CN116375727A - Bio-based epoxy monomer, medium-temperature curing epoxy resin system and preparation method - Google Patents
Bio-based epoxy monomer, medium-temperature curing epoxy resin system and preparation method Download PDFInfo
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- CN116375727A CN116375727A CN202310333763.7A CN202310333763A CN116375727A CN 116375727 A CN116375727 A CN 116375727A CN 202310333763 A CN202310333763 A CN 202310333763A CN 116375727 A CN116375727 A CN 116375727A
- Authority
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- China
- Prior art keywords
- monomer
- bio
- epoxy resin
- resin system
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 68
- 239000004593 Epoxy Substances 0.000 title claims abstract description 53
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 24
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004386 Erythritol Substances 0.000 claims abstract description 20
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims abstract description 20
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims abstract description 20
- 229940009714 erythritol Drugs 0.000 claims abstract description 20
- 235000019414 erythritol Nutrition 0.000 claims abstract description 20
- 229960003371 protocatechualdehyde Drugs 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- -1 anhydride compound Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical group O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 150000008064 anhydrides Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 30
- 239000011347 resin Substances 0.000 abstract description 30
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 42
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 125000003700 epoxy group Chemical group 0.000 description 14
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000006399 behavior Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000035876 healing Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 description 1
- 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 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method 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
- 229940117960 vanillin Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic 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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- 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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
-
- 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
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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)
- Epoxy Resins (AREA)
Abstract
The invention discloses a bio-based epoxy monomer, a medium-temperature curing epoxy resin system and a preparation method thereof, in particular to a preparation method of tetrahydroxy monomer by taking protocatechuic aldehyde and erythritol as raw materials; then, using tetrahydroxy monomer and epichlorohydrin as raw materials to prepare the bio-based epoxy monomer; the bio-based epoxy monomer and the catalyst are melted and mixed uniformly, then an anhydride compound is added at the temperature of 60-80 ℃ and prepolymerization is carried out to obtain a medium-temperature curing epoxy resin system; and then the high-performance degradable multifunctional epoxy resin is obtained through medium-temperature curing. Compared with the existing biomass epoxy monomer and even the traditional commercial bisphenol A epoxy resin, the resin system has the advantages of low curing temperature and short curing time, can effectively save energy consumption, and has better comprehensive mechanical property and thermal property than the existing biomass epoxy system with dynamic reversible bond and mild degradation property, and better mechanical property and thermal property than the commercial bisphenol A epoxy resin system cured by the same curing agent.
Description
Technical Field
The invention relates to a novel bio-based epoxy monomer and a preparation method of a middle-temperature cured high-performance degradable multifunctional epoxy resin system, belonging to the technical fields of high polymer chemical synthesis and high-performance resin preparation.
Background
Epoxy resins are typical high-performance thermosetting resins and have great application value in the advanced industrial fields of electronic information, aerospace, electrical insulation, rail transit and the like. Currently, more than 90% of the epoxy monomers are derived from bisphenol a, which is not renewable and originates from petroleum resources. In view of limited petroleum resources, climate change, carbon dioxide emission and other environmental problems, biomass raw materials such as vegetable oil, lignin, isosorbide, starch, eugenol, vanillin, cardanol and the like have been widely used for synthesizing bio-based thermosetting epoxy resins, and have wide application prospects in the fields of coatings, adhesives, composite materials, electronic packaging and the like. However, most biobased epoxy monomer cured products have poor mechanical strength and glass transition temperature (T g ) Lower, thereby limiting their practical application. Research shows that the mechanical property and thermal property of the epoxy matrix can be improved by introducing a rigid structure into the epoxy monomer and using a high-temperature curing agent. In addition, as with other thermosetting resins, highly crosslinked network structures formed from biobased epoxy resins are difficult to recycle and their waste also causes serious environmental problems, and although some chemical and physical processes (e.g., mechanical milling, pyrolysis, etc.) have been used to process thermosetting resins, these processes generally require high energy consumption and harsh conditions. Therefore, the service life of the material is effectively prolonged, and the preparation of the easily degradable epoxy resin system can avoid excessive consumption of the material and reduce the energy consumption treatment of the waste material. Practice has shown that creating dynamic reversible bonds in polymeric systems allows crack repair to be achieved and extends material life, unfortunately, T is currently ubiquitous in epoxy resin systems with mild degradation behaviour based on dynamic reversible bonds g Lower mechanical strength, even if the individual epoxy resin system has excellent mechanical and thermal propertiesBut usually, a high-temperature curing agent is used, so that the curing temperature is higher and the energy consumption is higher. Therefore, the biological-based epoxy resin system with mild degradation behavior and high performance and dynamic reversible bond containing and actively developing low-medium temperature curing has important economic value and social significance for promoting the application of the biological-based epoxy resin.
