CN112517075A - 一种异构化催化剂及其制备方法,及β-异佛尔酮的制备方法 - Google Patents
一种异构化催化剂及其制备方法,及β-异佛尔酮的制备方法 Download PDFInfo
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- CN112517075A CN112517075A CN202011369912.8A CN202011369912A CN112517075A CN 112517075 A CN112517075 A CN 112517075A CN 202011369912 A CN202011369912 A CN 202011369912A CN 112517075 A CN112517075 A CN 112517075A
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- Prior art keywords
- isophorone
- catalyst
- acetate
- reaction
- beta
- Prior art date
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- LKOKKQDYMZUSCG-UHFFFAOYSA-N 3,5,5-Trimethyl-3-cyclohexen-1-one Chemical compound CC1=CC(C)(C)CC(=O)C1 LKOKKQDYMZUSCG-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229930192627 Naphthoquinone Natural products 0.000 claims abstract description 5
- 150000002791 naphthoquinones Chemical class 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 22
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 20
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 claims description 16
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Chemical class 0.000 claims description 11
- 239000002184 metal Chemical class 0.000 claims description 11
- 239000011258 core-shell material Substances 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000006249 magnetic particle Substances 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 claims description 2
- 229940105324 1,2-naphthoquinone Drugs 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- WOGWYSWDBYCVDY-UHFFFAOYSA-N 2-chlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C=CC1=O WOGWYSWDBYCVDY-UHFFFAOYSA-N 0.000 claims description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims description 2
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- KQPYUDDGWXQXHS-UHFFFAOYSA-N juglone Chemical compound O=C1C=CC(=O)C2=C1C=CC=C2O KQPYUDDGWXQXHS-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 235000012711 vitamin K3 Nutrition 0.000 claims description 2
- 239000011652 vitamin K3 Substances 0.000 claims description 2
