CN110386907B - Epoxy resin monomer containing imine bond, and preparation method and application thereof - Google Patents
Epoxy resin monomer containing imine bond, and preparation method and application thereof Download PDFInfo
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- CN110386907B CN110386907B CN201910527055.0A CN201910527055A CN110386907B CN 110386907 B CN110386907 B CN 110386907B CN 201910527055 A CN201910527055 A CN 201910527055A CN 110386907 B CN110386907 B CN 110386907B
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- China
- Prior art keywords
- epoxy resin
- anhydride
- curing agent
- imine bond
- epoxy
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 88
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 88
- 239000000178 monomer Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 37
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005263 alkylenediamine group Chemical group 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 150000004985 diamines Chemical class 0.000 abstract description 3
- 239000002262 Schiff base Substances 0.000 abstract description 2
- 150000004753 Schiff bases Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- -1 aldehyde compounds Chemical class 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical compound C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QVRVXSZKCXFBTE-UHFFFAOYSA-N n-[4-(6,7-dimethoxy-3,4-dihydro-1h-isoquinolin-2-yl)butyl]-2-(2-fluoroethoxy)-5-methylbenzamide Chemical compound C1C=2C=C(OC)C(OC)=CC=2CCN1CCCCNC(=O)C1=CC(C)=CC=C1OCCF QVRVXSZKCXFBTE-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to an epoxy resin monomer containing imine bond, a preparation method and application thereof, which is prepared by reacting an aldehyde group-containing epoxy compound with organic diamine through Schiff base. The epoxy resin monomer containing the imine bond is liquid at normal temperature, and has good technological properties; the prepared epoxy resin containing the imine bond not only has excellent heat resistance and mechanical properties, but also can be repeatedly processed and molded through hot pressing treatment, and the retention rate of thermal and mechanical properties of the repeatedly molded epoxy resin is higher than 90%; can also be degraded in amine solvents, solves the problem that the existing thermosetting epoxy resin is difficult to recycle, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of epoxy resin, and particularly relates to an epoxy resin monomer containing imine bonds, and a preparation method and application thereof.
Background
Epoxy resin is one of three general thermosetting resins at present, and is widely applied to the fields of adhesives, coatings, electronic packaging, advanced composite materials and the like because of good bonding property, dimensional stability, mechanical strength, chemical corrosion resistance and technological properties. However, the conventional epoxy resin has a highly crosslinked structure constructed by irreversible covalent bonds, the internal molecular topology of which is almost invariable, and which exhibits the property of being insoluble and infusible macroscopically. Therefore, once cured, the conventional epoxy resin products are difficult to recycle, and the increasing number of epoxy resin wastes year by year brings challenges to ecological environment protection. The existing treatment modes of the epoxy resin waste mainly comprise landfill, incineration, natural environment aging, freezing and crushing, supercritical fluid cracking and the like. However, these treatment methods have problems of secondary pollution to the environment, long treatment period, high equipment cost, etc. If the epoxy resin with the recyclable function is developed fundamentally, the epoxy resin has considerable economic value and also has important environmental protection significance.
At present, an important way to develop the recyclable epoxy resin is to introduce dynamic chemical bonds with stimulus responsiveness into the epoxy resin crosslinking structure, and the chemical bonds can undergo reversible exchange reaction or degradation reaction under the stimulus of specific external conditions, so that the epoxy resin is endowed with the characteristics of repeated processing, forming, degradation and the like. Imine bonds are typically dynamic covalent bonds, which can be formed by reacting aldehyde compounds with amine compounds under milder conditions via schiff base reactions, and reversible exchange reactions between imine bonds can occur under heating conditions. Therefore, the design and development of the epoxy resin containing the imine dynamic chemical bond is hopeful to endow the epoxy resin with a recoverable function, and is one way for solving the problem of recycling the epoxy resin. At present, a paper (Macromolecules 2018,51,9816-9824) is used for preparing an epoxy resin monomer containing imine bonds by using vanillin and p-hydroxyaniline as raw materials, and the epoxy resin monomer is cured by using an amine curing agent to obtain a resin product which has the functions of repeatable processing and forming, welding and degradability. However, the epoxy resin monomer is solid, has poor manufacturability, and the tensile strength of the cured product is only 45MPa, and the glass transition temperature is low (about 70 ℃). Therefore, there is a need to develop a recoverable epoxy resin containing imine bonds having properties comparable to those of general-purpose epoxy resins.
