CN116116464A - Mesoporous polymer M-P-CMP catalyst and preparation method and application thereof - Google Patents
Mesoporous polymer M-P-CMP catalyst and preparation method and application thereof Download PDFInfo
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- CN116116464A CN116116464A CN202211645499.2A CN202211645499A CN116116464A CN 116116464 A CN116116464 A CN 116116464A CN 202211645499 A CN202211645499 A CN 202211645499A CN 116116464 A CN116116464 A CN 116116464A
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- cmp
- catalyst
- isophorone
- reaction
- oxo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 title claims abstract description 18
- 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 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 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 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- -1 porphyrin transition metal Chemical class 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 7
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ANWXWWSYNQLVED-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-bromophenyl)-21,23-dihydroporphyrin Chemical compound Brc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(Br)cc2)c2ccc([nH]2)c(-c2ccc(Br)cc2)c2ccc(n2)c(-c2ccc(Br)cc2)c2ccc1[nH]2 ANWXWWSYNQLVED-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 150000004032 porphyrins Chemical group 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- ROTNQFPVXVZSRL-UHFFFAOYSA-N 4,4,6-trimethyl-7-oxabicyclo[4.1.0]heptan-2-one Chemical compound C1C(C)(C)CC(=O)C2OC21C ROTNQFPVXVZSRL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000013317 conjugated microporous polymer Substances 0.000 abstract 4
- 239000003513 alkali Substances 0.000 abstract 1
- 238000012661 block copolymerization Methods 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 208000016560 COFS syndrome Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XJJWWOUJWDTXJC-UHFFFAOYSA-N [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical group [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XJJWWOUJWDTXJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 235000011869 dried fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 238000005406 washing Methods 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- 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
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/37—Metal complexes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a mesoporous polymer M-P-CMP catalyst, which is formed by complexing tetrabromophenyl porphyrin transition metal complex and 1, 4-phenyl diboronic acid to generate a block copolymerization polymer supported transition metal catalyst; the catalyst can be applied to the preparation of isophorone oxide, and the specific process is as follows: in the presence of organic alkali, using conjugated microporous polymer M-P-CMP containing metal porphyrin skeleton as catalyst, using air or oxygen to oxidize beta-isophorone to generate oxo isophorone. After the reaction is finished, the catalyst M-P-CMP is collected through centrifugation and filtration, and the catalyst can be recycled through effective separation. The heterogeneous catalyst disclosed by the invention is stable in structure and high in activity, stability and selectivity. The catalyst has no residue and no falling off in the use process, and truly realizes the green catalysis process. Can be conveniently separated from the system and recycled after the reaction is finished, has good application effect, can be repeatedly used for many times, and does not reduce the efficiency.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and organic synthesis, relates to a technical application of a mesoporous polymer M-P-CMP catalyst, and in particular relates to a mesoporous polymer M-P-CMP catalyst, a preparation method and application thereof in preparation of oxo-isophorone.
Background
Oxo-isophorone (KIP) is a perfume, and is also a synthetic intermediate for some perfumes, and an important intermediate for the preparation of vitamins, carotenoids, etc.
The oxo-isophorone is a light yellow liquid at normal temperature, has strong fragrance of pure products, lasting fragrance, and slight sour and sweet costustoot and dried fruit fragrance, and has obvious perfuming effect on various cigarettes. Oxo-isophorone is a natural product that can be extracted directly from plants, but requires a large amount of raw materials and is extremely low in yield. In addition to the increasing demands on oxo-isophorone, environmental protection requirements are also becoming more stringent. Thus, it is becoming more and more important to develop a cheap, efficient and environment-friendly technology for synthesizing KIP.
The oxidation of beta-isophorone (beta-IP) to oxo-isophorone (KIP) is a typical use of molecular oxygen (O) 2 Or air). So far, a variety of catalysts have been studied. From the catalysts reported in the literature and patents, the transition metal salt catalyst is the main catalyst, and comprises a transition metal acetylacetonate complex catalyst and a Schiff base complex catalyst, which all surround transition metal and adopt proper organic base as conditions, so that good conversion rate and selectivity can be obtained.
