CN112795015A - A four-functional eugenol epoxy-functionalized cage silsesquioxane and its preparation method and application - Google Patents
A four-functional eugenol epoxy-functionalized cage silsesquioxane and its preparation method and application Download PDFInfo
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- CN112795015A CN112795015A CN202110156582.2A CN202110156582A CN112795015A CN 112795015 A CN112795015 A CN 112795015A CN 202110156582 A CN202110156582 A CN 202110156582A CN 112795015 A CN112795015 A CN 112795015A
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- tetrafunctional
- epoxy
- eugenol
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- functionalized cage
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- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 title claims abstract description 114
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000005770 Eugenol Substances 0.000 title claims abstract description 57
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229960002217 eugenol Drugs 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 41
- 239000004593 Epoxy Substances 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 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 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000003607 modifier Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004841 bisphenol A epoxy resin Substances 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
- 239000007788 liquid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- ZQSIJRDFPHDXIC-UHFFFAOYSA-N daidzein Chemical compound C1=CC(O)=CC=C1C1=COC2=CC(O)=CC=C2C1=O ZQSIJRDFPHDXIC-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VVOAZFWZEDHOOU-UHFFFAOYSA-N magnolol Chemical compound OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 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
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 241000598860 Garcinia hanburyi Species 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- QNVSXXGDAPORNA-UHFFFAOYSA-N Resveratrol Natural products OC1=CC=CC(C=CC=2C=C(O)C(O)=CC=2)=C1 QNVSXXGDAPORNA-UHFFFAOYSA-N 0.000 description 1
- LUKBXSAWLPMMSZ-OWOJBTEDSA-N Trans-resveratrol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC(O)=CC(O)=C1 LUKBXSAWLPMMSZ-OWOJBTEDSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 235000007240 daidzein Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 229940117709 gamboge Drugs 0.000 description 1
- TZBJGXHYKVUXJN-UHFFFAOYSA-N genistein Natural products C1=CC(O)=CC=C1C1=COC2=CC(O)=CC(O)=C2C1=O TZBJGXHYKVUXJN-UHFFFAOYSA-N 0.000 description 1
- 235000006539 genistein Nutrition 0.000 description 1
- 229940045109 genistein Drugs 0.000 description 1
- ZCOLJUOHXJRHDI-CMWLGVBASA-N genistein 7-O-beta-D-glucoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=C2C(=O)C(C=3C=CC(O)=CC=3)=COC2=C1 ZCOLJUOHXJRHDI-CMWLGVBASA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004754 hydrosilicons Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960003371 protocatechualdehyde Drugs 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 229940016667 resveratrol Drugs 0.000 description 1
- 235000021283 resveratrol Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940117960 vanillin Drugs 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
本发明公开了一种四官能度丁香酚环氧功能化的笼型倍半硅氧烷及其制备方法和应用。四官能度丁香酚环氧功能化的笼型倍半硅氧烷的结构式如下式(I)所示；本发明产品为生物基笼型倍半硅氧烷，具有柔顺的分子链结构，优异的热稳定性和耐水性，可单独用于制备生物基环氧树脂；还与炭基材料有较好的相容性，作为改性剂用于环氧树脂体系能够实现纳米尺度高度均匀分散，有效提高树脂在疏水、耐热和抗冲等方面的性能，在高性能杂化或复合材料的制备和应用领域具有广阔的应用前景。
The invention discloses a tetrafunctional eugenol epoxy-functionalized cage-type silsesquioxane and a preparation method and application thereof. The structural formula of the tetrafunctional eugenol epoxy-functionalized cage silsesquioxane is shown in the following formula (I); the product of the present invention is a bio-based cage silsesquioxane, which has a flexible molecular chain structure and excellent Thermal stability and water resistance, can be used alone to prepare bio-based epoxy resin; also has good compatibility with carbon-based materials, as a modifier used in epoxy resin system can achieve high nano-scale uniform dispersion, effective Improving the properties of the resin in terms of hydrophobicity, heat resistance and impact resistance has broad application prospects in the preparation and application of high-performance hybrid or composite materials.
Description
Technical Field
The invention relates to the technical field of silsesquioxane, in particular to a four-functionality eugenol epoxy functionalized cage type silsesquioxane, a preparation method thereof and application thereof in preparation of a bio-based epoxy resin nano hybrid material.