Disclosure of Invention
The invention aims to provide a novel bio-based epoxy monomer and a preparation method of a middle-temperature cured high-performance degradable multifunctional epoxy resin system. The epoxy monomer is synthesized by taking the biomass protocatechuic aldehyde, the erythritol and the epichlorohydrin as raw materials, so that the multifunctional high-performance epoxy resin system with self-repairing, shape memory and degradability is prepared by a medium-temperature curing process.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a novel bio-based epoxy monomer and a high-performance degradable multifunctional epoxy resin system cured at medium temperature are prepared, wherein the bio-based epoxy monomer is synthesized by using protocatechuic aldehyde, erythritol and epichlorohydrin as raw materials, and is a tetraepoxy monomer called DGEVP; the bio-based epoxy monomer is used as a raw material, an anhydride curing agent and a catalyst are added, and a medium-temperature curing program (less than or equal to 120 ℃) is adopted to obtain a high-performance degradable multifunctional epoxy resin system.
The invention discloses a preparation method of a bio-based epoxy monomer, which takes protocatechuic aldehyde and erythritol as raw materials to prepare a tetrahydroxy monomer; and then preparing the bio-based epoxy monomer by taking tetrahydroxy monomer and epichlorohydrin as raw materials.
In the invention, protocatechuic aldehyde and erythritol are used as raw materials, and react in the presence of a catalyst and in a solvent to prepare a tetrahydroxy monomer; preferably, the reaction is carried out at 70-100 ℃ for 12-24 hours; preferably, the catalyst is p-toluenesulfonic acid monohydrate (p-TSA.H2O) and the solvent is N, N-dimethylformamide; further preferably, the reaction is carried out in the presence of a water scavenger; the mol ratio of protocatechuic aldehyde to erythritol to p-toluenesulfonic acid monohydrate is 200: (100-120) to (4-6).
In the invention, tetrahydroxy monomers and epichlorohydrin are used as raw materials, and the bio-based epoxy monomers are prepared in the presence of organic ammonium salt and in an alkaline environment; preferably, the tetrahydroxy monomer (VP) and Epichlorohydrin (ECH) are reacted for 1 to 12 hours at a temperature of between 40 and 80 ℃ in the presence of an organic ammonium salt, and then are reacted for 2 to 4 hours in an alkaline environment to prepare the bio-based epoxy monomer; preferably, the organic ammonium salt is tetrabutylammonium bromide; adding sodium hydroxide solution to form an alkaline environment; further preferably, adding sodium hydroxide solution at room temperature, and then reacting for 2-4 hours to prepare the bio-based epoxy monomer; the molar ratio of the tetrahydroxy monomer to the epichlorohydrin to the tetrabutylammonium bromide is 1:40-250:1-3.
The invention discloses a medium-temperature curing epoxy resin system, which comprises the bio-based epoxy monomer, an anhydride curing agent and a catalyst, and is a novel bio-based medium-temperature curing high-performance degradable multifunctional epoxy resin system; and obtaining the high-performance degradable multifunctional epoxy resin through medium-temperature curing.
The invention discloses a preparation method of the medium-temperature cured epoxy resin system, which comprises the steps of uniformly mixing the biological-based epoxy monomer DGEVP and a catalyst in a melting way, then adding an anhydride compound at 60-80 ℃ for prepolymerization for 20-40 min to obtain the medium-temperature cured epoxy resin system; and then curing by adopting a medium-temperature (the curing temperature is lower than 125 ℃) curing program to obtain the high-performance degradable multifunctional epoxy resin. Wherein, the molar ratio of the epoxy group of the bio-based epoxy monomer to the anhydride group of the anhydride compound is 1:0.8-1.0; the catalyst accounts for 0.5 to 5 percent of the mass of the DGEVP; preferably, the temperature at which DGEVP is melt mixed with the catalyst is 140 to 210 ℃.
In the invention, the anhydride compound is low-melting point petroleum-based anhydride, bio-based anhydride or a mixture thereof, and mainly comprises glutaric anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenyl succinic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride or a mixture thereof.
In the invention, the catalyst is one or more of organic metal complexes, such as zinc acetylacetonate, zirconium acetylacetonate, aluminum acetylacetonate, iron acetylacetonate and cadmium acetylacetonate.
In the invention, the medium temperature curing program is in a step heating mode, and the preferable medium temperature curing program is 80 ℃/2h+100 ℃/2h+120 ℃/0-4 h.
