CN116285454A - Polymerizable monomer eutectic solvent, adhesive obtained by polymerization of polymerizable monomer eutectic solvent and preparation method of adhesive - Google Patents
Polymerizable monomer eutectic solvent, adhesive obtained by polymerization of polymerizable monomer eutectic solvent and preparation method of adhesive Download PDFInfo
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- CN116285454A CN116285454A CN202310287410.8A CN202310287410A CN116285454A CN 116285454 A CN116285454 A CN 116285454A CN 202310287410 A CN202310287410 A CN 202310287410A CN 116285454 A CN116285454 A CN 116285454A
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- hydrogen bond
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- eutectic solvent
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 76
- 239000000853 adhesive Substances 0.000 title claims abstract description 73
- 230000005496 eutectics Effects 0.000 title claims abstract description 72
- 239000000178 monomer Substances 0.000 title claims abstract description 72
- 239000002904 solvent Substances 0.000 title claims abstract description 71
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 63
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 239000000123 paper Substances 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000002023 wood Substances 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- -1 N-dimethylacrylamide Chemical compound 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 15
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- CHUPNGGCNPHUEN-UHFFFAOYSA-M potassium;ethanesulfonate Chemical compound [K+].CCS([O-])(=O)=O CHUPNGGCNPHUEN-UHFFFAOYSA-M 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 12
- 101100498930 Mus musculus Degs1 gene Proteins 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001510 metal chloride Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- QWJSAWXRUVVRLH-LREBCSMRSA-M 2-hydroxyethyl(trimethyl)azanium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound C[N+](C)(C)CCO.OC(=O)[C@H](O)[C@@H](O)C([O-])=O QWJSAWXRUVVRLH-LREBCSMRSA-M 0.000 description 1
- KZSXRDLXTFEHJM-UHFFFAOYSA-N 5-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(C(F)(F)F)=C1 KZSXRDLXTFEHJM-UHFFFAOYSA-N 0.000 description 1
- ZCUFTCUMEDALHC-UHFFFAOYSA-N CC[K] Chemical compound CC[K] ZCUFTCUMEDALHC-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Images
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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The invention provides a polymerizable monomer type eutectic solvent, an adhesive obtained by polymerization of the polymerizable monomer type eutectic solvent and a preparation method of the adhesive. The monomer type eutectic solvent is formed by mixing a hydrogen bond acceptor and a hydrogen bond donor at 50-90 ℃, wherein the hydrogen bond acceptor comprises inorganic metal salt, the hydrogen bond donor comprises acrylamide/acrylic acid monomer, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:0.2-1:15. The invention discloses raw materials of an adhesive, which comprises the following components: the monomer type eutectic solvent and an initiator. The preparation method of the adhesive comprises the following steps: and uniformly mixing the raw materials, and initiating polymerization under illumination. The invention innovatively provides a monomer type eutectic solvent for preparing an adhesive, which is prepared by directly mixing an inorganic metal salt hydrogen bond acceptor and a monomer hydrogen bond donor containing unsaturated double bonds. The adhesive disclosed by the invention has the advantages of simple preparation method, quick solidification, no solvent volatilization, convenient operation and high transparency, is suitable for bonding the surfaces of various substrates such as glass, ceramics, paper, wood, polymethyl methacrylate, metallic zinc, aluminum, titanium, stainless steel and the like, and can be separated from a bonded object after absorbing moisture.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polymerizable monomer type eutectic solvent, an adhesive obtained by polymerization and a preparation method thereof.
Background
The adhesive can bond two independent surfaces of articles together, has been widely used in the fields of industry and daily life such as medical treatment, automobiles, electronics, human-computer interfaces, product packaging, house construction, etc., and particularly, many adhesives having special properties have been manufactured. However, known adhesives tend to have poor bond strength and require some physicochemical means to release from the object upon release. The common method for removing adhesion mainly comprises solvent soaking, accelerated aging and the like, and is easy to cause surface corrosion in the separation process, and the solvent volatilization and other environmental problems can be caused. Thus, the biggest challenge in manufacturing an on-demand debonded adhesive is how to achieve easy switching between strongly bonded and non-bonded states using environmentally friendly triggers.
