CN114195651B - Underwater adhesive and preparation method thereof - Google Patents
Underwater adhesive and preparation method thereof Download PDFInfo
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- CN114195651B CN114195651B CN202111620582.XA CN202111620582A CN114195651B CN 114195651 B CN114195651 B CN 114195651B CN 202111620582 A CN202111620582 A CN 202111620582A CN 114195651 B CN114195651 B CN 114195651B
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- methylimidazole
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 96
- 239000000853 adhesive Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 28
- -1 1-ethyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000012430 organic reaction media Substances 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 2
- RFJSVARKFQELLL-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole;1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound CCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F RFJSVARKFQELLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- UNRVFVIZRXNZKT-UHFFFAOYSA-N CCCCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound CCCCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F UNRVFVIZRXNZKT-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 39
- 239000000758 substrate Substances 0.000 abstract description 24
- 239000007788 liquid Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 239000000017 hydrogel Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 31
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 21
- 239000011521 glass Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000003852 triazoles Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- PQHKBJOUOHLCCV-UHFFFAOYSA-N CC1(C=CC=CC1C(=O)C2=CC=C(C=C2)OCCO)O Chemical compound CC1(C=CC=CC1C(=O)C2=CC=C(C=C2)OCCO)O PQHKBJOUOHLCCV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000005923 long-lasting effect Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 244000140975 Prunus simonii Species 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
- C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F112/26—Nitrogen
- C08F112/28—Amines
-
- 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
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of hydrogel materials, and discloses a preparation method of a long-acting underwater adhesive with instant adhesion and high bonding strength when meeting water, which comprises the following steps: 1) The monomer is prepared through chemical synthesis; 2) Ultraviolet light is adopted to initiate free radical polymerization to prepare a liquid underwater adhesive; 3) The adhesive is uniformly coated on the surface of the substrate by a syringe to realize underwater adhesion. The adhesive obtained by the method can realize quick underwater adhesion within 20 seconds, has strong underwater bonding strength (350 kPa), and can maintain the adhesion effect for a long time (7 days). Not only makes up the defects that the solid adhesive has low bonding strength and is difficult to effectively adhere to complex surfaces, but also effectively solves the problem of low adhesion speed of common liquid adhesives, and can realize long-acting underwater adhesion.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a preparation method of a long-acting underwater adhesive with instant adhesion and high bonding strength when meeting water.
Background
The adhesive is widely applied to our daily life and industry. Currently, most adhesives on the market only achieve adhesion to dry objects in an air environment. However, in practical applications, it is often also desirable to bond wetted surfaces or to achieve adhesion in liquid media, such as implantable devices and wound dressings in the medical field, water-based energy devices, underwater sensors, repair of underwater materials, and the marine industry. Therefore, the development of new underwater adhesives that can be used in a wet/underwater environment has become an important goal in the adhesive research field.
Currently, research on underwater adhesive-based adhesives is advancing, and the adhesives can be classified into liquid adhesives and solid adhesives (tapes) according to their physical forms. The solid adhesive tape is simple to operate, but has weaker bonding strength than the liquid adhesive. For example, jianping, university of Hokkaido, et al, teach that an underwater adhesive tape is prepared based on a polymer of a cation-benzene ring structure, which is adhered only by pressing it against an underwater substrate, but has an adhesive strength of only 20 to 60kPa to glass under water. In addition, solid state tapes are often difficult to attach to substrates with complex surface structure morphologies due to physical morphology limitations. Liquid adhesives generally have strong adhesive strength, but require the glue to be cured under water to achieve strong interfacial bonding, and the curing process generally requires a certain time; in addition, curing of some glues requires external thermal stimulation or illumination, adding difficulty to the implementation of the adhering operation. For example, abraham Joy et al, university of Akron, U.S. developed a glue for underwater use with a bond strength of up to 100kPa, however, the method of implementation was cumbersome: when testing the bond strength, it took 5 minutes to apply glue under water, then hold under water for 15 minutes, and finally irradiate with ultraviolet light for 10 minutes.