- 229940041603 vitamin k 3 Drugs 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006845 Michael addition reaction Methods 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003335 secondary amines Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical compound CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HZNQSWJZTWOTKM-UHFFFAOYSA-N 2,3,4-trimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C(OC)=C1OC HZNQSWJZTWOTKM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ACYBVNYNIZTUIL-UHFFFAOYSA-N n'-benzylethane-1,2-diamine Chemical compound NCCNCC1=CC=CC=C1 ACYBVNYNIZTUIL-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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Abstract
本发明公开一种异构化催化剂及其制备方法,及β‑异佛尔酮的制备方法。所述异构化催化剂,其结构式示意为:
Description
技术领域
本发明涉及一种催化剂及有机合成领域,具体涉及异构化催化剂及α-异佛尔酮制备β-异佛尔酮的方法。
背景技术
β-异佛尔酮(3,5,5-三甲基环己-3-烯-1-酮)是合成维生素E、类胡萝卜素及各种香料的重要中间体,尤其是制备茶香酮(2,6,6-三甲基-2-环己烯-1,4-二酮,KIP)的重要原料。
β-异佛尔酮的常规制备方法是以α-异佛尔酮(3,5,5-三甲基环己-2-烯-1-酮)为原料,在催化剂的作用下通过异构化反应制备得到。β-异佛尔酮的生成涉及去共轭的平衡反应,因此其平衡浓度较低,需要通过精馏等方法不断抽提,促进反应向生成β-异佛尔酮方向移动。
长期以来,对于该异构化反应已有多种方法报道。使用的催化剂类型主要分为酸催化及碱催化两种,主要工艺如下:
美国专利US5907065A以Co3O4、CaO等金属氧化物为催化剂,采用减压精馏的方式进行异构化反应。虽然所得β-异佛尔酮纯度可达97%以上,但反应副产物较多,时空产率低。
在美国专利US4845303A中,以铁、钴、铬、铝等金属的乙酰丙酮配合物作为催化剂,采用反应精馏的方法制备β-异佛尔酮。虽然反应收率可达90-95%,催化剂用量也仅有0.1-1wt%。但反应的时空产率低,且催化剂溶于反应液,难以从体系中分离,不利于工业化应用。
美国专利US4005145A公开一种使用酸类物质进行异构化反应的方法。使用的酸类包括己二酸、三甲氧基苯甲酸等。经过反应精馏,产品纯度可达91%以上,但依旧面临着副产物较多,设备腐蚀严重的问题。
专利CN1288882A、CN1235954A公开了以碱金属化合物,包括氢氧化物、碳酸盐等为催化剂,经过异构化反应制备β-异佛尔酮的方法。该方法虽然所得产品纯度较高,但催化剂碱性较强,对设备腐蚀严重。且催化剂为均相,难以循环利用。
综上,亟需开发一种新型催化剂用于异构化制备β-异佛尔酮的反应,解决现有技术和工艺存在的不足。
发明内容
本发明提供一种异构化催化剂及其制备方法。所述催化剂制备简单,且活性基团通过化学键负载到载体上,催化剂稳定性强,可多次套用无明显活性损失。还提供一种β-异佛尔酮的制备方法,对α-异佛尔酮异构化生成β-异佛尔酮的反应具有高选择性及高收率,催化剂。反应工艺简单,对设备无腐蚀,工业应用性强。
为达到上述目的,本发明采用以下技术方案:
一种异构化催化剂,其结构式示意为:其中,R=、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、 优选-CH2CH2-;M表示Cr、Mn、Fe、Co、Ni、Cu、Zn,优选Zn;Ac表示乙酰氧基;表示核-壳结构磁性纳米粒子Fe3O4@SiO2。
一种制备本发明所述异构化催化剂的方法,包括以下步骤:
1)以3-氯丙基三乙氧基硅烷(CPTES)对核-壳结构磁性纳米粒子Fe3O4@SiO2(SMNP)进行修饰,得到卤代烷基修饰的磁性纳米粒子(MN-Cl);
2)卤代烷基修饰的磁性纳米粒子(MN-Cl)与伯二胺发生取代反应,得到胺基修饰的磁性纳米粒子;
3)使胺基修饰的磁性纳米粒子与邻甲酰苯甲酸发生取代反应制备邻甲酰苯甲酸修饰的磁性纳米粒子;
4)使邻甲酰苯甲酸修饰的磁性纳米粒子与金属离子配位,得到仲胺基与金属配合物修饰的磁性纳米粒子催化剂。