The eutectic solvent (deep eutectic solvent, DES) is a two-component or multi-component eutectic mixture of hydrogen bond acceptors (HBA, such as quaternary ammonium salts) and hydrogen bond donors (HBD, such as amide, carboxylic acid, and polyol compounds) in stoichiometric proportions, with the freezing point significantly lower than the melting point of the individual component purities. The advent of eutectic gel adhesives provides a solution for preparing on-demand debonded adhesives. The bonding principle is that the eutectic gel can generate interaction forces such as hydrogen bonds, metal complexation, ion-dipole interaction, electrostatic interaction and the like with the substrate surface, and can be effectively attached to different substrate surfaces. On the other hand, the hydrogen bonding is easily affected by water molecules, and the bonding strength is weakened after water is absorbed, so that quick nondestructive debonding can be realized. A common method of preparing a eutectic gel adhesive is to first prepare DES, then dissolve the polymerizable monomers in DES, and finally initiate the polymerization reaction to form a network of polymer material comprising DES Chemical Engineering Journal 2022, 442, 136289.
The monomeric eutectic solvents (monomeric deep eutectic solvent, mDES) are a novel class of DES whose hydrogen bond donor moiety itself is a monomer containing a polymerizable double bond functionality. The hydrogen bond donor component in mDES is both a solvent medium and a polymerized monomer during its polymerization. Depending on the monomer structure, the hydrogen bond donor component may also be a special functional filler. Likewise, mDES obtains an adhesive material by thermally or photo-initiated polymerization, and de-adhesion is achieved by an environmentally friendly moisture uptake method. The current preparation method of mDES generally uses quaternary ammonium salt compounds, such as choline dihydrogen citrate, choline chloride or choline tartrate, as hydrogen bond acceptors, and uses monomers with amine, amide, hydroxyl or carboxylic acid groups, such as acrylic acid, methacrylic acid, acrylamide or methacrylamide, as hydrogen bond donors, and the { chinese patent application number: 201811465819.X, 201910853528.6, 202011540620.6, 202110972589.1, 202111268968.9}. Although there has been a study of eutectic gel adhesives { chinese patent application No. 202111268968.9; chemical Engineering Journal 2022, 442, 136289. The adhesive is prepared by preparing a eutectic solvent from choline chloride and urea, then adding acrylic acid and an initiator, and irradiating with ultraviolet light. At present, research reports on monomer type eutectic solvents and corresponding adhesives prepared by taking inorganic metal salts as hydrogen bond acceptors and unsaturated double bond-containing monomers as hydrogen bond donors are not seen.
Disclosure of Invention
The invention aims to provide a polymerizable monomer type eutectic solvent, an adhesive obtained by polymerization and a preparation method thereof, wherein the monomer type eutectic solvent has the advantages of simple preparation method, 100% of atom utilization rate, low cost and the like, and can be polymerized by ultraviolet irradiation, and the adhesive has the advantages of simple preparation process, quick solidification, no Volatile Organic Compounds (VOCs), high transparency, high adhesion, adhesion removal according to requirements and the like, and is suitable for bonding various base materials.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the first aspect of the present invention provides a monomer type eutectic solvent for preparing an adhesive, which comprises the following raw materials: a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond donor contains an unsaturated double bond.
Preferably, the hydrogen bond donor is an acrylamide or acrylic monomer.
Preferably, the acrylamide or acrylic acid (ester) monomer is one or more of acrylamide, N-isopropyl acrylamide, N-dimethyl acrylamide, acrylic acid, methacrylic acid and hydroxyethyl methacrylate.
Preferably, the hydrogen bond acceptor comprises one or more of zinc tetrafluoroborate, ferric chloride, copper chloride, magnesium chloride, aluminum chloride, lithium perchlorate, lithium nitrate, lithium acetate, sodium trifluoroacetate, potassium ethylsulfonate, and zinc acetate.
Preferably, the molar ratio between the hydrogen bond acceptor and the hydrogen bond donor is 1:0.2-1:15.