The novel bio-based epoxy monomer adopts the high-performance degradable multifunctional epoxy resin body cured at medium temperature, and has excellent mechanical properties and bending strength: 105-156 MPa and impact strength: 13.5 to 32kJ/cm 2 Tensile strength: 45-81 MPa; good heat resistance, T g : 113-158 ℃; and has multifunctional properties such as self-repairing, shape memory and mild degradability.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention synthesizes the tetraepoxy monomer by adopting natural raw materials, and has high reaction activity due to higher content of epoxy groups. The process for preparing the tetraepoxy monomer is also applicable to the preparation of the epoxy monomer with multiple epoxy functional groups by the reaction of protocatechuic aldehyde and other polyol compounds and epichlorohydrin.
(2) The invention takes anhydride as a curing agent, adopts a medium-temperature curing program (80 ℃/2h+100 ℃/2h+120 ℃/0-4 h) to obtain a high-performance resin system with multifunction such as self-repairing, shape memory and mild acid degradability, and compared with the traditional commercial bisphenol A epoxy resin which is prepared from the traditional biomass epoxy monomer, the resin system has the advantages of low curing temperature and short curing time, can effectively save energy consumption, and the comprehensive mechanical property and thermal property of the curing system are obviously superior to those of the traditional reported biomass epoxy system with dynamic reversible bond and with mild degradation characteristic, and can be comparable with those of the traditional commercial bisphenol A epoxy resin system cured by the curing agent.
Drawings
FIG. 1 is a schematic diagram of the synthesis of VP and DGEVP.
FIG. 2 is a FTIR plot (a) of PCA, erythritol, VP, and DGEVP; VP (VP) 1 H NMR chart (b); VP (VP) 13 C NMR chart (C); DGEVP 1 H NMR chart (d); DG (differential g)EVP (enhanced video compression) 13 C NMR chart (e); LC-MS diagrams of VP (f) and DGEVP (g).
FIG. 3 is a graph showing the healing process of scratches on the surface of a sample of the cured product of example 1 at 200℃by scratching the surface of the cured product with a scalpel to form scratches having a depth of about 22. Mu.m, and then placing the scratches in an oven.
FIG. 4 is a graph showing the shape deformation and recovery at 130℃of the cured product sample of example 1, wherein the cured product was first bent at 130℃and set at room temperature, and then the bent sample was placed in an oven and recovered in a short period of time.
FIG. 5 is a DSC curve of the resin system of comparative example 1 of example 1 at 10℃per minute.
FIG. 6 is a graph (a) of degradation of the cured product of example 2 in 1M hydrochloric acid solution (acetone/water=9:1, v:v) at 50 ℃; real-time 1H NMR chart (b) of the major degradation product of the cured product of example 2 in 0.1M HCl solution (acetone/water=9:1, v:v) at 50 ℃.
FIG. 7 is a graph showing the healing process of scratches on the surface of a sample of the cured product of example 2 at 200 ℃.
FIG. 8 is a graph showing the shape deformation and recovery at 130℃and three shape memory cycles of the cured product sample of example 2.
Fig. 9 is a graph showing the healing process of scratches on the surface of the cured product sample of example 3 at 210 ℃.
FIG. 10 is a graph showing deformation and recovery of the cured product sample of example 3 at 176 ℃.
FIG. 11 is a graph showing the healing process of scratches on the surface of a sample of the cured product of example 3 at 200 ℃.
FIG. 12 is a graph showing deformation and recovery at 160℃of the cured product sample of example 4.
Detailed Description
The invention takes protocatechuic aldehyde, erythritol and epichlorohydrin as main raw materials to synthesize tetraepoxy group monomer (DGEVP), takes the epoxy group monomer as raw materials, adds anhydride curing agent and catalyst, and adopts a medium-temperature curing program (less than or equal to 120 ℃) to obtain a high-performance degradable multifunctional epoxy resin system. The invention prepares tetrahydroxy monomer by using protocatechuic aldehyde and erythritol as raw materials; and then preparing the bio-based epoxy monomer by taking tetrahydroxy monomer and epichlorohydrin as raw materials. Specific examples of reactions are as follows:
(1) Placing protocatechuic aldehyde, erythritol, p-toluenesulfonic acid monohydrate (p-TSA.H2O) serving as a catalyst, N-dimethylformamide serving as a solvent and petroleum ether serving as a water scavenger into a reactor provided with a water separator and a spherical condenser tube; under the protection of nitrogen, the mixture is reacted for 12 to 24 hours at the temperature of 70 to 100 ℃, the product is cooled, then poured into deionized water to separate out precipitate, filtered by suction and washed by water, and finally dried in a vacuum oven to obtain the tetrahydroxy monomer product (VP).
