to form an adhesive layer of 8mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was cleaned with 50mL of diethyl ether for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in Table 1.
Example 18:
4g of the aerogel-containing degradable adhesive of example 6 was uniformly applied to a glass surface of 10cm × 10cm to form an adhesive layer of 2.5mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was washed with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in Table 1.
Example 19:
3g of the aerogel-containing degradable adhesive of example 7 was uniformly applied to a metal surface of 10cm × 10cm to form an adhesive layer of 2mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was washed with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in Table 1.
Example 20:
13g of the aerogel-containing degradable adhesive of example 8 was uniformly applied to a 10cm × 10cm fiber surface to form a 10mm adhesive layer, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was washed with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in table 1.
Example 21:
an adhesive layer of 9mm was formed by uniformly coating 11g of the aerogel-containing degradable adhesive of example 9 on a glass surface of 10cm × 10cm, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, and then the adhesive layer was cleaned with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in table 1.
Example 22:
6g of the aerogel-containing degradable adhesive of example 10 was uniformly applied to a plastic surface of 10cm × 10cm to form an adhesive layer of 4mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was washed with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in Table 1.
Example 23:
3g of the aerogel-containing degradable adhesive of example 11 was uniformly applied to a fiber surface of 10cm × 10cm to form an adhesive layer of 1.5mm, the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was washed with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel-containing degradable adhesive to the metal surface was measured again, and the results are shown in Table 1.
Example 24:
9.5g of the aerogel containing degradable adhesive of example 12 was uniformly coated on a metal surface of 10cm × 10cm to form an adhesive layer of 7mm, the adhesive strength of the aerogel containing degradable adhesive to the metal surface was measured by an ST-D200 adhesive adhesion tester, the adhesive layer was washed with 50mL of deionized water for half an hour, and the adhesive strength of the aerogel containing degradable adhesive to the metal surface was measured again, and the results are shown in table 1.
Comparative example 1:
3g of an inorganic adhesive aluminosilicate sealant (model DB5016, thermal conductivity 0.53W/(m.K), non-degradable) is uniformly coated on a metal surface of 10cm multiplied by 10cm to form an adhesive layer of 2mm, an ST-D200 adhesive adhesion tester is used for measuring the adhesive strength of the degradable adhesive containing aerogel and the metal surface, then 50mL of deionized water is used for cleaning the adhesive layer for half an hour, and the adhesive strength of the degradable adhesive containing aerogel and the metal surface is measured again, and the result is shown in Table 1.
Comparative example 2:
3g of organic adhesive epoxy resin AB glue (model E-60HP, heat conductivity coefficient 0.061W/(m.K), non-degradable) is uniformly coated on a metal surface of 10cm multiplied by 10cm to form an adhesive layer of 2mm, the adhesive strength of the degradable adhesive containing aerogel and the metal surface is measured by an ST-D200 adhesive adhesion tester, then the adhesive layer is cleaned by 50mL of deionized water for half an hour, and the adhesive strength of the degradable adhesive containing aerogel and the metal surface is measured again, and the results are shown in Table 1.
TABLE 1 adhesive strength of the adhesive and the material surface in examples 13 to 24 and comparative examples 1 to 2
As can be seen from the measurement results of the inventive examples and comparative examples: the adhesive strength of the degradable adhesives in examples 13 to 24 was higher than that of the inorganic adhesive and the organic adhesive in comparative examples 1 to 2. After being cleaned by deionized water and an organic solvent, the adhesive strength of the degradable adhesives in the examples 13-24 disappears, while the adhesive strength of the inorganic adhesive in the comparative example 1 is slightly reduced, and the adhesive strength of the adhesive in the comparative example 2 is unchanged. The test result shows that the degradable adhesive provided by the invention has good adhesion performance and is easy to clean by water.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (10)
1. A preparation method of a degradable adhesive is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing the hydrogen bond acceptor, the aerogel and a solvent, and reacting to obtain a compound;
(2) and mixing the compound with a hydrogen bond donor, and removing the solvent after reaction to obtain the degradable adhesive.
2. The method for preparing the degradable adhesive according to claim 1, wherein: the hydrogen bond acceptor has a pore cavity with the pore diameter of 100-500nm, and the compound is the hydrogen bond acceptor with the pore cavity filled with aerogel.
3. The method for preparing the degradable adhesive according to claim 2, wherein: the hydrogen bond acceptor is one or a mixture of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
4. The method for preparing a degradable adhesive according to any one of claims 1 to 3, wherein: the hydrogen bond donor is one or more of oxalic acid, tartaric acid, citric acid, succinic acid, quinic acid, malic acid and ascorbic acid;
optionally, the solvent is methanol, ethanol, propanol or butanol.
5. The method for preparing a degradable adhesive according to any one of claims 1 to 3, wherein: the aerogel is SiO2Aerogel, Al2O3One or more of aerogel, cellulose aerogel, graphene aerogel, melamine-formaldehyde aerogel and resorcinol-formaldehyde aerogel.
6. The method for preparing a degradable adhesive according to any one of claims 1 to 3, wherein: mixing the hydrogen bond acceptor and the aerogel in the step (1) according to a molar ratio of 1: 0.1-1: 10;
optionally, the molar ratio of the hydrogen bond acceptor in the compound in the step (2) to the hydrogen bond donor is 1: 0.1-1: 20.
7. The method for preparing a degradable adhesive according to any one of claims 1 to 3, wherein: the reaction temperature in the step (1) and/or the step (2) is 0-180 ℃, and the reaction time is 1-10 h; preferably, the temperature in the step (2) is 90-150 ℃, and the time is 3-8 h.
8. The degradable adhesive prepared by the method for preparing the degradable adhesive according to any one of claims 1 to 7, wherein the degradable adhesive is prepared by: the time for the degradable adhesive to be completely degraded in the soil is 15-120 days.
9. The degradable adhesive of claim 8, wherein: the adhesive strength of the degradable adhesive is 6-8 MPa; the degradable adhesive has heat insulation performance, and the heat conductivity coefficient is less than 0.019W/(m.K);
the degradable adhesive is easy to remove, and can be removed by cleaning the degradable adhesive with water or an organic solvent.
10. Use of the degradable adhesive of claim 8 or 9 in the field of bonding articles.
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CN111234733A (en) * | 2020-02-24 | 2020-06-05 | 中国农业科学院麻类研究所 | Eutectic solvent, environment-friendly adhesive and preparation method thereof |
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US20210332270A1 (en) * | 2020-04-27 | 2021-10-28 | Taiwan Aerogel Technology Material Co., Ltd. | Method for producing a high temperature resistant, heat insulating, and fireproof composite glue composed of an aerogel and an inorganic fiber and the application of the related product |
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CN101792299A (en) * | 2010-01-08 | 2010-08-04 | 中国人民解放军国防科学技术大学 | Method for preparing heat-resisting alumina-silox aerogel thermal-protective composite material |
CN111234733A (en) * | 2020-02-24 | 2020-06-05 | 中国农业科学院麻类研究所 | Eutectic solvent, environment-friendly adhesive and preparation method thereof |
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