Background
Silsequioxanes (silsequioxanes) are a class of silsequioxanes having (RSiO)3/2)nThe empirical T-type organosilicon materials can be classified into random, trapezoidal, cage-shaped, and macrocyclic structures, depending on the structure. Among them, Polyhedral Oligomeric Silsesquioxane (POSS for short) is a class of nanoscale body-type molecules with precise configuration, and is also a class of Silsesquioxane which is researched more at present. Structurally, POSS consists of an inorganic cage core skeleton of Si-O-Si and organic substituents covered on the periphery. The size of POSS is usually 1-3 nm, the Si-O-Si cage-shaped inner core in the structure can endow the POSS with advantages in the aspects of heat and mechanics, organic substituent groups connected with the inner core can enable the POSS to be compatible with organic matters, biological systems or surfaces, and the substituent groups can be functionalized and derivatized accurately and quantitatively. The unique inorganic-organic structure of POSS makes its molecular structure easy to design, and has outstanding heat-resisting, oxidation-resisting, hydrophobic, low dielectric and mechanical properties, these characteristics make POSS become a kind of very promising nanometer structure unit, have a great potential in the preparation field of advanced functional nano-materials. However, the existing POSS has very limited varieties and is difficult to meet the requirements of material preparation, thereby restricting the development of POSS.
Epoxy resins have been developed into a large class of thermosetting resins because of their excellent mechanical and electrical properties, and are widely used in the fields of adhesives, structural composites, electronic semiconductor packaging, and the like. But the toughness is poor and the performance is greatly influenced by the epoxy resin matrix. At present, most of epoxy resins are prepared from petrochemical products with limited resources, wherein most of epoxy resin prepolymers are prepared by reacting bisphenol A with epichlorohydrin. However, bisphenol a has been classified as carcinogenic mutagenic and reproductive toxic and is considered an endocrine disrupter and is severely limited in its use. In addition, the price of bisphenol A is greatly fluctuated by the international crude oil price and is not reproducible; the cured product has poor flame retardancy and electrical properties, and is limited in application in high-tech fields. Therefore, bisphenol a epoxy resins have been banned from use in related fields in contact with food and human bodies in many countries of the world, and it is of great significance to develop environmentally friendly epoxy resins that can replace bisphenol a epoxy resins.
Currently, many bio-based epoxies are used for the modification of epoxy resins, mainly derived from cardanol, eugenol, vanillin, tannic acid, gallic acid, etc. (Wan et al,2020), and vanillin (Huang et al,2019, Memon et al,2020, Liu et al,2020), gamboge (Noe et al,2019), resveratrol (Tian et al,2020), magnolol (Qi et al,2020), protocatechuic aldehyde (Xie et al,2020), genistein (Dai et al,2019), daidzein (Ma and Li,2019) and salicylaldehyde (Li and Cai,2020), among others. The bio-based epoxy resin mainly comprises linear or branched aliphatic and aromatic micromolecules, has no advantages in many aspects such as thermal stability, flame retardance and the like, and is often single in effect. In addition, the poor compatibility of POSS and carbon-based materials leads to the unsatisfactory combination property of the composite materials, and is also one of the problems to be solved.
Disclosure of Invention
The invention aims at the problems and provides a four-functionality eugenol epoxy functionalized cage-type silsesquioxane. The bio-based POSS is viscous and liquid at normal temperature, has excellent thermal stability and better compatibility with carbon-based materials, can be directly used as a base material to prepare bio-based epoxy resin, can also be used as a bio-based modifier to be compounded to other epoxy resin systems, can realize nanoscale highly uniform dispersion with other epoxy resin matrixes, and effectively improves the performances of the resin in various aspects such as water resistance, heat resistance, impact resistance and the like.