The second aspect of the present invention provides an adhesive comprising the following raw material components, each independently stored: the monomeric eutectic solvent of the first aspect, further comprising an initiator. The monomer type eutectic solvent and the initiator.
Preferably, the initiator is a photoinitiator; including one or more of 2-oxoglutarate, 2-hydroxy-2-methyl-1-phenyl-1-propanone (PI 1173), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropenode (PI 2959).
The adhesive described herein, passing the shear tensile test, has a tensile strength with the substrate of >0.1MPa.
The third aspect of the present invention provides a method for preparing the adhesive, comprising the steps of:
step 1: mixing the hydrogen bond acceptor and the hydrogen bond donor, and stirring at a certain temperature and time until a uniform solution is formed, thus obtaining a monomer type eutectic solvent;
step 2: adding an initiator into the solution prepared in the step 1, uniformly mixing, and polymerizing under certain reaction conditions to obtain an adhesive;
preferably, the certain temperature in the step 1 is any value between 50 ℃ and 90 ℃ and the time is any value between 0.5h and 24 h;
preferably, the polymerization condition of the step 2 is ultraviolet irradiation polymerization, and the ultraviolet curing reaction time is determined by corresponding polymerization reaction and irradiation power.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention creatively discovers that a monomer type eutectic solvent can be formed by mixing different monomer type hydrogen bond donors and hydrogen bond acceptors under certain conditions, and the eutectic solvent can be applied to preparing special adhesives with high adhesive strength, high transparency and mild adhesion removal.
(2) According to the adhesive provided by the invention, the monomer type eutectic solvent and the initiator are selected as raw materials, and a hydrogen bond network is generated between polymers formed by a hydrogen bond acceptor and a hydrogen bond donor, so that the effect of dissipating mechanical force is achieved, and the adhesive has the advantages of high bonding strength and moisture triggering and releasing; meanwhile, the raw materials are easy to obtain, so that the performance and the safety are improved, and the cost of the raw materials is reduced; in addition, the adhesive is suitable for bonding various substrates such as glass, ceramic, paper, wood, polymethyl methacrylate (PMMA), metallic zinc, aluminum, titanium, stainless steel and the like, becomes an adhesive which is green, low in cost, high in strength, simple in process and easy to debond, and has a great application prospect.
Drawings
FIG. 1 mDES pictures of different molar ratios prepared from zinc tetrafluoroborate and acrylamide in example 1
FIG. 2A photograph of zinc tetrafluoroborate and mDES composed of different kinds of monomers in example 2
FIG. 3A photograph of mDES composed of a metal salt and different acrylic monomers in example 3
FIG. 4A photograph of the mDES of acrylamide monomer and different metal chlorides in example 4
FIG. 5A photograph of mDES composed of acrylamide monomer and other metal salts in example 5
FIG. 6 is a DSC of the monomeric eutectic solvent mDES-4 prepared in example 1
FIG. 7 is a nuclear magnetic pattern of the monomeric eutectic solvent mDES-4 and monomeric acrylamide (AAm) prepared in example 1
FIG. 8 Nuclear magnetic resonance image of the adhesive prepared in example 8
FIG. 9 DSC of the adhesive prepared in example 8
FIG. 10 stress-strain diagram of the adhesive prepared in example 8
FIG. 11 is a graph showing transmittance of the adhesive prepared in example 8 of the present invention
FIG. 12 is a graph showing the adhesion properties of the adhesive prepared in example 8 to various substrates
FIG. 13 is a graph showing the adhesion property of the adhesive prepared in example 14 to a glass substrate
FIG. 14 shows an adhesion test chart in example 15
FIG. 15 is a graph showing the results of the adhesion performance in water at 90℃after the adhesive prepared in example 8 has adhered to a glass substrate
Detailed Description
The drawings are for illustrative purposes only and are not to be construed as limiting the invention.
The present invention will be described in detail by examples. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention further. In the following examples, all of the various raw materials used were commercially available unless otherwise specified.