Therefore, there is a need to develop an underwater adhesive which has the advantages of spontaneous and rapid underwater adhesion, high bonding strength and durable adhesion effect.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a long-acting underwater adhesive with instant adhesion and high bonding strength when meeting water. The method of the invention firstly synthesizes the monomer with a hydrophobic structure (benzene ring) and a physical interaction unit (amine), then prepares the underwater adhesive which is sticky when meeting water by utilizing the free radical polymerization reaction of the monomer in an organic reagent, and provides a specific implementation method of the adhesive. The adhesive can realize quick adhesion to a substrate within 20 seconds, has ideal underwater bonding strength (350 kPa), and can maintain long-term adhesion effect in water (7 days). Therefore, the adhesive not only can make up the defects that the solid adhesive has low bonding strength and is difficult to attach to a complex surface structure, but also can effectively solve the problems of low adhesion speed and limited long-term stability of the existing liquid adhesive.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides an adhesive monomer of formula (I),
wherein R1 and R2 are methyl, ethyl, isopropyl or ethanol simultaneously, or R1 and R2 are connected into a ring and combined with N between the two to form an imidazolyl or triazinyl.
Preferably, R1, R2 are both methyl, or R1 and R2 are linked to form a ring and combine with N therebetween to form an imidazolyl or triazinyl group.
In a second aspect, the present invention provides a method for preparing an adhesive monomer represented by the above formula (I), where the method is: dissolving alkaline substances in a solvent, adding amine substances under stirring conditions and protective atmosphere (nitrogen or inert gas, preferably nitrogen), slowly dropwise adding p-chloromethyl styrene, reacting at 50-60 ℃ for 24-30 hours (preferably at 50 ℃ for 24 hours) after the dropwise adding is finished, and performing aftertreatment on the obtained reaction solution to obtain an adhesive monomer shown in a formula (I);
the alkaline substance is sodium bicarbonate or potassium carbonate; the amine substance is dimethylamine, diethylamine, diisopropylamine, di-n-propylamine, imidazole, triazole, diethanolamine (preferably dimethylamine, imidazole or triazole); the ratio of the alkaline substance, the amine substance and the p-chloromethyl styrene substance is 1-2:0.05-5: 1.
when the amine substance is a gaseous substance at ordinary temperature, the amine substance may be added as an aqueous solution of the amine substance, and the concentration of the aqueous solution of the amine substance is 0.0005 to 0.01mol/mL (preferably 0.0008 mol/mL).
Further, the solvent includes, but is not limited to, ethanol, acetone, a mixed solution of water and acetone in a volume ratio of 1:1-2, tetrahydrofuran, dimethylsulfoxide, N-dimethylformamide, dichloromethane, chloroform, carbon tetrachloride, toluene, or the like.
Still further, the volume of the solvent is 2-20mL/g based on the mass of the alkaline substance.
Further, the present invention provides two methods of post-processing:
1. the post-treatment is as follows: filtering the reaction liquid, taking filtrate, removing solvent by rotary evaporation, purifying the obtained viscous liquid by an alkaline alumina chromatographic column, collecting eluent containing a target compound, volatilizing the solvent at room temperature, and obtaining an adhesive monomer shown in the formula (I); the eluent for purifying the basic alumina chromatographic column is petroleum ether, ethyl acetate, toluene, methylene dichloride, tetrahydrofuran, chloroform, hexane, carbon tetrachloride or the like.
2. The post-treatment is as follows: filtering the reaction solution, removing solvent by rotary evaporation, diluting the obtained viscous liquid with organic solvent A, adding deionized water, washing to remove unreacted amine molecules, back-extracting the obtained organic phase with 1-3M (preferably 2M) hydrochloric acid solution, neutralizing the water phase with 3-5M (preferably 4M) sodium hydroxide solution, adding organic solvent B, extracting, mixing the organic phases, and anhydrous MgSO 4 Drying and distilling under reduced pressure to obtain the adhesive monomer.
The organic solvent A and the organic solvent B are respectively and independently diethyl ether, acetone, ethyl acetate, benzene, toluene or hexane.