Disclosure of Invention
The invention aims to provide an epoxy resin monomer containing imine bonds, a preparation method and application thereof, and solves the problem that the existing thermosetting epoxy resin is difficult to recycle.
The invention provides an epoxy resin monomer containing imine bond, which has the following structural general formula:
wherein R is 1 Methoxy or hydrogen; r is R 2 Is that
At least one of them.
The invention also provides a preparation method of the epoxy resin monomer containing the imine bond, which comprises the following steps:
respectively dissolving an epoxy compound containing aldehyde groups and organic diamine in an organic solvent according to a molar ratio of 2:1 to obtain a solution 1 and a solution 2; and (3) dropwise adding the solution 2 into the solution 1 at room temperature under stirring, reacting for 2-12 h at 40-60 ℃ after the dropwise adding is finished, and then distilling the organic solvent under reduced pressure to obtain the epoxy resin monomer containing imine bonds.
The aldehyde group-containing epoxy compound is
Wherein R is 1 Methoxy or hydrogen.
When R is 1 When methoxy, the aldehyde group-containing epoxy compound 1 has the following structure:
aldehyde group-containing epoxy compound 1 was produced according to the method described in document 1 (Indian J Chem B2008, 47, 903-909).
When R is 1 When hydrogen, the aldehyde group-containing epoxy compound 2 has the following structure:
aldehyde group-containing epoxy compound 2 was prepared according to the method described in document 2 (chemphyscom 2010, 11, 659-664).
The organic diamine is
Of alkanediamines, isophoronediamine, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane, 3-dimethyl-4, 4-diaminodicyclohexylmethane, methylcyclohexanediamineAt least one kind.
The organic solvent is at least one of methanol, ethanol, butanol, tetrahydrofuran and dimethylformamide.
The invention also provides application of the epoxy resin monomer containing the imine bond, and the epoxy resin monomer containing the imine bond is obtained by heating and curing with a curing agent.
The curing agent is one of an amine curing agent, an anhydride curing agent and an imidazole curing agent.
Further, the amine curing agent is diethylene triamine, triethylene tetramine, tetraethylene pentamine, m-phenylenediamine, diamino diphenyl methane, diamino diphenyl sulfone,
At least one of alkanediamine, isophoronediamine, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane, 3-dimethyl-4, 4-diaminodicyclohexylmethane, methylcyclohexanediamine.
Further, the acid anhydride curing agent is at least one of phthalic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride and methylnadic anhydride.
Further, the imidazole curing agent is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and 1-cyanoethyl-2-undecylimidazole.
The epoxy resin containing imine bond provided by the invention can be repeatedly processed and molded by hot pressing under the conditions that the pressure is 0.3-1.0 Mpa, the temperature is 150-200 ℃ and the hot pressing time is 1-3 h.
The epoxy resin containing imine bond can be degraded in amine solvent at 25-80 ℃ within 2-12 h.
Further, the amine solvent is: butylamine, n-hexylamine, ethylenediamine, butanediamine, and diEthylene triamine, triethylene tetramine, tetraethylene pentamine,
At least one of alkanediamine, isophoronediamine, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane, 3-dimethyl-4, 4-diaminodicyclohexylmethane, methylcyclohexanediamine.
The invention designs an epoxy resin monomer containing imine bonds, which introduces imine dynamic covalent bonds into an epoxy resin crosslinking structure through a curing reaction with a curing agent to obtain the epoxy resin containing the imine bonds. By utilizing the principle that imine bond can generate dynamic exchange reaction under the heating condition, the epoxy resin cross-linked network structure can generate dynamic rearrangement under the hot-pressing condition, thereby endowing the epoxy resin with the function of repeatable processing and forming. In the same way, the principle that imine bonds can generate dynamic exchange reaction of amine compounds is utilized, the obtained epoxy resin is placed in an amine solvent, and under the heating condition, the imine bonds in the epoxy resin crosslinking structure and amine groups of the amine solvent can generate exchange reaction, so that the epoxy resin crosslinking structure is broken down, and the degradation of the epoxy resin is realized.