Example 1
Monomer type eutectic solvent formed by mixing zinc tetrafluoroborate and acrylamide in different molar ratios
According to zinc tetrafluoroborate: the molar ratio of the acrylamide is 1:0.2-1:15, zinc tetrafluoroborate and acrylamide with different masses are weighed and mixed in a reaction vessel, and then the mixture is stirred at about 60 ℃ for about half an hour, so that a series of monomer eutectic solvents with different molar ratios can be prepared (figure 1). The monomer-based eutectic solvent was designated mDES-x according to the change in the molar ratio x of hydrogen bond acceptor/hydrogen bond donor. As can be seen from fig. 1, the mixture of acrylamide and zinc tetrafluoroborate is heated and stirred to be changed from solid state to uniform liquid state, which indicates that zinc tetrafluoroborate and acrylamide can form a monomer type eutectic solvent with different molar ratios, wherein the molar ratio ranges from 1:0.2 to 1:15.
Example 2
Monomer type eutectic solvent formed by mixing zinc tetrafluoroborate and different monomers
Zinc tetrafluoroborate: the zinc tetrafluoroborate and the monomer are weighed according to the molar ratio of 1:5, wherein the monomers are respectively acrylamide (AAm), N-isopropyl acrylamide (NIPAM), N-dimethyl acrylamide (DMA) and hydroxyethyl methacrylate (HEMA), and then the monomers are mixed in a reaction container and stirred for 0.5h at 65 ℃ to form the monomer type eutectic solvent. The diagram of the monomer type eutectic solvent composed of zinc tetrafluoroborate and different monomers is shown in figure 2.
As can be seen from fig. 2, the mixture of zinc tetrafluoroborate and AAm, DMA, NIPAM, HEMA was heated and stirred to form a uniform liquid, which indicates that zinc tetrafluoroborate and different monomers can form a monomer-type eutectic solvent.
Example 3
Monomer type eutectic solvent formed by mixing metal salt and acrylic monomer
The metal salt is as follows: the molar ratio of the monomers is 1:5, metal salt and the monomers are weighed, wherein the metal salt can be lithium chloride, sodium trifluoroacetate, lithium nitrate and lithium acetate, and the monomers are acrylic acid (AAc), methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAA) respectively, and then the monomers are mixed in a reaction container and stirred for 0.5h at 65 ℃ to form the monomer type eutectic solvent. The monomeric eutectic solvents of the metal salts and the different monomers are shown in figure 3.
As can be seen from fig. 3, the mixture of the metal salt and AAc, MAA, HEMA is uniformly liquid after being heated and stirred, which indicates that the metal salt and different monomers can form a monomer type eutectic solvent.
Example 4
Monomer type eutectic solvent composed of acrylamide monomer and different metal chlorides
With hydrogen bond acceptors: the molar ratio of acrylamide is 1:5, and hydrogen bond acceptor metal is weighed for chlorinationAnd acrylamide, wherein the hydrogen bond acceptor metal chlorides are respectively ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O), copper chloride dihydrate (CuCl) 2 ·2H 2 O), magnesium chloride hexahydrate (MgCl) 2 ·6H 2 O), lithium chloride (LiCl), aluminum chloride, hexahydrate (AlCl) 3 ·6H 2 O), mixing in a reaction vessel, and stirring for 1h at 65 ℃ to form the monomer type eutectic solvent. The diagram of the monomeric eutectic solvents for different metal chlorides is shown in fig. 4.
As can be seen from fig. 4, the mixture of acrylamide and different hydrogen bond acceptor metal chlorides is heated and stirred to change from solid state to uniform liquid state, which indicates that the acrylamide monomer and different metal chlorides can form a monomer type eutectic solvent.
Example 5
Monomer eutectic solvent composed of acrylamide monomer and other hydrogen bond acceptor inorganic metal salt
With hydrogen bond acceptors: the molar ratio of the acrylamide to the hydrogen bond acceptor is 1:5, wherein the hydrogen bond acceptor is lithium perchlorate, sodium acetate and ethyl potassium xanthate (CH) 3 CH 2 OS 2 K) Zinc acetate (Zn (CH) 3 COO) 2 ) Mixing in a reaction vessel, and stirring at 65 ℃ for 1h to form the monomer type eutectic solvent. The monomeric eutectic solvent patterns for different hydrogen bond acceptors are shown in figure 5.