(2) Adding the obtained tetrahydroxy monomer VP and Epoxy Chloropropane (ECH), reacting tetrabutylammonium bromide in a reactor at 40-80 ℃ for 1-12 hours, then dropwise adding sodium hydroxide solution at room temperature, continuing to react for 2-4 hours after the dropwise adding is finished, obtaining a crude product through suction filtration, adding dichloromethane and water, collecting an organic layer, drying the obtained organic layer by using anhydrous magnesium sulfate, removing a solvent and possible ECH by using a rotary evaporator, and finally drying to obtain the target epoxy monomer (DGEVP).
In the technical proposal, the mol ratio of protocatechuic aldehyde, erythritol, paratoluenesulfonic acid monohydrate, N-dimethylformamide and petroleum ether is 200:100-120:4-6:300-500:2000-4000; the molar ratio of the tetrahydroxy monomer VP to the Epoxy Chloropropane (ECH) to the tetrabutylammonium bromide is 1:40-250:1-3.
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be further and clearly described below by means of the detailed description and the accompanying drawings, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Furthermore, unless otherwise defined, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The raw materials, specific preparation operations and performance tests of the invention are conventional techniques.
Synthesis example preparation of Tetraepoxy monomer
(1) Protocatechuic aldehyde (PCA, 0.2 mol), erythritol (0.1 mol), p-toluenesulfonic acid monohydrate (p-TSA. H) 2 O,0.0042 mmol), solvent N, N-dimethylformamide (0.39 mol) and water scavenger petroleum ether (3.3 mol) were placed in a reactor equipped with a water separator and a spherical condenser. The mixture is reacted for 24 hours at 90 ℃ under the protection of nitrogen, the product is cooled, then poured into deionized water to separate out precipitate, filtered by suction and washed with deionized water for five times, and finally dried for 6 hours in a vacuum oven to obtain the tetrahydroxy monomer product (VP). FIG. 1 (a) shows a schematic synthesis of VP.
(2) The obtained tetrahydroxy monomer VP (10 g, 0.0026 mol) and Epichlorohydrin (ECH) (51 g, 0.551 mol) were sequentially added into a reactor, tetrabutylammonium bromide (1 g,0.0031 mol) was reacted at 80℃for 3 hours, then an aqueous sodium hydroxide solution (40 wt%,11 g) was added dropwise at room temperature, the reaction was continued for 3 hours, a crude product was obtained by suction filtration, methylene chloride and water were added, an organic layer was collected, the obtained organic layer was dried with anhydrous magnesium sulfate, the solvent was removed by a rotary evaporator, and finally vacuum-dried at 90℃for 5 hours, to obtain the objective epoxy monomer (DGEVP). Fig. 1 (b) shows a schematic diagram of DGEVP synthesis.
FIG. 2 is an infrared spectrum (FTIR) plot of PCA, erythritol, VP, and DGEVP; nuclear magnetic resonance spectrum of VP 1 H NMR) and carbon nuclear magnetic resonance spectroscopy 13 C NMR) map; DGEVP 1 H NMR 13 C NMR chart; liquid chromatography-mass spectrometry (LC-MS) images of VP and DGEVP. VE is obtained by condensation of PCA with erythritol and DGEVP is obtained by reaction of hydroxyl groups on VE with ECH. As shown in FIG. 1 (a), the FTIR spectrum of PCA shows that the spectrum of the PCA is shown in the presence of hydroxyl groups (about 3190-3300 cm -1 ) C-H in benzene ring (3047 cm) -1 ) C-H (2890-2725 cm) in aldehyde group (-CHO) -1 ），-CHO（1750 cm -1 ) And aromatic rings (1650, 1600 and 1530 cm) -1 ) A kind of electronic deviceCharacteristic absorption peaks. FTIR spectra of erythritol showed-OH (3100-3500 cm) -1 ) C-H (2965 and 2908 cm) -1 ，1406 cm -1 ) Primary and secondary alcohols (1080 and 1050 cm) -1 ）C-O（972 cm -1 ) Is characterized by an absorption peak. A new change in the FTIR spectrum of VP compared to the spectra of PCA and erythritol, at 1005 cm -1 、1280 cm -1 、1160 cm -1 And 1107cm -1 A new strong characteristic peak is arranged at the position, this is due to the formation of-C-O-C-, C-O-, C-O-C, furthermore, no characteristic peak of-CHO appears in the FTIR spectrum of VP. After VP and ECH react, at 910 cm -1 Characteristic peaks appear at the sites, which are characteristic peaks of epoxy groups, and at the same time at 3100-3500 cm -1 No significant-OH peak appears, which means that the bio-based tetrafunctional epoxy monomer DGEVP was successfully synthesized.