In a third aspect, the invention provides an application of an adhesive monomer shown in the formula (I) in the preparation of an adhesive, in particular to an application in the preparation of an underwater adhesive.
Specifically, the application is:
uniformly dispersing the adhesive monomer shown in the formula (I) and a photoinitiator in an organic reaction medium, and carrying out homopolymerization for 0.1-48 h (preferably carrying out homopolymerization for 4h under 32W ultraviolet light) under the ultraviolet light at 15-60 ℃ (the embodiment of the invention is normal-temperature reaction and the temperature is increased more quickly) to obtain the adhesive; the ratio of the adhesive monomer shown in the formula (I) to the substance of the photoinitiator is 10-100:1.
Preferably, the organic reaction medium is an organic solvent or an ionic liquid. Specifically, the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide; the ionic liquid is 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazole chlorohydrate, 1-butyl-2, 3-dimethylimidazole chlorohydrate, 1-ethyl-3-methylimidazole bromosalt, 1-octyl-3-methylimidazole tetrafluoroborate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazolium dicyano amine salt, 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt or 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt, and the like. Particular preference is given to 1-ethyl-3-methylimidazolium tetrafluoroborate, dimethyl sulfoxide or N, N-dimethylformamide, most preferably N, N-dimethylformamide.
Specifically, the mass ratio of the adhesive monomer shown in the formula (I) to the organic reaction medium is 1:1-4.
Preferably, the photoinitiator is azobisisobutyrimidine hydrochloride, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, 2-hydroxy-2-methyl-1-phenylpropion, 1-hydroxycyclohexylphenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, and the like.
The adhesive is pressed for 20s to 1h under the pressure of 0.1 to 200N, and the adhesive can be finished.
The underwater adhesive prepared by the method is in a viscous liquid shape.
The adhesive has high bonding strength on various substrates, especially ceramic substrates, and has better performance on the substrates of spherical grain surface, random rough surface and grass grain surface, and optimal performance on the substrates of spherical grain surface.
Compared with the prior art, the invention has the beneficial effects that:
compared with the existing underwater liquid adhesive, the adhesive obtained by the method has the advantages of high bonding speed (within 20 s), strong underwater bonding strength (350 kPa), and long-term adhesion effect (7 days).
Drawings
FIG. 1 is a schematic reaction scheme of the synthetic method of the present invention: synthetic pathways for monomers I (A), II (B), III (C);
FIG. 2 is a schematic view of an underwater implementation of the adhesive of the present invention;
FIG. 3 is a graph showing the adhesion properties of the adhesive (monomer I) prepared in example 1 to glass under water;
FIG. 4 is a graph showing the adhesion properties of the adhesive (monomer II) prepared in example 2 to glass under water;
FIG. 5 is a graph showing the adhesion properties of the adhesive (monomer III) prepared in example 3 to glass under water;
FIG. 6 is a graph showing the adhesion properties of the adhesives prepared in examples 4 and 5 (different solvents) to glass under water.
Fig. 7 shows the bonding strength of the adhesives described in examples 3 and 6 to substrates of different materials.
Fig. 8 adhesion strength of the adhesives described in examples 3 and 6 to substrates of different structural morphologies.
FIG. 9 is a graph comparing the adhesive properties of the adhesives of examples 3 and 6 with the adhesive properties of the same type, wherein the adhesive strength is the adhesive strength to glass, and the adhesive time is the minimum time required for achieving the corresponding adhesive strength in the literature; the data in the figures are derived from the following documents:
Xing Li,Yan Deng,Jinlei Lai,Gai Zhao,Shengyi Dong.Journal of the American Chemical Society 2020,142,5371–5379.
Hailong Fan,Jiahui Wang,Jian Ping Gong.Advanced Functional Materials, 2021,31,2009334.
Ping Rao,Tao Lin Sun,Liang Chen,Riku Takahashi,Gento Shinohara,Hui Guo, Daniel R.King,Takayuki Kurokawa,Jian Ping Gong*.Advanced Materials 2018,30,1801884.