As can be seen from fig. 5, the mixture of acrylamide and other hydrogen bond acceptor inorganic metal salts is heated and stirred to change from solid state to uniform liquid state, which indicates that acrylamide monomer and other hydrogen bond acceptors can form monomer type eutectic solvent.
Example 6
Differential Scanning Calorimeter (DSC) characterization of the monomeric eutectic solvent abbreviated mDES-4 in example 1
Whether the melting point of the monomeric eutectic solvent mDES-4 prepared in example 1 was lower than that of each single component was confirmed by DSC, indicating whether the monomeric eutectic solvent was prepared. Specifically, about 10mg of the monomeric eutectic solvent mDES-4 prepared in example 1 was taken as a standardIn an aluminum crucible, nitrogen (N) 2 ) DSC test is carried out in atmosphere, the temperature range is-100-80 ℃, and the temperature rising and reducing rate is 10 ℃/min.
The DSC test results are shown in FIG. 6, from which it can be seen that the melting point of the monomeric eutectic solvent mDES-4 prepared in example 1 is 42.5℃which is far lower than that of the one-component zinc tetrafluoroborate (T) m =158 to 168 ℃) or acrylamide (T m =82 to 86 ℃), indicating that the monomer-type eutectic solvent mDES-4 described in example 1 was successfully prepared.
Example 7
Nuclear magnetic characterization of the monomeric eutectic solvent abbreviated mDES-4 in example 1
20. Mu.L or 15mg of acrylamide monomer (AAm) of the monomer type eutectic solvent obtained in example 1 was dissolved in 0.5mL of heavy water (D 2 O), the presence or absence of polymerization of the hydrogen bond donor during heating is characterized by nuclear magnetism. The nuclear magnetic test results are shown in FIG. 7.
From FIG. 7 1 As can be seen from the H-NMR spectrum, only characteristic peaks corresponding to acrylamide (AAm) monomer were observed at 5.64ppm, 6.32ppm and 6.51ppm of mDES-4 in example 1, and no characteristic peaks of the polymer were found.
Example 8
The present embodiment provides a monomer-based eutectic solvent-based adhesive comprising
Acrylamide 1.4216g;
1.159g of zinc tetrafluoroborate;
0.0088g of photoinitiator 2-oxoglutarate;
and is prepared as follows:
step 1: and weighing acrylamide and zinc tetrafluoroborate, heating and stirring in a container at 60 ℃ to form a uniform solution, and thus completing the preparation of the monomer type eutectic solvent.
Step 2: weighing an initiator, adding the initiator into the eutectic solvent in the step 1 for dissolution, and then coating the solution on the surface of a substrate and curing the substrate by ultraviolet irradiation. The power of the ultraviolet lamp light source is 30W, and the irradiation time is 20min.
Example 9
Nuclear magnetic characterization of the adhesive prepared in example 8
Example 9 was performed using the same procedure as in example 8, except that the solution prepared in step 2 was added between the jaws covered with release film surfaces on both sides, the jaws were separated by silicone rubber, and the sample was prepared by uv irradiation. The test was performed on a nuclear magnetic resonance spectrometer. Specifically, 10 to 15mg of the adhesive prepared in example 8 was dissolved in 0.5mL of heavy water (D 2 O) whether the prepared adhesive is polymerized or not by nuclear magnetic characterization. The nuclear magnetic resonance results are shown in FIG. 8.
FIG. 8 is a graph of the binding agent described in example 1, mDES-4 and example 8 1 H NMR nuclear magnetic spectrum. As can be seen from FIG. 8, the adhesive curve of example 8 shows two new peaks at 1.5ppm to 2.5ppm, corresponding to the characteristic absorption peaks of protons at the main chain carbon atoms in polyacrylamide (PAAm), respectively, indicating that mDES-4 forms polymer PAAm after UV light irradiation. The monomer conversion rate can be calculated to be up to 99% through a nuclear magnetic spectrum.