To further determine the chemical structure of VP and DGEVP, we used 1 H NMR and 13 C NMR characterizes the structure of the product, in VP 1 In the H NMR nuclear magnetic spectrum, δ=8.97 ppm is hydrogen proton in OH linked to benzene ring, and δ=6.83, 6.76, 6.58 ppm corresponds to hydrogen proton in benzene ring; hydrogen protons in δ=5.58 ppm corresponding-O-CH-O-; corresponding to-CH-O and-C-CH at delta = 4.18 ppm and 3.90-3.67 ppm 2 Hydrogen protons in, VP 13 The chemical shift and peak number in C NMR also corresponds one-to-one to the carbon atoms in VP. Furthermore, the LC-MS spectrum shows a molar mass of VP of 385.0911g/mol, which is consistent with the theoretical value of 385.0900 g/mol. This means that VP was successfully synthesized. In the 1H NMR spectrum of DGEVP, hydrogen protons in epoxy groups are at δ=3.42-3.31 ppm,2.89ppm and 2.76ppm, and-O-CH is at δ=3.76-3.64 ppm 2 Hydrogen protons in-CH at delta=3.88-3.79 ppm 2 -O-CH 2 Hydrogen protons in C-are in aldehyde structure at δ=5.58 ppm and in benzene ring at δ= 7.10,7.00 and 6.94 ppm. With VP 1 In comparison to the H NMR spectrum, DGEVP 1 The H NMR spectrum showed no proton peak in the phenolic hydroxyl group at 8.97 ppm. Furthermore, DGEVP 13 The chemical shift and the number of peaks in C NMR correspond one-to-one with the carbon atoms in VP, while LC-MS spectrum shows that DGEVP has a molar mass of 609.1948g/mol, andthe theoretical value is 609.1948 g/mol. This means that DGEVP was successfully synthesized.
Example 1 Medium temperature curing epoxy resin System and high Performance degradable multifunctional epoxy resin
A mixture of 100g DGEVP and 1.25g zinc acetylacetonate (ZAA) was heated and stirred at 140℃to a clear liquid, then 33g Glutaric Anhydride (GA) was added at 80℃and stirred for 20min to give a homogeneous prepolymer medium temperature cure epoxy system. Subsequently, the prepolymer was poured into a preheated mold, the bubbles were removed in a vacuum oven at 80℃and then cured according to a temperature program of 80℃/2h+100℃/2h to obtain a cured product.
Comparative example 1
A mixture of 100g of bisphenol A epoxy resin (E51) and 1.25g of zinc acetylacetonate (ZAA) was heated at 140℃and the clear liquid was stirred, then 30g of Glutaric Anhydride (GA) was added at 80℃and stirred for 20min to give a homogeneous prepolymer. Subsequently, the prepolymer was poured into a preheated mold, the bubbles were removed in a vacuum oven at 80℃and then cured according to a temperature program of 80℃/2h+100℃/2h to obtain a cured product.
Comparative example 1-1
A mixture of 100g of bisphenol A epoxy resin (E51) and 1.25g of zinc acetylacetonate (ZAA) was heated and stirred at 140℃to a transparent liquid, then 30g of Glutaric Anhydride (GA) was added at 80℃and stirred for 20min to give a uniform prepolymer. Subsequently, the prepolymer was poured into a preheated mold, the bubbles were removed in a vacuum oven at 80℃and then cured according to the temperature program of 80℃C/2h+100℃C/2h+140℃C/2h+180℃C/2h to obtain a cured product.
Table 1 shows the mechanical property data, resin system reaction activation energy (Ea), conversion rate of epoxy groups (. Alpha.) and glass transition temperature (T) of the cured resin system of example 1, comparative examples 1-1 and comparative examples 1-2 g ). As can be seen from Table 1, the resin system prepared from the biomass epoxy resin synthesized by the method has better mechanical property and thermal property than the traditional commercial bisphenol A epoxy resin cured at medium temperature and high temperature, and the resin system has better reaction activation energyE a Lower, even at medium temperature curingIn addition, the resin system also has high epoxy group conversion rate, and the invention has obviously higher T than the prior bisphenol A epoxy resin (DGEBA) g Overcomes the defect of the prior biomass epoxy resin T g The problem of inferior to bisphenol a epoxy resins. In particular, DGEVP cured products have not only mild acid degradation behavior, but also good crack self-healing ability at 200 ℃ (FIG. 3), at a temperature of about T g +20℃ had good shape deformation and recovery ability (FIG. 4). The traditional bisphenol A epoxy resin cured by anhydride has no acid degradation behavior, and the cured DGEVP is extremely easy to degrade under the acid condition.
a,b,c Flexural strength, impact strength and tensile strength tests were carried out with reference to the resin casting performance test standard GB/T2567-2008.
d The apparent activation energy was calculated using the Kissinger extremum method.
e : based on the infrared spectrum of the sample, the conversion of the epoxy groups was calculated using an internal standard method.
f Obtaining T using DMA g 。
g 50mg of the sample was immersed in 10ml of hydrochloric acid solution to observe degradation time.
