CN114195651A - Underwater adhesive and preparation method thereof - Google Patents
Underwater adhesive and preparation method thereof Download PDFInfo
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- CN114195651A CN114195651A CN202111620582.XA CN202111620582A CN114195651A CN 114195651 A CN114195651 A CN 114195651A CN 202111620582 A CN202111620582 A CN 202111620582A CN 114195651 A CN114195651 A CN 114195651A
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- adhesive monomer
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- 239000000853 adhesive Substances 0.000 title claims abstract description 99
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 12
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 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 description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000012430 organic reaction media Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 150000003852 triazoles Chemical class 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000004306 triazinyl group Chemical group 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 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
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000011261 inert gas Substances 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
- 239000011259 mixed solution Substances 0.000 claims description 2
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 27
- 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
- 239000011521 glass Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- -1 1-ethyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000005923 long-lasting effect Effects 0.000 description 3
- 238000003825 pressing Methods 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
- 238000004821 distillation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- 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
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 244000140975 Prunus simonii Species 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MKHFCTXNDRMIDR-UHFFFAOYSA-N cyanoiminomethylideneazanide;1-ethyl-3-methylimidazol-3-ium Chemical compound [N-]=C=NC#N.CCN1C=C[N+](C)=C1 MKHFCTXNDRMIDR-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect 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
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 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
- RVKZDIDATLDTNR-UHFFFAOYSA-N sulfanylideneeuropium Chemical compound [Eu]=S RVKZDIDATLDTNR-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
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- 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) preparing a monomer by chemical synthesis; 2) preparing a liquid underwater adhesive by ultraviolet light initiated free radical polymerization; 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 20s, has strong underwater bonding strength (350 kPa), and can maintain the adhesion effect for a long time (more than 7 days). The defects that the solid adhesive is low in bonding strength and difficult to effectively adhere to a complex surface are overcome, the problem that the ordinary liquid adhesive is low in adhesion speed is effectively solved, and long-acting underwater adhesion can be achieved.
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
Adhesives are widely used in our daily life and industry. Currently, most adhesives on the market can only achieve adhesion to dry objects in an air environment. In practical applications, however, it is often also necessary to adhere wet 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, underwater material leak repair, and the marine industry, among others. Therefore, the development of new underwater adhesives that can be used in humid/underwater environments has been an important goal in the field of adhesive research.
At present, research on the underwater adhesion-based adhesives is being continuously advanced, and the adhesives can be classified into liquid adhesives and solid adhesives (tapes) according to their physical forms. Solid state adhesive tapes are easy to handle, but have a weak adhesive strength compared to liquid state adhesives. For example, professor Gong Jian Nu et al at Hokkaido university prepared an underwater adhesive tape based on a polymer of cation-benzene ring structure, which was only pressed against an underwater substrate to achieve adhesion, but its adhesion strength to glass under water was only 20-60 kPa. In addition, solid state tapes are often difficult to attach to substrates having complex surface texture topographies due to physical limitations. The liquid adhesive is generally strong in bonding strength, but strong interface bonding can be realized only by curing the adhesive under water, and the curing process generally needs a certain time; in addition, some glues require external thermal stimulation or light for curing, which makes the adhesion operation difficult. For example, Abraham Joy et al, Ackeron university, USA, developed a glue for underwater use, the bonding strength of which can reach 100kPa, but the implementation method is cumbersome: when testing the bond strength, it took 5 minutes to spread the glue under water, then hold under water for 15 minutes and finally irradiate with uv light for 10 minutes.