Example 10
DSC characterization of the adhesive prepared in example 8
Example 10 was performed using the same procedure as in example 8, except that the solution prepared in step 2 was added to the middle of the clamping plate with the release film surfaces on both sides, the layers were separated by silicone rubber, and the sample was prepared after uv irradiation. The adhesive prepared in example 8 was confirmed to be crystalline or amorphous structure by Differential Scanning Calorimeter (DSC). Specifically, about 10mg of the adhesive prepared in example 8 was taken in an aluminum crucible at a temperature ranging from-100 to 120℃and a heating rate of 10℃per minute. As can be seen from DSC test results FIG. 9, the DSC curve of the adhesive shows no crystallization peak in the temperature range of-100 to 120 ℃, revealing that the adhesive is an amorphous structure, the glass transition temperature (T g ) 72.8 ℃.
Example 11
Stress-strain diagram test of adhesive prepared in example 8
Example 11 was performed using the same procedure as in example 8, except that the solution prepared in step 2 was added to a silicone dumbbell mold in example 11. The tensile properties of dumbbell-shaped samples after uv irradiation were tested, with a tensile rate of 50mm/min. The test results are shown in FIG. 10.
As can be seen from fig. 10, the maximum fracture length of the adhesive is about 12% and the maximum fracture stress reaches 40MPa. The stress-strain curve results indicate that the adhesive prepared in example 8 has excellent mechanical properties.
Example 12
Transmittance test of the adhesive prepared in example 8
Example 12 the same procedure as in example 8 was followed except that the solution prepared in step 2 was added to the middle of a splint having release film surfaces on both sides, the spacers were separated by silicone rubber to control the thickness, and ultraviolet light irradiation was used to prepare 3X 1mm 3 A sheet. The transmittance curve of the sample was measured on an ultraviolet-visible spectrophotometer, and the result is shown in fig. 11.
FIG. 11 is an ultraviolet-visible (UV-Vis) spectrum of the sample obtained in example 12 as described. The film described in example 12 showed a transmittance of more than 87% in the wavelength range of 400-800nm due to no phase separation or light absorption. An adhesive film having a thickness of 1mm was placed on the colored pattern, which was clearly visible to the naked eye (fig. 11 inset), showing excellent optical clarity.
Example 13
Adhesion Performance test of the adhesive prepared in example 8 to bond various substrates
Example 13 the same procedure as in example 8 was followed, except that the adhesion performance of the adhesive to various substrates was tested in example 13 by ultraviolet curing after the solution prepared in step 2 was applied to the surfaces of the various substrates.
FIG. 12 is a schematic photograph showing a weight of 3kg lifted after the adhesive prepared in example 13 has adhered various substrates of glass, ceramic, paper, wood, PMMA, zinc, aluminum, titanium, stainless steel, etc., the adhesive adhered to the substrate has a spreading area of approximately 9cm 2 The weight mass was about 3kg. FIG. 12 showsThe adhesive prepared by the invention can be firmly combined with various base materials, and has excellent adhesive property.
Example 14
Preparation of adhesives based on other monomer-type eutectic solvents and adhesion performance test thereof
Example 14 was carried out using the same procedure as in example 8, except that the hydrogen bond acceptor and hydrogen bond donor combination used in example 14 was (1) zinc tetrafluoroborate and hydroxyethyl methacrylate, (2) zinc tetrafluoroborate and N-isopropylacrylamide, (3) zinc tetrafluoroborate and N, N-dimethylacrylamide, and (4) lithium chloride and acrylic acid, respectively. The corresponding adhesives were designated G-Zn/HEMA, G-Zn/NIPAM, G-Zn/DMA, G-Li/AAc.
FIG. 13 is a schematic photograph showing the performance of the adhesive-bonded glass substrate prepared in example 14 in lifting a weight, the adhesive-bonded substrate having an area of approximately 9cm 2 The weight mass was about 3kg. Fig. 13 shows that the adhesive based on the other monomer type eutectic solvent prepared in the present invention can be firmly combined with various substrates, and has excellent adhesive properties.
Example 15
Preparation of monomer type eutectic adhesive under different illumination conditions
Referring to example 8, the ultraviolet lamp irradiation time of example 15 was 10min, 20min and 40min to initiate polymerization.