In the prior art, protocatechuic aldehyde and 4, 4-diaminodiphenyl ether (ODA) are used as raw materials to synthesize semi-bio-based PH-ODA, epichlorohydrin and NaOH are used as raw materials, a two-step method is used to synthesize semi-bio-based flame-retardant epoxy prepolymer, a curing agent DDM is used to cure the PH-ODA-EP of the epoxy prepolymer, so that the PH-ODA-EP/DDM of an epoxy cured product is obtained, ea is higher than DGEBA/DDM, the reactivity of a PH-ODA-EP/DDM curing system is lower than that of a DGEBA/DDM curing system, the curing temperature of 190 ℃ is needed, and the epoxy resin-based epoxy prepolymer contains a part of petroleum-based raw material ODA and is not fully utilized. Compared with the prior reported cured object system containing the double epoxy monomers with the spiral acetal, the single-ring acetal and the double-ring acetal structures, the epoxy resin/anhydride curing system has good self-repairing behavior, low curing temperature and low production energy consumption.
The resin system of the present invention has low curing temperature, and the existing acetal-containing epoxy/anhydride system has the defect of higher curing temperature, and the DSC curve of the resin system in the comparative example 1 of the example 1 is shown in FIG. 5, and the reaction temperature of DGEVP/GA/ZAA is obviously lower than that of E51/GA/ZAA.
Example 2
A mixture of 100g DGEVP and 2.5g zinc acetylacetonate (ZAA) was heated and stirred at 140℃to a clear liquid, then 33g Glutaric Anhydride (GA) was added at 80℃and stirred for 20min to give a homogeneous prepolymer. Subsequently, the prepolymer was poured into a preheated mold, the bubbles were removed in a vacuum oven, and then cured according to a temperature program of 80 ℃/2h+100 ℃/2h to obtain a cured product.
Comparative example 2
A mixture of 100g of E51 and 2.5g of zinc acetylacetonate (ZAA) was heated and stirred at 140℃to a clear liquid, then 30g of Glutaric Anhydride (GA) was added at 80℃and stirred for a further 20min to give a homogeneous prepolymer. Subsequently, the prepolymer was poured into a preheated mold, the bubbles were removed in a vacuum oven, and then cured according to the temperature program of 80 ℃/2h+100 ℃/2h+140 ℃/2 h+180 ℃/2h to obtain a cured product.
Table 2 shows the mechanical property data of the cured product samples of example 2 and comparative example 2, E of the resin system a Conversion of epoxy groups alpha and T g . As can be seen from Table 2, the resin system prepared from the biomass epoxy resin synthesized by the method has better mechanical property and thermal property than the traditional commercial bisphenol A epoxy resin cured at medium temperature and high temperature, and the resin system has better reaction activation energy E a Lower, even after medium temperature curing treatment, the resin system has high epoxy group conversion rate. DGEVP cured products were very susceptible to degradation under acidic conditions (fig. 6 (a)), and cured product samples were monitored for degradation products in 0.1M HCl solution (acetone/water=9:1, v:v) at 50 ℃ using real-time nmr, see fig. 6 (b). In addition, DGEVP cured products had good crack self-healing ability at 200 ℃ (fig. 7). DGEVP cured product at T g Has good temperature aboveGood shape deformation and recovery (fig. 8).
Example III
A mixture of 100g DGEVP and 5.0g zirconium acetylacetonate (AAZ) was heated and stirred at 200℃to a clear liquid, then 55g methyl hexahydrophthalic anhydride (MeHHPA) was added at 80℃and stirred for 20min to give a homogeneous prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, followed by a temperature program of 80℃per 2h+100℃per 2h+120℃per 4h to obtain a cured product.
Comparative example 3
A mixture of 100g of E51 and 5.0g of zirconium acetylacetonate (AAZ) was heated and stirred at 200℃to a clear liquid, then 45g of methyl hexahydrophthalic anhydride (MeHHPA) was added at 80℃and stirred for 20min to give a homogeneous prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, followed by 80 ℃/2h+100 ℃/2h+140 ℃/2 h+180 ℃/2h according to the temperature program to obtain a cured product.