Advantageous effects
(1) The epoxy resin monomer containing the imine bond provided by the invention has a relatively rigid non-coplanar six-membered ring structure, so that the obtained epoxy resin monomer is liquid, has good manufacturability, and has heat resistance and mechanical property equivalent to those of conventional epoxy resin after curing.
(2) The epoxy resin containing the imine bond provided by the invention not only has excellent heat resistance and mechanical properties, but also can be repeatedly processed and molded through hot pressing treatment, and the retention rate of thermal and mechanical properties of the repeatedly molded epoxy resin is higher than 90%; can also be degraded in amine solvents, solves the problem that the existing thermosetting epoxy resin is difficult to recycle, and has wide application prospect.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Experimental test 1: structural characterization
Adopts infrared spectrum, 1 HNMR and elemental analysis characterize the structure of the imine bond containing epoxy monomer in the examples below.
Experiment test 2: viscosity test:
the viscosity of the epoxy resin monomer containing imine bonds in the following examples was tested in accordance with the GB/T22314-2008 test standard using a rotational viscometer.
Experimental test 3: epoxy equivalent test:
the viscosity of the imine bond-containing epoxy monomer in the following examples was measured using titration in accordance with ASTM-D1652 test standard.
Experimental test 3: tensile Property test
The epoxy tensile properties of the imine bond in the following examples were tested using a universal mechanical tester in accordance with ASTM-D638 test standard.
Experimental test 4: glass transition temperature test
The epoxy glass transition temperature of the imine bond in the following examples was tested using a dynamic mechanical analyzer. The test adopts a single cantilever beam mode, the heating rate is 3 ℃/min, and the peak temperature of the loss tangent value-temperature curve is taken as the glass transition temperature.
Example 1
35.6g of epoxy compound 2 containing aldehyde group and 80mL of anhydrous methanol were added to a vessel at normal temperature, and the mixture was stirred uniformly to obtain a transparent solution. Will be 17.0g
Dissolving alkanediamine in 60mL anhydrous methanol, placing in a constant pressure dropping funnel, and slowly dropping to the aldehyde group-containing ring under rapid stirring at room temperatureIn the solution of the oxygen compound 2, after the dripping is finished, heating to 60 ℃ for reaction for 4 hours, and after the reaction is finished, distilling under reduced pressure to remove the absolute methanol solvent to obtain the epoxy resin monomer containing imine bonds, wherein the structure is as follows:
characterization of imine bond-containing epoxy resin monomer structure, viscosity and epoxy equivalent:
infrared spectrum (potassium bromide tablet): 1635cm -1 (-CH＝N-)，1608cm -1 And 1512cm -1 (benzene ring), 910cm -1 (epoxy group).
1 HNMR (DMSO-d 6, ppm δ): 8.4-8.6 (2H, -CH=N-) 7.0-7.9 (8H, benzene ring), 3.9-4.2 (4H, -O-CH) 2 (-), 3.0 (1H, -CH-) in the epoxy group, 2.3-2.6 (4H, -CH in epoxy group) 2 (-), 1.4-2.0 (9H, six membered alicyclic rings-CH-and-CH) 2 -)，0.8-1.0(9H，-CH 3 )。
Elemental analysis: c (C) 30 H 38 N 2 O 4 ；
Calculated values: c:73.44%; h:7.81%; n:5.71%;
actual measurement value: c:73.38%; h:7.94; n:7.66%.
Epoxy monomer viscosity: 9570cps (25 ℃ C.)
Epoxy monomer epoxy equivalent: 255
Preparation of epoxy resin containing imine bond
25.5g of epoxy resin monomer containing imine bond, 16.8g of methyl hexahydrophthalic anhydride and 0.2g of 2-ethyl-4 methyl imidazole are stirred and mixed uniformly at room temperature, the obtained epoxy resin mixture is introduced into a stainless steel mold, after degassing for 1h under vacuum condition, the epoxy resin mixture is cured for 1h at 120 ℃, cured for 2h at 140 ℃, cured for 1h at 170 ℃, cooled and demolded to obtain the epoxy resin containing imine bond, and the properties are shown in table 1.