In US patent US4046813a KIP is prepared by reacting β -IP with an oxygen-enriched gas in the presence of an organic nitrogen base with a weak acid or an organic acid metal salt, alkoxide of lead, vanadium, chromium, manganese, iron or cobalt salt as a catalyst, which has a high conversion rate but is prone to produce a high polymerization by-product and side reactions of rearrangement of β -IP to α -IP. In US6300521B1 and US6297404B1, beta-IP is oxidized to KIP by passing air at room temperature for several hours in the presence of ammonium acetate or lithium acetate using a metal complex of schiff base as a catalyst. The scheme has the defect that byproducts such as 2, 6-trimethylcyclohexane-1, 4-dione and 3, 5-trimethyl-cyclohex-2-en-4-hydroxy-1-one are generated, and the structures and properties of the byproducts are similar, so that the separation and purification of the products are difficult.
In US patent US4898985a, beta-IP is oxidized to KIP using a phthalocyanine metal complex as a catalyst, triethylamine as an additive, and ethylene glycol dimethyl ether as a solvent. Compared with the previous method, the method suppresses the polymerization and side reaction of beta-isophorone with a considerable yield, but the phthalocyanine complex catalyst is expensive. In addition, the system of triethylamine and ethylene glycol dimethyl ether has very low ignition point and certain hidden technical trouble.
In summary, in the current reaction for preparing KIP by oxidizing beta-IP, a homogeneous catalytic system is mostly adopted, and after the reaction is finished, the catalyst is not easy to recover, so that the cost is increased and the environment is polluted.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a mesoporous polymer M-P-CMP catalyst and a preparation method thereof, wherein the catalyst can be applied to the preparation of isophorone oxide, and the heterogeneous catalyst has stable structure and high activity, stability and selectivity. The catalyst has no residue and no falling off in the use process, and truly realizes the green catalysis process. Can be conveniently separated from the system and recycled after the reaction is finished, has good application effect, can be repeatedly used for many times, and does not reduce the efficiency.
The invention is realized by the following technical scheme:
a mesoporous polymer M-P-CMP catalyst has the following structural formula:
wherein the cation M is Fe 3+ 、Cr 3+ 、V 3+ 、Ti 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ One of the following; the anion X is Cl - 、Br - 、F - 、NO 3 - 、SO 4 2- 、CH 3 COO - One of them.
The further improvement method of the invention is as follows:
a preparation method of a mesoporous polymer M-P-CMP catalyst comprises the following steps:
(1) Synthesis of 5,10,15, 20-tetra- (4-bromophenyl) porphyrin transition metal complex
Heating 5,10,15, 20-tetra (4-bromophenyl) porphyrin and transition metal salt MX in a solvent DMF for reaction, and performing post-treatment after the reaction is finished to obtain a 5,10,15, 20-tetra- (4-bromophenyl) porphyrin transition metal complex which is named as [ p-Br ]] 4 PM；
The chemical reaction equation is:
(2) Synthesis of M-P-CMP
[p-Br] 4 PM and 1, 4-phenyl-diboronic acid were mixed in solvent 1, 4-dioxane (32 ml) and K was added 2 CO 3 And aqueous solution of tetra (triphenylphosphine) palladium, heating and stirring to react, and after the reaction is finished, performing post-treatment to obtain M-P-CMP;
the chemical reaction equation is:
wherein the cation M is Fe 3+ 、Cr 3+ 、V 3+ 、Ti 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ One of the following; the anion X is Cl - 、Br - 、F - 、NO 3 - 、SO 4 2- 、CH 3 COO - One of them.
Further, in the step (1), the molar ratio of the 5,10,15, 20-tetra (4-bromophenyl) porphyrin to the transition metal salt MX is 1:25-30, the temperature of the heating reaction is 140-160 ℃, and the reaction time is 8-14 h.