Fig. 14 is the adhesion properties of examples 8 and 15 obtained by performing lap shear experiments. The results show that the shear strength tends to increase along with the prolongation of the illumination time of the ultraviolet light, but the shear strength is not obviously improved after the illumination time reaches a certain duration, which indicates that the strong interface interaction is not greatly changed once the strong interface interaction is completed.
Example 16
Test of debonding Property of the adhesive prepared in example 13 in 90 ℃ Water after bonding glass substrates
Example 16 the same procedure was followed as in example 13, with the glass as the bonding substrate being cured, and then the spliced glass was immersed in water at 90 ℃. Shear strength was tested by lap shear test to obtain the adhesive properties of the adhesive and the change rule with the soaking time, and the results are shown in fig. 15:
fig. 15 shows the bonding strength of the lap test piece after immersion in water. The bond strength of example 16 was reduced from 8.86MPa to 2.99MPa in only 10 min. After 60min, the bonding strength was reduced to 0.16MPa. In the formulation of example 13, polyacrylamide (PAAm) produced after mDES polymerization acts as a superabsorbent polymer. Therefore, water can gradually diffuse into the bulk binder and interface as a donor and acceptor of hydrogen, breaking the original hydrogen bond network, thereby deteriorating interfacial cohesion and adhesion.
Claims (8)
1. The monomer type eutectic solvent is characterized in that the preparation raw materials comprise: a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is an inorganic metal salt, and the hydrogen bond donor is an acrylamide/acrylic monomer containing unsaturated double bonds. Wherein the molar ratio between the hydrogen bond acceptor and the hydrogen bond donor is 1:0.2-1:15.
2. The monomeric eutectic solvent of claim 1, wherein the acrylamide/acrylic monomer comprises one or more of acrylamide, N-isopropylacrylamide, N-dimethylacrylamide, acrylic acid, methacrylic acid, hydroxyethyl methacrylate.
3. The monomeric eutectic solvent of claim 1, wherein the hydrogen bond acceptor comprises one or more of zinc tetrafluoroborate, ferric trichloride, cupric chloride, magnesium chloride, aluminum chloride, lithium perchlorate, lithium nitrate, lithium acetate, sodium trifluoroacetate, potassium ethylsulfonate, zinc acetate.
4. A method for preparing the monomeric eutectic solvent according to any one of claims 1 to 3, wherein the method comprises the steps of: and mixing the hydrogen bond acceptor and the hydrogen bond donor, and stirring at 50-90 ℃ until the solid is completely dissolved, thus obtaining the monomer type eutectic solvent.
5. An adhesive comprising the following raw material components, each of which is stored independently: a monomeric eutectic solvent, initiator according to any one of claims 1 to 3. Wherein the dosage (molar quantity) of the initiator is 0.01-1% of hydrogen bond donor.
6. The adhesive of claim 5, wherein the initiator is a photoinitiator; preferably, the photoinitiator comprises one or more of 2-oxoglutarate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionne.
7. A method of preparing the adhesive of any one of claims 5 to 6, comprising the steps of:
step 1: mixing a hydrogen bond acceptor and a hydrogen bond donor, and stirring at a certain temperature until a uniform solution is formed, thus obtaining a monomer type eutectic solvent;
step 2: adding an initiator into the solution prepared in the step 1, uniformly mixing, and polymerizing under the illumination condition to obtain an adhesive;
preferably, the temperature in the step 1 is 50-90 ℃ and the time is 0.5-2 h;
preferably, the polymerization conditions of step 2 are ultraviolet irradiation polymerization.