Therefore, it is highly desirable to develop an underwater adhesive which can perform spontaneous and rapid underwater adhesion, has high bonding strength and has a 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 monomers with hydrophobic structures (benzene rings) and physical interaction units (amine), and then utilizes the free radical polymerization reaction of the monomers in organic reagents to prepare the underwater adhesive which can be adhered when meeting water, and provides a specific implementation method of the adhesive. The adhesive can realize quick adhesion to a substrate within 20s, has ideal underwater bonding strength (350 kPa) and can keep 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 effectively solves the problems that the existing liquid adhesive has low adhesion speed and limited long-term stability.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
in a first aspect, the invention provides an adhesive monomer represented by formula (I),
wherein R1 and R2 are methyl, ethyl, isopropyl or ethanol groups simultaneously, or R1 and R2 are connected to form a ring and are combined with N between the two to form an imidazolyl group or a triazinyl group.
Preferably, R1, R2 are both methyl, or R1 and R2 are linked to form a ring and combine with the N between to form an imidazolyl or triazinyl group.
In a second aspect, the present invention provides a method for preparing an adhesive monomer represented by formula (I), the method comprising: dissolving an alkaline substance in a solvent, adding an amine substance under the stirring condition and in a protective atmosphere (nitrogen or inert gas, preferably nitrogen), then slowly dropwise adding p-chloromethyl styrene, reacting at 50-60 ℃ for 24-30 hours (preferably at 50 ℃ for 24 hours) after dropwise adding is finished, and carrying out post-treatment on the obtained reaction liquid to obtain an adhesive monomer shown in the formula (I);
the alkaline substance is sodium bicarbonate or potassium carbonate; the amine substance is dimethylamine, diethylamine, diisopropylamine, di-n-propylamine, imidazole, triazole and diethanolamine (preferably dimethylamine, imidazole or triazole); the amount 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 gaseous at normal temperature, the amine substance can be added in the form of an aqueous solution of the amine substance, and the concentration of the aqueous solution of the amine substance is 0.0005-0.01 mol/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, dimethyl sulfoxide, N-dimethylformamide, dichloromethane, chloroform, carbon tetrachloride, toluene, or the like.
Further, the volume of the solvent is 2-20mL/g based on the mass of the basic substance.
Further, the present invention provides two methods of post-treatment:
1. the post-treatment comprises the following steps: filtering the reaction solution, taking filtrate, performing rotary evaporation to remove the solvent, purifying the obtained viscous liquid by using an alkaline alumina chromatographic column, collecting eluent containing a target compound, and volatilizing at room temperature to remove the solvent to obtain the adhesive monomer shown in the formula (I); the eluent for the basic alumina chromatographic column purification is petroleum ether, ethyl acetate, toluene, dichloromethane, tetrahydrofuran, chloroform, hexane or carbon tetrachloride and the like.
2. The post-treatment comprises the following steps: filtering the reaction solution, taking filtrate, performing rotary evaporation to remove the solvent, diluting the obtained viscous liquid with an organic solvent A, adding deionized water for washing to remove unreacted amine molecules, back-extracting the obtained organic phase with 1-3M (preferably 2M) hydrochloric acid solution, taking the water phase for neutralizing with 3-5M (preferably 4M) sodium hydroxide solution, adding an organic solvent B for extraction, combining the organic phases, and performing anhydrous MgSO4Drying 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 the adhesive monomer shown in the formula (I) in preparing an adhesive, in particular an application in preparing an underwater adhesive.
Specifically, the application is as follows:
uniformly dispersing an adhesive monomer shown in the formula (I) and a photoinitiator in an organic reaction medium, and performing homopolymerization for 0.1-48 h (preferably, performing homopolymerization for 4h under 32W ultraviolet light) under the ultraviolet light of 15-60 ℃ (the embodiment of the invention adopts normal-temperature reaction, temperature rise and faster reaction); the mass ratio of the adhesive monomer shown in the formula (I) to 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-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazolium hexafluorophosphate, 1-butyl-2, 3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide or 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide Imine salts, and the like. Particularly preferred is 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 azobisisobutyramidine hydrochloride, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, or the like.
The adhesive is pressed for 20 s-1 h under the pressure of 0.1-200N, and then the adhesion can be completed.
The underwater adhesive prepared by the method is in a viscous liquid state.