Chunyan Cui,Chuanchuan Fan,Yuanhao Wu,Meng Xiao,Tengling Wu, Dongfei Zhang,Xinyu Chen,Bo Liu,Ziyang Xu,Bo Qu,Wenguang Liu.Advanced Materials 2019,31,1905761.
Xing Su,Yang Luo,Zhuoling Tian,Zuoying Yuan,Yiming Han,Runfeng Dong, Liang Xu,Yuting Feng,Xiaozhi Liu,Jianyong Huang.Materials Horizons,2020,7,2651–2661.
Xing Su,Wenyue Xie,Pudi Wang,Zhuoling Tian,Hao Wang,Zuoying Yuan, Xiaozhi Liu,Jianyong Huang.Materials Horizons,2021,8,2199–2207.。
Detailed Description
The present invention will be described in further detail below with reference to the drawings and examples, it being understood that the following description is of the most preferred embodiments of the invention and should not be construed as limiting the scope of the invention.
Example 1
In a 500mL three-necked round bottom flask equipped with a condensing reflux, a thermometer and magnetic stirring, 55.3g (0.4 mol) of potassium carbonate was first dissolved in 200mL of absolute ethanol, 20mL of an aqueous solution of 4wt% (0.72 g,0.016 mol) of dimethylamine was added, then 30.5g (0.2 mol) of p-chloromethylstyrene was slowly dropped, nitrogen was introduced for 30 minutes, the reaction mixture was heated to 50℃after stirring uniformly and reacted for 24 hours, the reaction product was filtered and the solvent ethanol was removed through rotary evaporation of the filtrate, to obtain an orange yellow viscous liquid. Purifying with alkaline alumina chromatographic column, eluting with petroleum ether, purifying with column to obtain eluent containing target compound, volatilizing at room temperature for 3 hr to remove eluent, and obtaining light yellow transparent oily liquid product (monomer I) (figure 1A) 12 mL.
The underwater adhesive was prepared by homogeneously dissolving and dispersing 0.322g (0.002 mol) of the monomer obtained above and 4mg (0.00002 mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylbenzophenone (photoinitiator) in 1.254 g of 1-ethyl-3-methylimidazole tetrafluoroborate, and homopolymerizing for 4 hours under the action of 32W UV light.
Injecting 0.5mL of the prepared adhesive into water through a syringe on one glass substrate, covering the other glass substrate, and pressing for 20s in water with a force of 1N to realize the quick underwater adhesion of the adhesive (figure 2); the bond strength was tested at various times and long-lasting underwater adhesion was found to be achieved (fig. 3).
Example 2
In a 500mL three-necked round bottom flask equipped with a reflux condenser, thermometer and magnetic stirrer, 10.5g (0.12 mol) of sodium bicarbonate was first dissolved in 200mL of water/acetone (v/v=1:1), then 27.22g (0.3 mol) of imidazole was added and stirred well at room temperature for about 30min. Then, 15.22. 15.22g (0.1 mol) of p-chloromethylstyrene was slowly added dropwise with a constant pressure dropping funnel, nitrogen was introduced for 30 minutes, and the reaction system was stirred at 50℃for 24 hours. After the reaction was completed, cooled to room temperature, the solid salt was filtered to give a reddish-wine liquid, acetone was removed from the filtrate by rotary evaporation, the remaining solution was diluted with 500mL of diethyl ether, and unreacted imidazole was removed by washing with 50mL of deionized water 6 times, the obtained organic phase was back-extracted with 300mL of 2m HCl solution, and the lower aqueous phase solution was neutralized with 200mL of 4m NaOH solution. Then extracted 3 times with 50mL diethyl ether and dried over anhydrous MgSO 4 Drying and distillation under reduced pressure gave 11mL of a pale yellow oily liquid, monomer II (FIG. 1B).
The underwater adhesive was prepared by homogeneously dissolving and dispersing 0.368g (0.002 mol) of the monomer obtained above and 4mg (0.00002 mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylbenzophenone (photoinitiator) in 1.254 g of 1-ethyl-3-methylimidazole tetrafluoroborate, and homopolymerizing for 4 hours under the action of 32W UV light.