The specific technical scheme is as follows:
a tetrafunctional eugenol epoxy functionalized cage type silsesquioxane has a structural formula shown as the following formula (I):
the glass transition temperature of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane is 10.7 ℃, and the initial thermal decomposition temperature (T) is in a nitrogen atmosphere-5％) The temperature was 375 ℃ and the residual carbon content at 800 ℃ was 46.0%. Obviously superior to other prior four-functionality POSS, such as four-functionality hydrosilicon functionalized cage type silsesquioxane (marked as DDSQ-4H) or four-functionality vinyl functionalized cage type silsesquioxane (marked as DDSQ-4Vi)
The invention discloses a tetrafunctional eugenol epoxy functionalized cage type silsesquioxane which has a novel structure, and a biological-based monomer molecular chain with the body type structure is soft and smooth and is in a viscous liquid state at normal temperature; the resin has excellent thermal stability, high initial thermal decomposition temperature and high carbon residue, can be independently used as a base material to prepare bio-based epoxy resin, and has excellent performances of high temperature resistance, water resistance and high impact resistance; and the compatibility with carbon-based materials is good, an epoxy resin cross-linked network can be introduced in a co-curing mode, and the epoxy resin cross-linked network is highly and uniformly dispersed in other resin matrixes through characterization, so that the high-temperature resistance, water resistance and impact resistance of the epoxy resin cross-linked network are fully exerted.
The invention also discloses a preparation method of the tetrafunctional eugenol epoxy functionalized cage type silsesquioxane, which comprises the following steps:
(a) under the inert atmosphere, mixing tetrafunctional hydrosilation functionalized cage-type silsesquioxane with a structural formula shown as the following formula (II), eugenol epoxy monomer, solvent and catalyst to perform hydrosilylation reaction until the reaction is complete;
(b) separating and purifying the reaction mother liquor in the step (a) to obtain the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane.
In step (a):
the inert atmosphere is a gas conventional in the art, such as nitrogen, argon, and the like.
The DDSQ-4H reference reports (chem. commun.,2017,53,10370) preparation.
The preparation reference of the eugenol epoxy monomer reports (ACS Sustainable chem. Eng.2018,6,8856-8867) preparation, and the purity of the eugenol epoxy monomer is more than 98 percent.
A tetrafunctional hydrosilyl functionalized cage-type silsesquioxane, based on molar mass: eugenol epoxy monomer ═ 1: 4-20, preferably 1: 6 to 10.
The solvent is selected from one or more of toluene, tetrahydrofuran and isopropanol; toluene is preferred.
The solvent is 5-15 times of the eugenol epoxy monomer by mass.
The solvent is required to be dried before use.
The catalyst is selected from platinum catalysts; preferably one or more of a Karster catalyst, chloroplatinic acid and platinum dioxide.
The concentration of the catalyst is 10-200 ppm in terms of the mole number of the reaction functional groups; the catalyst concentration is calculated by the content of platinum in the catalyst; preferably 100 to 150 ppm.
The temperature of the hydrosilylation reaction is 80-120 ℃.
In the step (b), the separation and purification method comprises the following steps: the reaction mother liquor is subject to rotary evaporation to remove low-boiling-point substances, the crude product is added with petroleum ether, stirred and washed for several times, and then vacuum drying is carried out.
Preferably, the washing is carried out under heating.
Tests show that the crude product shows excellent separation effect in petroleum ether, and other common separation and purification reagents, such as diethyl ether, cyclohexane, n-hexane, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, dichloromethane, acetone, chloroform, toluene and the like, are difficult to purify or have poor purification effect.
The invention also discloses application of the tetrafunctional eugenol epoxy functionalized cage type silsesquioxane in preparation of epoxy resin.
The method specifically comprises the following steps:
the biological epoxy resin nanometer hybrid material is prepared by taking the four-functionality eugenol epoxy functionalized cage-type silsesquioxane and other epoxy resin which can be selectively added as raw materials and curing the raw materials.
The four-functionality eugenol epoxy functionalized cage-type silsesquioxane and the epoxy resin can realize uniform dispersion in a nanometer scale, so that no special requirement is imposed on the dosage of the four-functionality eugenol epoxy functionalized cage-type silsesquioxane and the epoxy resin, and the four-functionality eugenol epoxy functionalized cage-type silsesquioxane and the epoxy resin can be mixed in any proportion.
The tetrafunctional eugenol epoxy functionalized cage type silsesquioxane can be independently used as a raw material, and a biological epoxy resin material is prepared by curing. The resin material has excellent high temperature resistance, water resistance and impact resistance.
The tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane can be blended with epoxy resin commonly used in the field and then cured to prepare a bio-based epoxy resin nano hybrid material. The interior of the prepared bio-based epoxy resin hybrid material is characterized, and the fact that the four-functionality eugenol epoxy functionalized cage-type silsesquioxane is completely and uniformly distributed in a nanoscale manner can be found, so that the high-temperature resistance, the water resistance and the shock resistance of the cage-type silsesquioxane are fully exerted.
The epoxy resin is selected from the group common in the art, including bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin, and the like.
The curing agent used for the curing is not particularly required and is selected from the common categories in the field, such as polyamine type, anhydride type, phenolic type and the like.
Compared with the prior art, the invention has the following gain effects:
1. the invention discloses a four-functionality eugenol epoxy functionalized cage-type silsesquioxane, wherein a biological-based monomer molecular chain with a body structure is flexible, is liquid at room temperature, has excellent thermal stability and water resistance, and is cured to prepare a biological-based epoxy resin with the biological-based monomer molecular chain as a base material, which has excellent high-temperature resistance, water resistance and impact resistance.
2. The four-functionality eugenol epoxy functionalized cage-type silsesquioxane disclosed by the invention also has better compatibility with carbon-based materials, can be used as a biological epoxy resin modifier, can introduce an epoxy resin cross-linking network in a co-curing mode, can be highly and uniformly dispersed in other resin matrixes, can be mixed in any proportion, and effectively improves the comprehensive performance of the resin.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a tetrafunctional eugenol epoxy functionalized cage type silsesquioxane;
FIG. 2 is a nuclear magnetic silicon spectrum of a tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane;
FIG. 3 is a matrix-assisted laser desorption ionization time-of-flight mass spectrum of a tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane;
FIG. 4 is a graph comparing thermogravimetric curves of tetrafunctional eugenol epoxy functionalized cage silsesquioxane (DDSQ-4EUEP), tetrafunctional hydrosilation functionalized cage silsesquioxane (DDSQ-4H), and or tetrafunctional vinyl functionalized cage silsesquioxane (DDSQ-4Vi) in a nitrogen atmosphere;
FIG. 5 is a transmission electron microscope image of the interior of the epoxy resin composite material;
FIG. 6 is a graph of the nano-IR intensity distribution of Si-O groups inside the epoxy resin composite.
Detailed Description
Example 1
DDSQ-4H (3.0g, 2.3mmol), excess high purity eugenol epoxy (6.1g, 28mmol), dry toluene (43g) and Kansted catalyst (platinum content 150ppm) were added to a flask equipped with a magnetic stirrer and reflux condenser under a nitrogen atmosphere. The system is stirred for more than 24h at 100 ℃ to ensure complete reaction. Removing low-boiling-point substances from the mixed solution by rotary evaporation, adding petroleum ether into the crude product, stirring and washing the crude product for a plurality of times at 60 ℃, and drying the crude product in vacuum to obtain liquid, namely the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane with the yield of 95 percent.
FIGS. 1 to 3 show nuclear magnetic hydrogen spectra, silicon spectra and mass spectra of the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane prepared by the invention, and the characterization can confirm that the prepared product conforms to the structure of the formula (I).
Example 2
DDSQ-4H (3.0g, 2.3mmol), high purity eugenol epoxy (2.0g, 9.2mmol), dry toluene (10g) and platinum dioxide (platinum content 100ppm) were added to a flask equipped with a magnetic stirrer and a reflux condenser under a nitrogen atmosphere. The system is stirred for more than 24h at 100 ℃ to ensure complete reaction. Removing low-boiling-point substances from the mixed solution by rotary evaporation, adding petroleum ether into the crude product, stirring and washing the crude product for a plurality of times at 50 ℃, and drying the crude product in vacuum to obtain liquid, namely the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane with the yield of 88 percent.
Example 3
DDSQ-4H (3.0g, 2.3mmol), excess high purity eugenol epoxy (10.0g, 46mmol), dry toluene (150g) and chloroplatinic acid (platinum content 100ppm) were added to a flask equipped with a magnetic stirrer and reflux condenser under a nitrogen atmosphere. The system is stirred for more than 24 hours at 90 ℃ to ensure complete reaction. Removing low-boiling-point substances from the mixed solution by rotary evaporation, adding petroleum ether into the crude product, stirring and washing the crude product for a plurality of times at 60 ℃, and drying the crude product in vacuum to obtain the liquid, namely the tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane with the yield of 93 percent.