The adhesive has high bonding strength on various substrates, particularly ceramic substrates, and has better performance on a spherical surface substrate, a random rough surface substrate and a grass grain surface substrate in terms of the micro-morphology of the substrates, and the optimal performance on the spherical surface substrate.
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-time (more than 7 days) maintenance of the adhesion effect.
Drawings
FIG. 1 is a schematic reaction scheme of the synthesis method of the present invention: synthetic routes 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 of adhesion performance of the adhesive (monomer I) prepared in example 1 to glass underwater;
FIG. 4 is a graph of adhesion performance of the adhesive (monomer II) prepared in example 2 to glass underwater;
FIG. 5 is a graph of adhesion performance of the adhesive prepared in example 3 (monomer III) to glass underwater;
FIG. 6 is a graph of adhesion of the adhesives prepared in examples 4 and 5 (different solvents) to glass underwater.
Fig. 7 bond strength of the adhesives described in examples 3 and 6 to substrates of different materials.
FIG. 8 bond strength of the adhesives described in examples 3 and 6 to substrates of different structural topographies.
FIG. 9 is a graph comparing the bonding performance of the adhesives of examples 3 and 6 with that of the same type of adhesive, wherein the bond strengths are the bond strength to glass and the bonding time is selected from the minimum time required to achieve the respective bond strengths as described in the literature; the data in the figure 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 with reference to the following drawings and examples, it being understood that the following description is only the most preferred embodiment of the present invention and should not be taken as limiting the scope of the present invention.
Example 1
In a 500mL three-necked round-bottom flask equipped with a reflux condenser, a thermometer and a magnetic stirrer, 55.3g (0.4mol) of potassium carbonate was first dissolved in 200mL of absolute ethanol, 20mL of an aqueous solution of dimethylamine having a concentration of 4 wt% (0.72g,0.016mol) was added, then 30.5g (0.2mol) of p-chloromethylstyrene was slowly added dropwise, nitrogen was introduced for 30min, the reaction mixture was heated to 50 ℃ after uniform stirring and continued to react for 24h, the reaction product was filtered and the solvent ethanol was removed by rotary evaporation of the filtrate to give an orange-yellow viscous liquid. Purifying with alkaline alumina chromatographic column, eluting with petroleum ether to obtain eluent containing target compound, and volatilizing at room temperature for 3 hr to remove the eluent to obtain yellowish transparent oily liquid product 12mL, namely monomer I (FIG. 1A).
0.322g (0.002mol) of the obtained monomer and 4mg (0.00002mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (photoinitiator) are uniformly dissolved and dispersed in 1.294g of 1-ethyl-3-methyl imidazole tetrafluoroborate, and homopolymerization is carried out for 4h under the action of 32W UV light, so as to prepare the underwater adhesive.
Injecting 0.5mL of the prepared adhesive water on a glass substrate by an injector, then covering the other glass substrate, and pressing for 20s in the water with 1N force to realize the rapid underwater adhesion of the adhesive (figure 2); the adhesive strength was tested at different times and found to achieve long-lasting underwater adhesion (fig. 3).
Example 2
In a 500mL three-necked round-bottom flask equipped with reflux condenser, thermometer and magnetic stirring, first 10.5g (0.12mol) of sodium bicarbonate was dissolved in 200mL of water/acetone (v/v ═ 1:1) and then 27.22g (0.3mol) of imidazole was added and stirred well at room temperature for about 30 min. Then, 15.22g (0.1mol) of p-chloromethyl styrene is slowly dropped into the reaction kettle by a constant pressure dropping funnel, nitrogen is introduced for 30min, and the reaction system is stirred and reacts for 24h at the temperature of 50 ℃. After the reaction was complete, cooled to room temperature, the solid salts were filtered to give a wine-red liquid, the acetone was removed by rotary evaporation of the filtrate, the remaining solution was diluted with 500mL of diethyl ether and washed with 50mL of deionized water for 6 times to remove unreacted imidazole, the organic phase obtained was back-extracted with 300mL of 2M HCl solution, the lower aqueous phase was neutralized with 200mL of 4M NaOH solution. Then extracted 3 times with 50mL of diethyl ether and MgSO4Drying and reduced pressure distillation gave 11mL of a pale yellow oily liquid, monomer II (FIG. 1B).