催化剂制备反应方程式示例如下:
本发明所述步骤1)中,所述核-壳结构磁性纳米粒子Fe3O4@SiO2(SMNP),参照文献《羧基化核壳磁性纳米Fe3O4吸附剂的制备及对Cu2+吸附性能》,高等学校化学学报,2012,33(1):107-113制备。
作为一个优选的方案,本发明所述步骤1)中,3-氯丙基三乙氧基硅烷(CPTES)与SMNP的反应在溶剂中进行,所用溶剂包括甲醇、乙醇、甲苯、乙腈、二氯甲烷、丙酮、正己烷、环己烷等中的一种或多种,其中优选甲苯。
本发明所述步骤1)中,SMNP与CPTES的质量比为1:0.5-5,优选1:1-3。
本发明所述步骤1)的反应温度为60-120℃,优选80-110℃。反应时间8-30h,优选10-15h。
本发明所述步骤2)中,所述伯二胺包括乙二胺、丙二胺、丁二胺、己二胺、邻苯二胺、间苯二胺、对苯二胺、1,4-环己烷二胺中的一种或多种,优选乙二胺、丙二胺、丁二胺、己二胺中的一种或多种,更优选乙二胺。
作为一个优选的方案,本发明所述步骤2)中,MN-Cl与伯二胺反应在溶剂中进行,所用溶剂包括甲醇、乙醇、甲苯、乙腈、水、丙酮、正己烷、环己烷等中的一种或多种,优选乙醇。
本发明所述步骤2)中,MN-Cl与伯二胺的质量比为1:2-10,优选1:4-8。
本发明所述步骤2)的反应温度为0-50℃,优选20-40℃。反应时间为15-50h,优选20-40h。
作为一个优选的方案,本发明所述步骤3)中胺基修饰的磁性纳米粒子与邻甲酰苯甲酸的反应在溶剂中进行。所用溶剂包括甲醇、乙醇、四氢呋喃、乙腈、二氯甲烷、丙酮、正己烷、环己烷、乙酸乙酯等中的一种或多种,优选乙腈。
本发明所述步骤3)中,所述胺基修饰的磁性纳米粒子与邻甲酰苯甲酸的质量比为1:5-30,优选1:8-15。
本发明所述步骤3)中,反应温度为20-120℃,优选60-90℃。反应时间为10-60h,优选30-50h。
本发明所述步骤4)中,所得邻甲酰苯甲酸修饰的磁性粒子与金属离子配位反应在相应金属乙酸盐水溶液中进行,所用金属乙酸盐包括乙酸铬、乙酸锰、乙酸铁、乙酸钴、乙酸镍、乙酸铜、乙酸锌等中的一种或多种,优选乙酸锌。
本发明所述步骤4)中,所述邻甲酰苯甲酸修饰的磁性纳米粒子与金属乙酸盐的质量比为1:1-40,优选1:10-20。
本发明所述步骤4)中,反应温度为10-100℃,优选60-80℃。反应时间为5-80h,优选40-50h。
一种β-异佛尔酮的制备方法,α-异佛尔酮在本发明所述的异构化催化剂和助剂的存在下,通过异构化反应制备β-异佛尔酮。
本发明所述β-异佛尔酮的制备方法中,所述异构化催化剂相对于α-异佛尔酮用量为0.1-10wt%,优选0.5-2wt%。
本发明所述β-异佛尔酮的制备方法中,所述助剂为苯醌、萘醌类物质中的一种或多种,优选包括苯醌、叔丁基对苯醌、甲基苯醌、2-氯-1,4-苯醌、1,2-萘醌、1,4-萘醌、5-羟基对萘醌、甲萘醌等中的一种或多种;优选萘醌类物质,更优选为1,4-萘醌。
本发明所述β-异佛尔酮的制备方法中,所述助剂用量相对于α-异佛尔酮用量为0.05-5wt%,优选0.2-2wt%。
本发明所述β-异佛尔酮的制备方法中,所述反应可以通过本领域公知的反应器中进行,优选通过反应精馏工艺在塔式反应器中进行,反应器理论塔板数为20-50块,优选30-40;反应温度100-300℃,优选210-250℃。回流比10-50:1,优选30-40:1。
本发明所述的技术方案具有如下优点:
(1)核-壳结构磁性纳米粒子Fe3O4@SiO2(SMNP)作为催化剂载体,使得负载催化剂具有纳米尺度的分散效果,从而提高了负载催化剂的分散性,从而提高催化剂的利用率。此外,在磁性纳米粒子表面包裹SiO2层,形成核-壳结构,可以避免金属内核被酸性介质腐蚀,同时有效避免了催化剂的团聚,提高了催化剂的使用寿命。
(2)通过3-氯丙基三乙氧基硅烷(CPTES)与伯二胺的进一步修饰,可在磁性载体表面引入起主要催化作用的仲胺基团。并且,可以通过调整不同伯二胺的使用,引入不同取代的仲胺基团,获得最佳催化效果。此外,在引入仲胺基的同时,剩余伯胺基可进一步与邻甲酰苯甲酸反应生成亚胺,亚胺键及羧基可与金属离子配位,得到仲胺基与金属配合物修饰的磁性纳米粒子催化剂,可有效稳定α-异佛尔酮异构化反应过程中生成的碳负离子中间体,避免发生迈克尔加成(产物结构为)及羰基缩合(产物结构为)等副反应,提高反应选择性,避免了反应精馏过程中塔釜重组分的累积。同时,避免了产品β-异佛尔酮向α-异佛尔酮的转化。
(3)所述助剂含有多原子共轭体系,对带电中间体,包括离子、自由基等,可以通过离域作用起到稳定作用。因此同样可以起到避免重组分的累积和β-异佛尔酮向α-异佛尔酮的转化的作用,提高反应选择性。
(4)此外,催化剂中仲胺基及金属离子均是通过化学键连接到催化剂载体上,键合作用比一般吸附力更强,从而可以提高催化剂在循环套用中的稳定性,避免催化剂活性组分流失。催化剂可套用20次,反应转化率、产物选择性及产品纯度无明显降低。