Thermal stability test
FIG. 4 shows a comparison of thermal weight loss curves of tetrafunctional eugenol epoxy functionalized cage-type silsesquioxane, tetrafunctional hydrosilation functionalized cage-type silsesquioxane and tetrafunctional vinyl functionalized cage-type silsesquioxane under nitrogen atmosphere, and the related thermal stability data are shown in Table 1 below. It can be seen that the eugenol epoxy functionalized cage-like silsesquioxane has excellent thermal stability, the initial thermal decomposition temperature reaches 375 ℃, the carbon residue at 800 ℃ is as high as 46 percent, and is far higher than the other two.
The tetrafunctional vinyl functionalized cage type silsesquioxane in table 1 is synthesized by itself by the following preparation process: 4Na-DDSQ (10.0g, 8.64mmol), purified triethylamine (10.49g, 103.7mmol) and dry THF (200mL) were added to a flask equipped with a magnetic stirrer and a reflux condenser under a nitrogen atmosphere, and the system was placed at 0 ℃ and mixed uniformly. The mixed solution is slowly injected with vinyl dimethylchlorosilane (12.5g, 103.6mmol) through a syringe, the system reacts for 2h at 0 ℃, and the reaction continues for 20h at 10 ℃. After the reaction is finished, solid precipitates are separated and removed, a liquid phase part is collected, the solvent and other low-boiling substances are removed by rotary evaporation, the crude product is dissolved in dichloromethane and precipitated by methanol (repeated once), the methanol is leached for three times, and the crude product is dried in vacuum (60 ℃,20 h).
TABLE 1
Application example
The preparation method of the bio-based epoxy resin nano hybrid material comprises the following specific steps: mixing four-functionality eugenol epoxy functionalized cage-type silsesquioxane and bisphenol A epoxy resin (DGEBA) according to a mass ratio of 1:4, dissolving in acetone, vigorously stirring and ultrasonically dispersing, adding a curing agent 3,3' -diaminodiphenyl sulfone according to a stoichiometric ratio [ N-H/epoxy (mol) ═ 1/1] of reaction groups and the like after heating and volatilizing the acetone, and raising the temperature to 105 ℃ and vigorously stirring until the system is uniform and transparent. Removing gas in vacuum (100-110 ℃), pouring into a preheated polytetrafluoroethylene mould for curing (140 ℃,2 hours, 160 ℃,2 hours, 180 ℃,2 hours).
The impact strength test is based on GB/T1043.1-2008 standard
The measurement is finished on a pendulum bob impactor, and a sample (120 multiplied by 10 multiplied by 4 mm) is measured by adopting a simple beam mode3) The notched impact strength of each sample was averaged over five specimens.
The thermal stability, hydrophobicity and impact resistance data of the bio-based epoxy resin nano-hybrid material are shown in the following table 2.
The transmission electron microscope picture and the Si-O group nanometer infrared intensity distribution picture of the internal distribution condition of the cage-type silsesquioxane modifier in the bisphenol A epoxy resin matrix are respectively shown in fig. 5 and fig. 6, and the observation of the picture in fig. 5 and fig. 6 can determine that the four-functionality eugenol epoxy functionalized cage-type silsesquioxane can be highly and uniformly dispersed in the bisphenol A epoxy resin matrix in a nanometer scale.
Comparative application
Bisphenol A epoxy resin (DGEBA) and curing agent 3,3' -diamino diphenyl sulfone are mixed according to the stoichiometric ratio of reactive groups and the like [ N-H/epoxy group (mol) ═ 1/1], and the mixture is heated to 105 ℃ and stirred vigorously until the system is uniform and transparent. Removing gas in vacuum (100-110 ℃), pouring into a preheated polytetrafluoroethylene mould for curing (140 ℃,2 hours, 160 ℃,2 hours, 180 ℃,2 hours). The resin thermal stability, hydrophobicity and impact performance data are shown in table 2.
TABLE 2
The principles, embodiments and applications of the present invention have been described herein using specific examples, which are provided only to assist in understanding the methods and key points of the present invention. This summary should not be construed to limit the present invention.
Claims (10)
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