0.368g (0.002mol) of the obtained monomer and 4mg (0.00002mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (photoinitiator) are uniformly dissolved and dispersed in 1.294g of 1-ethyl-3-methyl imidazole tetrafluoroborate, and homopolymerization is carried out for 4h under the action of 32W UV light, so as to prepare the underwater adhesive.
Injecting 0.5mL of the prepared adhesive water on a glass substrate by an injector, then covering the other glass substrate, and pressing for 20s in the water with 1N force to realize the rapid underwater adhesion of the adhesive (figure 2); the adhesive strength was tested at different times and found to achieve long-lasting underwater adhesion (fig. 4).
Example 3
In a 500mL three-necked round-bottom flask equipped with reflux condenser, thermometer and magnetic stirring, first 10.5g (0.12mol) of sodium bicarbonate are dissolved in 200mL of water/acetone (v/v ═ 1:1) and then 27.22g (0.3mol) of triazole are added and stirred well at room temperature for about 30 min. Then, 15.22g (0.1mol) of p-chloromethyl styrene is slowly dropped into the reaction kettle by a constant pressure dropping funnel, nitrogen is introduced for 30min, and the reaction system is stirred and reacts for 24h at the temperature of 50 ℃. After the reaction was complete, cooled to room temperature, the solid salts were filtered to give a wine-red liquid, the acetone was removed by rotary evaporation of the filtrate, the remaining solution was diluted with 500mL of diethyl ether and washed with 50mL of deionized water for 6 times to remove unreacted imidazole, the organic phase obtained was back-extracted with 300mL of 2M HCl solution, the lower aqueous phase was neutralized with 200mL of 4M NaOH solution. Then extracted 3 times with 50mL of diethyl ether and MgSO4Drying and distillation under reduced pressure gave 10mL of a pale yellow oily liquid, monomer III (FIG. 1C).
0.37g (0.002mol) of the obtained monomer and 4mg (0.00002mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (photoinitiator) are uniformly dissolved and dispersed in 1.294g of 1-ethyl-3-methyl imidazole tetrafluoroborate, and homopolymerization is carried out for 4h under the action of 32W UV light, so as to prepare the underwater adhesive.
Injecting 0.5mL of the prepared adhesive water on a glass substrate by an injector, then covering the other glass substrate, and pressing for 20s in the water with 1N force to realize the rapid underwater adhesion of the adhesive (figure 2); the adhesive strength was tested at different times and found to achieve long-lasting underwater adhesion (fig. 5).
Example 4
In a 500mL three-necked round-bottom flask equipped with reflux condenser, thermometer and magnetic stirring, first 10.5g (0.12mol) of sodium bicarbonate are dissolved in 200mL of water/acetone (v/v ═ 1:1) and then 27.22g (0.3mol) of triazole are added and stirred well at room temperature for about 30 min. Then, 15.22g (0.1mol) of p-chloromethyl styrene is slowly dropped into the reaction kettle by a constant pressure dropping funnel, nitrogen is introduced for 30min, and the reaction system is stirred and reacts for 24h at the temperature of 50 ℃. Cooling to room temperature after the reaction is completed, filtering out solid salt to obtain wine red liquid, removing acetone by rotary evaporation of filtrate, and using 500mL of ethyl acetate for residual solutionThe ether was diluted and washed 6 times with 50mL of deionized water to remove unreacted imidazole, 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 of diethyl ether and MgSO4Drying and distilling under reduced pressure to obtain 10mL of light yellow oily liquid.