Further, in the step (2)The [ p-Br ]] 4 PM, 1, 4-phenyldiboronic acid, K 2 CO 3 And the molar ratio of the tetra (triphenylphosphine) palladium is 1:2-10:6-10:0.05-0.15; the temperature of the stirring reaction is 100-180 ℃ and the time is 18-36 h.
The invention further improves the scheme as follows:
application of mesoporous polymer M-P-CMP catalyst in preparing oxo-isophorone, comprising the following steps: in the presence of organic base, using polymer M-P-CMP catalyst and molecular oxygen or oxygen-enriched gas to make beta-isophorone (beta-IP) produce oxidation reaction to prepare oxo isophorone.
Further, the organic base is one or more than two of pyridine, 4-methylpyridine, 2-methylpyridine, aniline, methylimidazole or diphenylamine.
Further, the molecular oxygen or oxygen-enriched gas is oxygen or air. The oxygen flow per hour is usually 50 to 1000L, preferably 100 to 500L, based on 1 kg of beta-IP. For other oxygen-containing gases, the ventilation can be correspondingly converted according to the oxygen content. Particularly, under the condition of pure oxygen, the reaction can be carried out under the condition of pressurization, and the oxygen pressure can be controlled to be 0.2-2 mpa.
Further, the mass ratio of the beta-isophorone to the M-P-CMP catalyst to the organic base is 1:0.001-0.05:0.025-40.
Further, the temperature of the oxidation reaction is 50 to 85 ℃, preferably 60 to 75 ℃.
Further, the polymer M x P-CMP catalyst can be recycled, and the specific recycling process is as follows: after the reaction is finished, stopping stirring, cooling at room temperature and standing for 3-8 hours, collecting a precipitate through centrifugation, cleaning with water, tetrahydrofuran, methanol and acetone, performing Soxhlet extraction by taking tetrahydrofuran, methanol and acetone as solvents, and performing vacuum drying to obtain a solid, namely the recovered M-P-CMP catalyst, and continuing to be used for the beta-isophorone oxidation reaction.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a catalytic manganese porphyrin unit is added into the COFS for the first time, and a skeleton containing the catalytic manganese unit is synthesized in a multi-element manner, so that a catalyst with high activity, stability and selectivity is obtained, and a stable complex is formed. The supported transition metal complex catalyst has the following characteristics that (1) the catalyst has good thermal stability; (2) The catalyst has small particle size, a large contact surface in the catalyst, and good diffusivity in a reaction system, so that the catalyst has excellent catalytic activity; (3) The catalyst can be recycled by simple treatment.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1: mnP-CMP catalyst preparation
(1) Manganese 5,10,15, 20-tetrakis- (4-bromophenyl) porphyrin ([ p-Br)] 4 PMn) synthesis
5,10,15, 20-tetra (4-bromophenyl) porphyrin (600 mg, 0.64 mmol) and MnCl 2 (3g) After placing in a round bottom flask and drying 2 h under vacuum, DMF (200 ml) degassed with nitrogen was added. The mixture was stirred at 150℃overnight, cooled to room temperature, and 40ml of hydrochloric acid (3M) solution was added dropwise. The precipitate was filtered, washed with 40ml of hydrochloric acid (3M) solution and H 2 O (400 ml. Times.2) was washed. The crude product is recrystallized twice by chloroform and methanol to obtain tan powder [ p-Br ]] 4 PMn (492 mg, 0.48 mmo 1) in 75% yield.
(2) Synthesis of MnP-CMP
Will [ p-BR] 4 PMn (394 mg,0.4 mmol) and 1, 4-phenyl-diboronic acid (133 mg,0.8 mmol) were mixed in 1, 4-dioxane (32 ml) and degassed via three freeze-pump-thaw cycles. Adding K to the mixture 2 CO 3 (442 mg,3.2 mmol) and tetrakis (triphenylphosphine) palladium (0) (46.4 mg, 40. Mu. Mol) in water (8 ml). The mixture was degassed with argon through three freeze-pump-thaw cycles, stirred at 110 ℃ for 24 hours, cooled at room temperature and poured into water. The precipitate was collected by filtration and thoroughly washed with water, tetrahydrofuran, methanol and acetone. Tetrahydrofuran, methanol and acetone are used as solvents, soxhlet extraction and vacuum drying are carried out, and MnP-CMP (296 and mg) is obtained as a dark blue solid.