(5)通过化学修饰在磁性粒子表面引入具有催化活性的仲胺基团及金属离子,避免了单独使用有机碱或无机碱催化时,催化剂溶解在体系中,对设备腐蚀且难以回收利用的缺点。催化剂应用于β-异佛尔酮的制备中,催化剂具有催化高效性和专一性,绿色环保。
具体实施方式
下面结合实施例对本发明作进一步的详细说明,本发明的范围包括但不局限于所列举的实施例。
气相色谱分析条件:安捷伦气相色谱,色谱柱HP-5进行在线测定,二阶程序升温,初始温度50℃,保持1min后以5℃/min速率升至80℃;再以10℃/min速率升至250℃。载气高纯N2,分流比100:1。气化室温度250℃,检测器为FID,检测器温度250℃。
红外测试仪器:Vetex-70傅里叶变换红外光谱仪(德国布鲁克公司)。
实施例1
取60g核-壳结构磁性纳米粒子(SMNP)分散于1.5L甲苯中,超声30min使其分散均匀。机械搅拌下加入60g CPTES,随后在N2氛围下110℃反应12h。反应结束后冷却至室温,固体磁性分离,并以无水乙醇洗涤,烘干后得到表面以卤代烷基修饰的磁性纳米粒子(MN-Cl)。IR:2923cm-1,2852cm-1(亚甲基振动),680cm-1(C-Cl键)。
取60g MN-Cl分散于1.5L乙醇中,加入300g乙二胺,超声30min使其分散均匀。随后在N2氛围下25℃反应24h。反应结束后固体磁性分离,并以无水乙醇洗涤,烘干后得到胺基修饰的磁性纳米粒子。IR:2922cm-1,2852cm-1(亚甲基振动),1590cm-1(伯胺键)。
取60g胺基修饰的磁性纳米粒子,分散于1.5L乙腈中,加入600g邻甲酰苯甲酸,超声30min使其分散均匀。随后在N2氛围下70℃反应30h。反应结束后固体磁性分离,并以乙腈洗涤,烘干后得到邻甲酰苯甲酸修饰的磁性纳米粒子。IR:2924cm-1,2851cm-1(亚甲基振动),1642cm-1(亚胺键),1700cm-1(羧基)。
取60g邻甲酰苯甲酸修饰的磁性纳米粒子,分散于1.5L去离子水中,加入600g乙酸锌。超声30min使其分散均匀。随后在N2氛围下60℃反应48h。反应结束后固体磁性分离,并以去离子水洗涤,烘干后得到仲胺基与金属配合物修饰的磁性纳米粒子催化剂(催化剂a)。IR:2922cm-1,2852cm-1(亚甲基振动),1640cm-1(亚胺键),560cm-1(金属配位键)。
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%催化剂a,0.5wt%1,4-萘醌的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率98.2%,β-异佛尔酮选择性99.95%,重组分选择性0.05%,产品β-异佛尔酮纯度94.0%。
实施例2
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%催化剂a,0.5wt%苯醌的α-异佛尔酮,在绝压0.1MPa,220℃,回流比40:1条件下进行精馏反应。α-异佛尔酮转化率97.8%,β-异佛尔酮选择性95.89%,重组分选择性4.11%,产品β-异佛尔酮纯度88.9%。
实施例3
取60g实施例1制备的MN-Cl分散于1.5L乙醇中,加入300g己二胺,超声30min使其分散均匀。随后在N2氛围下25℃反应24h。反应结束后固体磁性分离,并以无水乙醇洗涤,烘干后得到己二胺修饰的磁性纳米粒子。
其余操作参照实施例1,得到仲胺基与金属配合物修饰的磁性纳米粒子(催化剂b)
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%催化剂b,0.5wt%1,4-萘醌的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率93.2%,β-异佛尔酮选择性99.91%,重组分选择性0.09%,产品β-异佛尔酮纯度93.7%。
实施例4
取60g实施例1制备的邻甲酰苯甲酸修饰的磁性纳米粒子,分散于1.5L去离子水中,加入600g乙酸镍。超声30min使其分散均匀。随后在N2氛围下60℃反应48h。反应结束后固体磁性分离,并以去离子水洗涤,烘干后得到仲胺基与金属配合物修饰的磁性纳米粒子催化剂(催化剂c)。
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%催化剂c,0.5wt%1,4-萘醌的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率98.0%,β-异佛尔酮选择性96.02%,重组分选择性3.98%,产品β-异佛尔酮纯度90.7%。
实施例1中催化剂反应结束后磁性分离,并以乙醇洗涤。烘干后按照实施例1中反应精馏的条件,将催化剂进行套用,实验数据如下表1:
表1催化剂a套用数据
对比例1