8. An adhesive according to any one of claims 5 to 7, wherein the adhesive is suitable for bonding a wide variety of substrates such as glass, ceramic, paper, wood, polymethyl methacrylate, metallic zinc, aluminum, titanium, stainless steel, and the like.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070021962A (en) * | 2005-08-19 | 2007-02-23 | 주식회사 엘지화학 | Electrolyte comprising eutectic mixture |
| KR20070071731A (en) * | 2005-12-30 | 2007-07-04 | 주식회사 엘지화학 | Electrochromic device having electrolyte comprising eutectic mixture |
| US20070191517A1 (en) * | 2005-08-19 | 2007-08-16 | Lg Chem, Ltd. | Acrylic pressure sensitive adhesive composition |
| CN101243134A (en) * | 2005-08-19 | 2008-08-13 | 株式会社Lg化学 | Electrolyte comprising eutectic mixture and electrochemical device using the same |
| CN111253520A (en) * | 2018-12-03 | 2020-06-09 | 华南理工大学 | Polymerizable eutectic solvent for self-repairing material, conductive elastomer and preparation method |
| CN112242561A (en) * | 2020-10-14 | 2021-01-19 | 哈尔滨工业大学（深圳） | Eutectic solvent electrolyte, preparation method thereof and lithium metal battery |
| CN112341958A (en) * | 2020-11-20 | 2021-02-09 | 中国农业科学院麻类研究所 | Preparation method of adhesive capable of simultaneously resisting high temperature and low temperature |
| KR102276980B1 (en) * | 2020-01-03 | 2021-07-13 | 건국대학교 산학협력단 | Complex deep eutectic solvent and extraction method of useful component using the same |
| CN113621100A (en) * | 2021-08-24 | 2021-11-09 | 华南理工大学 | Polymerizable eutectic solvent, dry-type ion conductor prepared from polymerizable eutectic solvent and preparation method of dry-type ion conductor |
| CN114193764A (en) * | 2021-12-10 | 2022-03-18 | 珠海赛纳三维科技有限公司 | Material for three-dimensional molding, three-dimensional object, and printing method therefor |
| CN114262403A (en) * | 2021-12-17 | 2022-04-01 | 江南大学 | High-transparency self-repairing self-adhesive conductive elastic material and preparation method thereof |
-
2023
- 2023-03-22 CN CN202310287410.8A patent/CN116285454A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070021962A (en) * | 2005-08-19 | 2007-02-23 | 주식회사 엘지화학 | Electrolyte comprising eutectic mixture |
| US20070191517A1 (en) * | 2005-08-19 | 2007-08-16 | Lg Chem, Ltd. | Acrylic pressure sensitive adhesive composition |
| CN101243154A (en) * | 2005-08-19 | 2008-08-13 | Lg化学株式会社 | Acrylic pressure sensitive adhesive composition |
| CN101243134A (en) * | 2005-08-19 | 2008-08-13 | 株式会社Lg化学 | Electrolyte comprising eutectic mixture and electrochemical device using the same |
| KR20070071731A (en) * | 2005-12-30 | 2007-07-04 | 주식회사 엘지화학 | Electrochromic device having electrolyte comprising eutectic mixture |
| CN111253520A (en) * | 2018-12-03 | 2020-06-09 | 华南理工大学 | Polymerizable eutectic solvent for self-repairing material, conductive elastomer and preparation method |
| KR102276980B1 (en) * | 2020-01-03 | 2021-07-13 | 건국대학교 산학협력단 | Complex deep eutectic solvent and extraction method of useful component using the same |
| CN112242561A (en) * | 2020-10-14 | 2021-01-19 | 哈尔滨工业大学（深圳） | Eutectic solvent electrolyte, preparation method thereof and lithium metal battery |
| CN112341958A (en) * | 2020-11-20 | 2021-02-09 | 中国农业科学院麻类研究所 | Preparation method of adhesive capable of simultaneously resisting high temperature and low temperature |
| CN113621100A (en) * | 2021-08-24 | 2021-11-09 | 华南理工大学 | Polymerizable eutectic solvent, dry-type ion conductor prepared from polymerizable eutectic solvent and preparation method of dry-type ion conductor |
| CN114193764A (en) * | 2021-12-10 | 2022-03-18 | 珠海赛纳三维科技有限公司 | Material for three-dimensional molding, three-dimensional object, and printing method therefor |
| CN114262403A (en) * | 2021-12-17 | 2022-04-01 | 江南大学 | High-transparency self-repairing self-adhesive conductive elastic material and preparation method thereof |
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