Injecting 0.5mL of the prepared adhesive into water through a syringe on one glass substrate, covering the other glass substrate, and pressing for 20s in water with a force of 1N to realize the quick underwater adhesion of the adhesive (figure 2); the bond strength was tested at various times and long-lasting underwater adhesion was found to be achieved (fig. 4).
Example 3
In a 500mL three-necked round bottom flask equipped with a reflux condenser, thermometer and magnetic stirrer, 10.5g (0.12 mol) of sodium bicarbonate was first dissolved in 200mL of water/acetone (v/v=1:1), followed by addition of 27.22g (0.3 mol) of triazole and stirring thoroughly at room temperature for about 30min. Then 15.22g (0.1 mol) of p-chloromethylstyrene was slowly added dropwise with a constant pressure dropping funnel, nitrogen was introduced for 30min, and the reaction system was stirred at 50℃for 24 hours. After the reaction was completed, cooled to room temperature, the solid salt was filtered to give a reddish-wine liquid, acetone was removed from the filtrate by rotary evaporation, the remaining solution was diluted with 500mL of diethyl ether, and unreacted imidazole was removed by washing with 50mL of deionized water 6 times, the obtained organic phase was back-extracted with 300mL of 2m HCl solution, and the lower aqueous phase solution was neutralized with 200mL of 4m NaOH solution. Then extracted 3 times with 50mL diethyl ether and dried over anhydrous MgSO 4 Drying and distillation under reduced pressure gave 10mL of a pale yellow oily liquid, monomer III (FIG. 1C).
The underwater adhesive was prepared by homogeneously dissolving and dispersing 0.37g (0.002 mol) of the monomer obtained above and 4mg (0.00002 mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylbenzophenone (photoinitiator) in 1.254 g of 1-ethyl-3-methylimidazole tetrafluoroborate, and homopolymerizing for 4 hours under the action of 32W UV light.
Injecting 0.5mL of the prepared adhesive into water through a syringe on one glass substrate, covering the other glass substrate, and pressing for 20s in water with a force of 1N to realize the quick underwater adhesion of the adhesive (figure 2); the bond strength was tested at various times and long-lasting underwater adhesion was found to be achieved (fig. 5).
Example 4
In a 500mL three-necked round bottom flask equipped with a reflux condenser, thermometer and magnetic stirrer, 10.5g (0.12 mol) of sodium bicarbonate was first dissolved in 200mL of water/acetone (v/v=1:1), followed by addition of 27.22g (0.3 mol) of triazole and stirring thoroughly at room temperature for about 30min. Then 15.22g (0.1 mol) of p-chloromethylstyrene was slowly added dropwise with a constant pressure dropping funnel, nitrogen was introduced for 30min, and the reaction system was stirred at 50℃for 24 hours. After the reaction was completed, cooled to room temperature, the solid salt was filtered to give a reddish wine liquid, acetone was removed from the filtrate by rotary evaporation, and the remaining solution was diluted with 500mL of diethyl ether, andthe unreacted imidazole was removed by washing 6 times with 50mL of deionized water, and the resulting organic phase was back-extracted with 300mL of 2M HCl solution and the lower aqueous phase was neutralized with 200mL of 4M NaOH solution. Then extracted 3 times with 50mL diethyl ether and dried over anhydrous MgSO 4 Drying and distillation under reduced pressure gave 10mL of a pale yellow oily liquid.
The underwater adhesive was prepared by homogeneously dissolving and dispersing 0.37g (0.002 mol) of the monomer obtained above and 4mg (0.00002 mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionyl ketone (photoinitiator) in 1.1g of dimethyl sulfoxide, and carrying out homopolymerization under the action of 32W UV light for 4 hours.
The prepared adhesive was injected with 0.5mL of water through a syringe on one glass substrate, then the other glass substrate was covered, and the adhesive was applied with a force of 1N in water for 20s, thereby achieving underwater adhesion of the adhesive (fig. 6).