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%催化剂a的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率97.5%,β-异佛尔酮选择性92.42%,重组分选择性7.58%,产品β-异佛尔酮纯度84.8%。
对比例2
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%实施例1制备的邻甲酰苯甲酸修饰的磁性纳米粒子,0.5wt%1,4-萘醌的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率97.7%,β-异佛尔酮选择性93.20%,重组分选择性6.80%,产品β-异佛尔酮纯度83.9%。
对比例3
将邻甲酰苯甲酸替换为乙醛酸,其余条件参考实施例1,制备得到对比催化剂1。
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%对比催化剂1,0.5wt%1,4-萘醌的的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率97.3%,β-异佛尔酮选择性93.80%,重组分选择性6.20%,产品β-异佛尔酮纯度85.3%。
对比例4
将乙二胺替换为N-苄基乙二胺,其余条件参考实施例1,制备得到对比催化剂2,该催化剂不含活性仲胺基团。
向塔板数35块的板式塔式反应器塔釜加入1000g含有1.0wt%对比催化剂2,0.5wt%1,4-萘醌的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率45.6%,β-异佛尔酮选择性80.75%,重组分选择性19.25%,产品β-异佛尔酮纯度40.36%。
对比例5
向塔板数35块的板式塔式反应器塔釜加入1000g含有含有1.0wt%催化剂a,0.5wt%环己酮的α-异佛尔酮,在绝压0.1MPa,220℃,回流比30:1条件下进行精馏反应。α-异佛尔酮转化率97.3%,β-异佛尔酮选择性92.82%,重组分选择性7.18%,产品β-异佛尔酮纯度85.0%。
以上具体实施方式,并非对本发明的技术方案作任何形式的限制。凡是依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化与修饰,均落入本发明的保护范围之内。
Claims (10)
2.一种制备权利要求1所述异构化催化剂的方法,包括以下步骤:
1)以3-氯丙基三乙氧基硅烷对核-壳结构磁性纳米粒子Fe3O4@SiO2进行修饰,得到卤代烷基修饰的磁性纳米粒子;
2)卤代烷基修饰的磁性纳米粒子与伯二胺发生取代反应,得到胺基修饰的磁性纳米粒子;
3)使胺基修饰的磁性纳米粒子与邻甲酰苯甲酸发生取代反应制备邻甲酰苯甲酸修饰的磁性纳米粒子;
4)使邻甲酰苯甲酸修饰的磁性纳米粒子与金属离子配位,得到仲胺基与金属配合物修饰的磁性纳米粒子催化剂。
3.根据权利要求2所述的方法,其特征在于,所述步骤1)中,Fe3O4@SiO2与3-氯丙基三乙氧基硅烷的质量比为1:0.5-5,优选1:1-3。
4.根据权利要求2或3所述的方法,其特征在于,所述步骤2)中,所述伯二胺包括乙二胺、丙二胺、丁二胺、己二胺、邻苯二胺、间苯二胺、对苯二胺、1,4-环己烷二胺中的一种或多种,优选乙二胺、丙二胺、丁二胺、己二胺中的一种或多种,更优选乙二胺。
5.根据权利要求2-4任一项所述的方法,其特征在于,所述步骤2)中,卤代烷基修饰的磁性纳米粒子与伯二胺的质量比为1:2-10,优选1:4-8。
6.根据权利要求2-5任一项所述的方法,其特征在于,所述步骤3)中,所述胺基修饰的磁性纳米粒子与邻甲酰苯甲酸的质量比为1:5-30,优选1:8-15。
7.根据权利要求2-6任一项所述的方法,其特征在于,所述步骤4)中,所得邻甲酰苯甲酸修饰的磁性粒子与金属离子配位反应在相应金属乙酸盐水溶液中进行,所用金属乙酸盐包括乙酸铬、乙酸锰、乙酸铁、乙酸钴、乙酸镍、乙酸铜、乙酸锌中的一种或多种。
8.根据权利要求7所述的方法,其特征在于,所述步骤4)中,所述邻甲酰苯甲酸修饰的磁性纳米粒子与金属乙酸盐的质量比为1:1-40,优选1:10-20。
9.一种β-异佛尔酮的制备方法,包括以下步骤:α-异佛尔酮在权利要求1所述的异构化催化剂或权利要求2-8所述的方法制备的催化剂和助剂的存在下,通过异构化反应制备β-异佛尔酮。
10.根据权利要求9所述的方法,其特征在于,所述助剂为苯醌、萘醌类物质中的一种或多种,优选包括苯醌、叔丁基对苯醌、甲基苯醌、2-氯-1,4-苯醌、1,2-萘醌、1,4-萘醌、5-羟基对萘醌、甲萘醌中的一种或多种;优选萘醌类物质,更优选为1,4-萘醌;和/或,所述助剂用量相对于α-异佛尔酮用量为0.05-5wt%,优选0.2-2wt%。
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