Table 3 shows the mechanical property data of the cured product samples of example 3 and comparative example 3, ea of the resin system, the conversion rate α of epoxy groups of the cured resin system, and the glass transition temperature T g . As can be seen from Table 3, the resin system prepared by the biomass epoxy resin synthesized by the invention has better mechanical property and thermal property than the traditional commercial bisphenol A epoxy resin cured at medium temperature and high temperature, the resin system has lower reaction activation energy Ea, even though the resin system is cured at medium temperature, the resin system has high epoxy group conversion rate, and the cured product is extremely easy to degrade under acidic conditions. In addition, DGEVP cured products had good crack self-healing ability at 200 ℃ (fig. 9). DGEVP cured product at T g Above this temperature, the shape deformation and recovery ability were good (fig. 10).
Example IV
A mixture of 60g DGEVP and 0.5g zinc acetylacetonate (ZAA) was heated and stirred at 140℃to a clear liquid, then 22g citraconic anhydride was added at 80℃and stirred for 20min to give a homogeneous prepolymer. Subsequently, the prepolymer was poured into a preheated mold, and the bubbles were removed in a vacuum oven, followed by a temperature program of 80℃per 2h+100℃per 2h+120℃per 2h to obtain a cured product.
Comparative example 4
A mixture of 60g of E51 and 0.5g of zinc acetylacetonate (ZAA) was heated and stirred at 140℃to a clear liquid, then 18g of citraconic anhydride was added at 80℃and stirred for a further 20 minutes to give a homogeneous prepolymer. Subsequently, the prepolymer was poured into a preheated mold, the bubbles were removed in a vacuum oven, and then cured according to the temperature program of 80 ℃/2h+100 ℃/2h+140 ℃/2 h+180 ℃/2h to obtain a cured product.
Table 4 shows the mechanical property data, the resin system reaction activation energy Ea, the conversion rate α of epoxy groups of the cured resin system and the glass transition temperature Tg of the cured product samples of example 4 and comparative example 4. From table 4, it can be seen that the mechanical properties and thermal properties of the resin system prepared by the biomass epoxy resin synthesized by the invention at medium temperature are better than those of the traditional commercial bisphenol a epoxy resin cured at medium temperature and high temperature, the reaction activation energy Ea of the resin system is lower, the resin system has high epoxy group conversion rate even after the medium temperature curing treatment, and the cured product is extremely easy to degrade under acidic conditions. In addition, DGEVP cured products had good crack self-healing ability at 200 ℃ (fig. 11). DGEVP cured product at T g Above this temperature, the shape deformation and recovery ability were good (fig. 12).
Claims (10)
1. The bio-based epoxy monomer is characterized by having the following chemical structural formula:
2. the method for preparing the bio-based epoxy monomer according to claim 1, wherein protocatechuic aldehyde, erythritol and epichlorohydrin are used as raw materials to synthesize the bio-based epoxy monomer.
3. The method for preparing the bio-based epoxy monomer according to claim 2, wherein the tetra-hydroxyl monomer is prepared by using protocatechuic aldehyde and erythritol as raw materials; and then preparing the bio-based epoxy monomer by taking tetrahydroxy monomer and epichlorohydrin as raw materials.
4. The method for preparing the bio-based epoxy monomer according to claim 3, wherein protocatechuic aldehyde and erythritol are used as raw materials, and the tetrahydroxy monomer is prepared by reaction in the presence of a catalyst and in a solvent; the bio-based epoxy monomer is prepared by taking tetrahydroxy monomer and epichlorohydrin as raw materials in the presence of organic ammonium salt in an alkaline environment.
5. The method for preparing bio-based epoxy monomer according to claim 4, wherein the catalyst is p-toluenesulfonic acid monohydrate; the mol ratio of protocatechuic aldehyde to erythritol to p-toluenesulfonic acid monohydrate is 200: (100-120): (4-6); the organic ammonium salt is tetrabutylammonium bromide; adding sodium hydroxide solution to form an alkaline environment; the molar ratio of the tetrahydroxy monomer to the epichlorohydrin to the tetrabutylammonium bromide is 1:40-250:1-3.
6. A medium temperature cured epoxy resin system comprising the biobased epoxy monomer of claim 1, an anhydride curing agent and a catalyst.
7. The preparation method of the intermediate-temperature curing epoxy resin system as claimed in claim 6 is characterized in that the bio-based epoxy monomer as claimed in claim 1 and a catalyst are melted and mixed uniformly, then an anhydride compound is added at 60-80 ℃ and prepolymerized to obtain the intermediate-temperature curing epoxy resin system.
8. The method of preparing a medium temperature cure epoxy resin system according to claim 7, wherein the anhydride compound is a low melting point petroleum-based anhydride, a bio-based anhydride or a mixture thereof; the catalyst is an organometallic complex.
9. A high-performance degradable multifunctional epoxy resin is obtained by medium-temperature curing the medium-temperature curing epoxy resin system of claim 6.