And (3) uniformly dissolving and dispersing 0.37g (0.002mol) of the obtained monomer and 4mg (0.00002mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (photoinitiator) in 1.1g of dimethyl sulfoxide, and performing homopolymerization reaction for 4 hours under the action of 32W UV ultraviolet light to obtain the underwater adhesive.
The adhesive prepared was injected into water by a syringe in an amount of 0.5mL on one glass substrate, and then the other glass substrate was covered and pressed in water with a force of 1N for 20 seconds to achieve underwater adhesion of the adhesive (FIG. 6).
Example 5
In a 500mL three-necked round-bottom flask equipped with reflux condenser, thermometer and magnetic stirring, first 10.5g (0.12mol) of sodium bicarbonate are dissolved in 200mL of water/acetone (v/v ═ 1:1) and then 27.22g (0.3mol) of triazole are added and stirred well at room temperature for about 30 min. Then, 15.22g (0.1mol) of p-chloromethyl styrene is slowly dropped into the reaction kettle by a constant pressure dropping funnel, nitrogen is introduced for 30min, and the reaction system is stirred and reacts for 24h at the temperature of 50 ℃. After the reaction was complete, cooled to room temperature, the solid salts were filtered to give a wine-red liquid, the acetone was removed by rotary evaporation of the filtrate, the remaining solution was diluted with 500mL of diethyl ether and washed with 50mL of deionized water for 6 times to remove unreacted imidazole, the organic phase obtained was back-extracted with 300mL of 2M HCl solution, the lower aqueous phase was neutralized with 200mL of 4M NaOH solution. Then extracted 3 times with 50mL of diethyl ether and MgSO4Drying and distilling under reduced pressure to obtain 10mL of light yellow oily liquid.
And (3) uniformly dissolving and dispersing 0.37g (0.002mol) of the obtained monomer and 4mg (0.00002mol) of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (photoinitiator) in 0.945g of dimethylformamide, and performing homopolymerization reaction for 4 hours under the action of 32W UV ultraviolet light to obtain the underwater adhesive.
The adhesive prepared was injected into water by a syringe in an amount of 0.5mL on one glass substrate, and then the other glass substrate was covered and pressed in water with a force of 1N for 20 seconds to achieve underwater adhesion of the adhesive (FIG. 6).
Example 6
An adhesive was prepared in the same manner as in example 3.
The prepared adhesive is injected into 0.5mL of substrate (wood board, glass, polyethylene terephthalate (PET), glass, iron sheet, ceramic and organic glass) made of different materials in water through a syringe, then the substrate on the other side is covered, and the pressure is applied for 20s in the water under the force of 1N, so that the underwater adhesion of the adhesive can be realized (figure 7).
The prepared adhesive is injected with 0.5mL of water on substrates with different surface structure shapes (spherical surfaces, irregular rough surfaces and grass grain surfaces) by a syringe, then the other side of the substrate is covered, and the pressure is applied for 20s in the 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 is divided by the corresponding adhesive time to obtain relevant parameters describing the adhesive capacity, and the parameters are compared with the same parameters of the same kind of adhesives reported in the literature, so that the adhesive capacity of the adhesive is more prominent (figure 9).
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. An adhesive monomer shown in a formula (I),
wherein R1 and R2 are methyl, ethyl, isopropyl or ethanol groups simultaneously, or R1 and R2 are connected to form a ring and are combined with N between the two to form an imidazolyl group or a triazinyl group.
2. The method for preparing the adhesive monomer represented by the formula (I) according to claim 1, wherein the method comprises: dissolving an alkaline substance in a solvent, adding an amine substance under the stirring condition and in a protective atmosphere, then slowly dropwise adding p-chloromethyl styrene, reacting for 24-30 hours at 50-60 ℃ after dropwise adding is finished, and carrying out post-treatment on the obtained reaction liquid 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 and diethanolamine; the amount ratio of the alkaline substance, the amine substance and the p-chloromethyl styrene substance is 1-2: 0.05-5: 1.