Recovery of imine bond containing epoxy resins
The prepared epoxy resin containing imine bonds was pulverized by a grinder, and the obtained resin powder was hot-pressed at 170℃and a pressure of 0.3MPa for 2 hours to obtain a repeatedly molded epoxy resin, the properties of which are shown in Table 1.
10.0g of the epoxy resin containing imine bonds obtained after the first curing was placed in 40.0g of ethylenediamine and heated at 80℃for 2 hours, and the resin was completely dissolved.
Example 2
41.6g of an aldehyde group-containing epoxy compound 1 and 80mL of absolute ethyl alcohol are added into a container at normal temperature, and a transparent solution is obtained after uniform stirring. 17.0g isophorone diamine is dissolved in 80mL absolute ethyl alcohol, and is placed in a constant pressure dropping funnel, slowly added into the aldehyde group-containing epoxy compound 1 solution under the conditions of room temperature and rapid stirring, heated to 40 ℃ for reaction for 10 hours after the addition, and distilled under reduced pressure after the reaction is finished to remove the absolute ethyl alcohol solvent, thus obtaining the epoxy resin monomer containing imine bonds, the structure of which is as follows:
characterization of the imine bond-containing epoxy monomer structure, viscosity and epoxy equivalent:
infrared spectrum (potassium bromide tablet): 1633cm -1 (-CH＝N-)，1606cm -1 And 1510cm -1 (benzene ring), 912cm -1 (epoxy group).
1 HNMR (DMSO-d 6, ppm δ): 8.6-8.8 (2H, -CH=N-), 6.9-7.6 (6H, benzene ring), 3.9-4.2 (4H, -O-CH) 2 -)，3.8(6H，-O-CH 3 )，3.3-3.5(2H，-CH 2 -n=), 3.1 (1H, -CH-n=), 2.9 (2H, -CH-in epoxy), 2.3-2.6 (4H, -CH-in epoxy) 2 (-), 1.3-1.8 (6H, six membered alicyclic ring-CH) 2 -)，0.8-1.0(9H，-CH 3 )。
Elemental analysis: c (C) 32 H 42 N 2 O 6 ；
Calculated values: c:69.79%; h:7.69%; n:5.09%;
actual measurement value: c:69.89%; h:7.78; n:4.98%.
Epoxy monomer viscosity: 11550cps (25 ℃ C.)
Epoxy monomer epoxy equivalent: 282
Preparation of imine bond-containing epoxy resin:
28.2g of epoxy resin monomer containing imine bond and 5.3g of curing agent 4,4' -diamine dicyclohexylmethane are stirred and mixed uniformly at room temperature, the obtained epoxy resin mixture is introduced into a stainless steel mold, after degassing for 1h under vacuum, the epoxy resin mixture is cured for 2h at 80 ℃, after curing for 2h at 140 ℃, after cooling, the epoxy resin containing imine bond is obtained after demoulding, and the properties are shown in table 1. Recovery of imine bond containing epoxy resin:
the prepared epoxy resin containing imine bonds was pulverized by a grinder, and the obtained resin powder was hot-pressed at 160℃and a pressure of 0.8MPa for 3 hours to obtain a repeatedly molded epoxy resin, the properties of which are shown in Table 1.
10.0g of the epoxy resin containing imine bonds obtained after the first curing was placed in 40.0g of triethylenetetramine, and heated at 40℃for 6 hours, whereby the resin was completely dissolved.
Example 3
35.6g of epoxy compound 2 containing aldehyde group and 70mL of tetrahydrofuran were added into a vessel at normal temperature, and the mixture was stirred uniformly to obtain a transparent solution. 17.0g of methylcyclohexamethylenediamine is dissolved in 70mL of tetrahydrofuran, the solution is placed in a constant pressure dropping funnel, slowly added into the solution of the aldehyde-containing epoxy compound 2 under the conditions of room temperature and rapid stirring, heated to 50 ℃ for reaction for 6 hours after the addition, and absolute ethyl alcohol solvent is removed by reduced pressure distillation after the reaction is finished, so that an epoxy resin monomer containing imine bonds is obtained, wherein the structure is as follows:
characterization of the imine bond-containing epoxy monomer structure, viscosity and epoxy equivalent:
infrared spectrum (potassium bromide tablet): 1636cm -1 (-CH＝N-)，1595cm -1 And 1506cm -1 (benzene ring), 908cm -1 (epoxy group).