10. Use of the bio-based epoxy monomer of claim 1, the medium temperature cured epoxy resin system of claim 6 or the high performance degradable multifunctional epoxy resin of claim 9 for the preparation of high performance degradable multifunctional epoxy materials.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117003713A (en) * | 2023-07-14 | 2023-11-07 | 苏州大学 | Biomass epoxy monomer and biomass high-heat-resistance self-repairing epoxy resin |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016204647A (en) * | 2015-04-15 | 2016-12-08 | 三菱化学株式会社 | Polyfunctional epoxy resin and intermediate, epoxy resin composition, and cured product |
| CN109320521A (en) * | 2018-09-28 | 2019-02-12 | 中国科学院宁波材料技术与工程研究所 | Epoxy monomer and preparation method thereof, epoxy resin |
| CN110028652A (en) * | 2019-04-29 | 2019-07-19 | 上海华谊树脂有限公司 | A kind of high purity epoxy resins and preparation method thereof containing biphenyl structural |
| CN111004472A (en) * | 2019-12-15 | 2020-04-14 | 苏州大学 | Epoxy resin prepolymer with phase-splitting structure and preparation method and application thereof |
| CN112662276A (en) * | 2020-12-23 | 2021-04-16 | 华南理工大学 | Bio-based fireproof salt-tolerant water-based epoxy resin coating and preparation method thereof |
| CN113621219A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Fast-curing epoxy resin composite material and preparation method thereof |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
| CN114989762A (en) * | 2022-06-29 | 2022-09-02 | 东莞市德聚胶接技术有限公司 | Conductive adhesive for single-component semiconductor and preparation method thereof |
| CN115232589A (en) * | 2022-08-05 | 2022-10-25 | 东莞市德聚胶接技术有限公司 | High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof |
-
2023
- 2023-03-31 CN CN202310333763.7A patent/CN116375727B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016204647A (en) * | 2015-04-15 | 2016-12-08 | 三菱化学株式会社 | Polyfunctional epoxy resin and intermediate, epoxy resin composition, and cured product |
| CN109320521A (en) * | 2018-09-28 | 2019-02-12 | 中国科学院宁波材料技术与工程研究所 | Epoxy monomer and preparation method thereof, epoxy resin |
| CN110028652A (en) * | 2019-04-29 | 2019-07-19 | 上海华谊树脂有限公司 | A kind of high purity epoxy resins and preparation method thereof containing biphenyl structural |
| CN111004472A (en) * | 2019-12-15 | 2020-04-14 | 苏州大学 | Epoxy resin prepolymer with phase-splitting structure and preparation method and application thereof |
| CN112662276A (en) * | 2020-12-23 | 2021-04-16 | 华南理工大学 | Bio-based fireproof salt-tolerant water-based epoxy resin coating and preparation method thereof |
| CN113621219A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Fast-curing epoxy resin composite material and preparation method thereof |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
| CN114989762A (en) * | 2022-06-29 | 2022-09-02 | 东莞市德聚胶接技术有限公司 | Conductive adhesive for single-component semiconductor and preparation method thereof |
| CN115232589A (en) * | 2022-08-05 | 2022-10-25 | 东莞市德聚胶接技术有限公司 | High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| WANGCHAO YUAN ET AL.: "Synthesis of fully bio-based diepoxy monomer with dicyclo diacetal for high-performance, readily degradable thermosets", 《EUROPEAN POLYMER JOURNAL》, vol. 117, 15 May 2019 (2019-05-15), pages 200 - 207, XP085713428, DOI: 10.1016/j.eurpolymj.2019.05.028 * |
| WEIQI XIE ET AL.: "Biomass-derived Schiff base compound enabled fire-safe epoxy thermoset with excellent mechanical properties and high glass transition temperature", 《CHEMICAL ENGINEERING JOURNAL》, vol. 394, 2 December 2019 (2019-12-02), pages 1 - 10, XP086186941, DOI: 10.1016/j.cej.2019.123667 * |
| 吕银祥 等: "《现代信息材料导论》", vol. 2008, 30 September 2008, 华东理工大学出版社, pages: 198 - 199 * |
| 王德中: "《环氧树脂生产与应用》", vol. 2001, 30 June 2001, 化学工业出版社, pages: 165 - 167 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117003713A (en) * | 2023-07-14 | 2023-11-07 | 苏州大学 | Biomass epoxy monomer and biomass high-heat-resistance self-repairing epoxy resin |
| CN117003713B (en) * | 2023-07-14 | 2024-05-28 | 苏州大学 | Biomass epoxy monomer and biomass high-heat-resistance self-repairing epoxy resin |
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