Example 5
In a 500mL three-necked round bottom flask equipped with a reflux condenser, thermometer and magnetic stirrer, 10.5g (0.12 mol) of sodium bicarbonate was first dissolved in 200mL of water/acetone (v/v=1:1), followed by addition of 27.22g (0.3 mol) of triazole and stirring thoroughly at room temperature for about 30min. Then 15.22g (0.1 mol) of p-chloromethylstyrene was slowly added dropwise with a constant pressure dropping funnel, nitrogen was introduced for 30min, and the reaction system was stirred at 50℃for 24 hours. After the reaction was completed, cooled to room temperature, the solid salt was filtered to give a reddish-wine liquid, acetone was removed from the filtrate by rotary evaporation, the remaining solution was diluted with 500mL of diethyl ether, and unreacted imidazole was removed by washing with 50mL of deionized water 6 times, the obtained organic phase was back-extracted with 300mL of 2m HCl solution, and the lower aqueous phase solution was neutralized with 200mL of 4m NaOH solution. Then extracted 3 times with 50mL diethyl ether and dried over anhydrous MgSO 4 Drying and distillation under reduced pressure gave 10mL of a pale yellow oily liquid.
The underwater adhesive was prepared by homogeneously dissolving and dispersing 0.37g (0.002 mol) of the monomer obtained above and 4mg (0.00002 mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionyl ketone (photoinitiator) in 0.945g of dimethylformamide, and carrying out homopolymerization reaction for 4 hours under the action of 32W UV light.
The prepared adhesive was injected with 0.5mL of water through a syringe on one glass substrate, then the other glass substrate was covered, and the adhesive was applied with a force of 1N in water for 20s, thereby achieving underwater adhesion of the adhesive (fig. 6).
Example 6
An adhesive was prepared in the same manner as in example 3.
The prepared adhesive was injected with 0.5mL into water through an injector onto substrates of different materials (wood board, glass, polyethylene terephthalate PET, glass, iron sheet, ceramic, organic glass), then covered with the other side substrate, and pressed with 1N force in water for 20s, thus achieving the underwater adhesion of the adhesive (fig. 7).
The prepared adhesive is injected with 0.5mL of water through a syringe on substrates (spherical surface, random rough surface and grass grain surface) with different surface structure morphologies, then the other side substrate is covered, and the pressure is applied for 20s in water with 1N force, so that the underwater adhesion of the adhesive can be realized (figure 8).
The adhesive strength of the adhesive to glass was divided by the corresponding bonding time to obtain the relevant parameters describing the bonding ability, and compared with the same parameters reported in the literature for the same type of adhesive, the adhesive ability of the adhesive according to the invention was found to be more pronounced (fig. 9).
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (5)
1. An application of an adhesive monomer shown in a formula (I) in the preparation of an adhesive,
wherein R1 and R2 are methyl, ethyl or isopropyl at the same time, or R1 and R2 are connected into a ring and combined with N between the two to form an imidazolyl.
2. The application according to claim 1, characterized in that it is:
uniformly dispersing the adhesive monomer shown in the formula (I) and a photoinitiator in an organic reaction medium, and carrying out homopolymerization reaction for 0.1-48 h at 15-60 ℃ under ultraviolet light to prepare the adhesive; the ratio of the adhesive monomer shown in the formula (I) to the substance of the photoinitiator is 10-100:1.
3. Use according to claim 2, characterized in that the organic reaction medium is an organic solvent or an ionic liquid; the mass ratio of the adhesive monomer shown in the formula (I) to the organic reaction medium is 1:1-4.
4. A use according to claim 3, wherein: the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide; the ionic liquid is 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazole chlorohydrate, 1-butyl-2, 3-dimethylimidazole chlorohydrate, 1-ethyl-3-methylimidazole bromosalt, 1-octyl-3-methylimidazole tetrafluoroborate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazolium dicyano amine salt, 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt or 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt.
5. The use according to claim 2, wherein: the photoinitiator is azodiisobutylamidine hydrochloride, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-2-methyl-1-phenylpropion, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide or 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
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