1 HNMR(DMSO-d6，ppm δ): 8.1-8.8 (2H, -CH=N-), 7.0-7.6 (6H, benzene ring), 3.9-4.2 (4H, -O-CH) 2 -)，3.9(6H，-O-CH 3 ) 3.0 (2H, -CH-N=), 2.8 (2H, -CH-in epoxy), 2.3-2.5 (4H, -CH-in epoxy) 2 (-), 1.3-2.0 (7H, six membered alicyclic rings-CH-and-CH) 2 -)，0.9(3H，-CH 3 ). Elemental analysis: c (C) 29 H 36 N 2 O 6 ；
Calculated values: c:68.48%; h:7.13%; n:5.51%;
actual measurement value: c:68.56%; h:7.02; n:5.60%.
Epoxy monomer viscosity: 7660cps (25 ℃ C.)
Epoxy monomer epoxy equivalent: 258
Preparation of epoxy resin containing imine bond:
the epoxy resin mixture obtained by stirring and mixing 25.8g of epoxy resin monomer containing imine bond and 1.0g of curing agent 1-cyanoethyl-2-ethyl-4-methylimidazole at room temperature was introduced into a stainless steel mold, deaerated under vacuum for 1h, cured at 180 ℃ for 4h, cooled and demolded to obtain epoxy resin containing imine bond, the properties of which are shown in table 1.
Recovery of imine bond containing epoxy resin:
the prepared epoxy resin containing imine bonds was pulverized by a grinder, and the obtained resin powder was hot-pressed at 160℃and a pressure of 0.4MPa for 2 hours to obtain a repeatedly molded epoxy resin, the properties of which are shown in Table 1.
10.0g of the epoxy resin containing imine bonds obtained after the first curing was placed in 50.0g of isophorone diamine and heated at 25℃for 12 hours, and the resin was completely dissolved.
TABLE 1
Claims (7)
1. An imine bond-containing epoxy resin monomer, characterized in that: the structural formula is as follows:
2. a preparation method of an epoxy resin monomer containing imine bonds comprises the following steps:
at normal temperature, 35.6g of an aldehyde group-containing epoxy compound was added to a vessel
And 80mL of absolute methanol, and stirring uniformly to obtain a transparent solution; 17.0 g->
Dissolving alkylene diamine in 60mL of anhydrous methanol, placing in a constant pressure dropping funnel, slowly dropping the mixture into the aldehyde-containing epoxy compound solution at room temperature under the condition of rapid stirring, heating to 60 ℃ for reaction for 4 hours after the dropping, and distilling under reduced pressure to remove the anhydrous methanol solvent after the reaction is finished to obtain the epoxy resin monomer containing imine bonds.
3. Use of the imine bond-containing epoxy resin monomer according to claim 1, characterized in that: and heating and curing the epoxy resin with the curing agent to obtain the epoxy resin containing the imine bond.
4. A use according to claim 3, characterized in that: the curing agent is one of an amine curing agent, an anhydride curing agent and an imidazole curing agent.
5. The use according to claim 4, characterized in that: the amine curing agent is diethylene triamine, triethylene tetramine, tetraethylene pentamine, m-phenylenediamine, diaminodiphenyl methane, diaminodiphenyl sulfone,
Alkyldiamine, isophoronediamine, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminobisAt least one of cyclohexylmethane, 3-dimethyl-4, 4-diamino dicyclohexylmethane and methylcyclohexamethylenediamine.
6. The use according to claim 4, characterized in that: the anhydride curing agent is at least one of phthalic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride and methylnadic anhydride.
7. The use according to claim 4, characterized in that: the imidazole curing agent is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and 1-cyanoethyl-2-undecylimidazole.
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