3. the method for preparing the adhesive monomer represented by the formula (I) according to claim 2, wherein: the solvent is ethanol, acetone, a mixed solution of water and acetone in a volume ratio of 1: 1-2, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, dichloromethane, chloroform, carbon tetrachloride or toluene.
4. The method for preparing the adhesive monomer represented by the formula (I) according to claim 2, wherein: the volume of the solvent is 2-20mL/g based on the mass of the alkaline substance.
5. The method for preparing the adhesive monomer represented by the formula (I) according to claim 2, wherein: the protective atmosphere is nitrogen or inert gas.
6. The method for preparing the adhesive monomer represented by the formula (I) according to claim 2, wherein the post-treatment is: filtering the reaction solution, taking filtrate, performing rotary evaporation to remove the solvent, purifying the obtained viscous liquid by using an alkaline alumina chromatographic column, collecting eluent containing a target compound, and volatilizing at room temperature to remove the solvent to obtain the adhesive monomer shown in the formula (I); the eluent for purifying the basic alumina chromatographic column is petroleum ether, ethyl acetate, toluene, dichloromethane, tetrahydrofuran, chloroform, hexane or carbon tetrachloride.
7. Use of an adhesive monomer of formula (I) according to claim 1 in the preparation of an adhesive.
8. The use according to claim 7, characterized in that the use is:
uniformly dispersing an adhesive monomer shown in the formula (I) and a photoinitiator in an organic reaction medium, and performing homopolymerization reaction for 0.1-48 h at 15-60 ℃ under ultraviolet light to obtain the adhesive; the mass ratio of the adhesive monomer shown in the formula (I) to the photoinitiator is 10-100: 1.
9. Use according to claim 8, 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.
10. The use of claim 8, wherein: the photoinitiator is azobisisobutyramidine hydrochloride, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-2-methyl-1-phenyl acetone, 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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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003138220A (en) * | 2001-11-02 | 2003-05-14 | Fuji Xerox Co Ltd | Surface modifier and surface modifying method |
| CN108473621A (en) * | 2016-12-05 | 2018-08-31 | 株式会社Lg化学 | Modifying agent, modified conjugated diene Type of Collective object and preparation method thereof |
| CN108977031A (en) * | 2018-07-26 | 2018-12-11 | 福建华夏蓝新材料科技有限公司 | A kind of aqueous adhesive for shoes and preparation method thereof removing isocyanic acid |
| CN110699020A (en) * | 2019-11-20 | 2020-01-17 | 湖南大学 | Polyion liquid adhesive and preparation method thereof |
-
2021
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003138220A (en) * | 2001-11-02 | 2003-05-14 | Fuji Xerox Co Ltd | Surface modifier and surface modifying method |
| CN108473621A (en) * | 2016-12-05 | 2018-08-31 | 株式会社Lg化学 | Modifying agent, modified conjugated diene Type of Collective object and preparation method thereof |
| CN108977031A (en) * | 2018-07-26 | 2018-12-11 | 福建华夏蓝新材料科技有限公司 | A kind of aqueous adhesive for shoes and preparation method thereof removing isocyanic acid |
| CN110699020A (en) * | 2019-11-20 | 2020-01-17 | 湖南大学 | Polyion liquid adhesive and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| STN: "1H-Imidazole, 1-[(4-ethenylphenyl)methyl]- (CA INDEX NAME)", REGISTRY数据库（STN） * |
| STN: "Benzenemethanamine, 4-ethenyl-N, N-bis(1-methylethyl)- (CA INDEX NAME)", REGISTRY数据库（STN） * |
| STN: "Benzenemethanamine, 4-ethenyl-N, N-diethyl- (CA INDEX NAME)", REGISTRY数据库（STN） * |
| STN: "Ethanol, 2, 2\'-[[(4-ethenylphenyl)methyl]imino]bis- (CA INDEX NAME)", REGISTRY数据库（STN） * |
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