Example 2: preparation of oxo-isophorone by MnP-CMP catalysis of beta-isophorone
Beta-isophorone (12 g,87 mmol) was added to a 50ml two-necked flask, porphyrin material catalyst 0.18g MnP-CMP and rotor were added, the flask was sealed, then an oxygen balloon was attached, and 18ml pyridine solution was added. Reacting at 60-75 deg.C for 48 hr. The reaction conversion was 91% and the selectivity of oxo-isophorone was 85% as analyzed by gas chromatograph.
Example 3: preparation of oxo-isophorone by MnP-CMP catalysis of beta-isophorone
Beta-isophorone (12 g,87 mmol) was added to a 50ml two-necked flask, porphyrin catalyst 0.18g MnP-CMP and rotor were added, the flask was sealed, air was continuously vented, and 18ml pyridine solution was added. Reacting at 60-75 deg.C for 60 hr. The reaction conversion was 89% and the selectivity to oxo-isophorone was 81% as analyzed by gas chromatograph.
EXAMPLE 4 recycle of MnP-CMP catalyst
The reaction solution is separated by a differential centrifuge and centrifuged for 10 minutes at a rotation speed of 5000 r/min. Taking out supernatant, washing the lower solid with water, tetrahydrofuran, methanol and acetone, and drying in a vacuum drying oven at 90 deg.C for 5 hr. The obtained catalyst was subjected to a feeding experiment (as follows) according to item 1, and the application effect was good.
Table 1: experiments for MnP-CMP catalyst application
Example 5: other metals M * Preparation of oxo-isophorone by catalyzing beta-isophorone through P-CMP
Beta-isophorone (12 g,87 mmol) was added to a 50ml two-necked flask, and porphyrin material catalyst 0.18. 0.18g M was added * P-CMP（M * Cu, co, fe, zn) and a rotor, the flask was sealed and then attached with an oxygen balloon, and 18ml of pyridine solution was added. Reacting for several hours at 60-75 ℃. The beta-isophorone conversion and the selectivity to oxo-isophorone were analyzed by gas chromatography as follows:
table 2: m is M * Experiment for P-CMP catalyst application
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A mesoporous polymer M-P-CMP catalyst is characterized by having the following structural formula:
wherein the cation M is Fe 3+ 、Cr 3+ 、V 3+ 、Ti 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ One of the following; the anion X is Cl - 、Br - 、F - 、NO 3 - 、SO 4 2- 、CH 3 COO - One of them.
2. The method for preparing a mesoporous polymer M x P-CMP catalyst according to claim 1, comprising the steps of:
(1) Synthesis of 5,10,15, 20-tetra- (4-bromophenyl) porphyrin transition metal complex
Heating 5,10,15, 20-tetra (4-bromophenyl) porphyrin and transition metal salt MX in a solvent DMF for reaction, and performing post-treatment after the reaction is finished to obtain a 5,10,15, 20-tetra- (4-bromophenyl) porphyrin transition metal complex which is named as [ p-Br ]] 4 PM；
The chemical reaction equation is:
(2) Synthesis of M-P-CMP
[p-Br] 4 PM and 1, 4-phenyl-diboronic acid were mixed in solvent 1, 4-dioxane (32 ml) and K was added 2 CO 3 And aqueous solution of tetra (triphenylphosphine) palladium, heating and stirring to react, and after the reaction is finished, performing post-treatment to obtain M-P-CMP;
the chemical reaction equation is:
wherein the cation M is Fe 3+ 、Cr 3+ 、V 3+ 、Ti 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ One of the following; the anion X is Cl - 、Br - 、F - 、NO 3 - 、SO 4 2- 、CH 3 COO - One of them.
3. The method for preparing a mesoporous polymer M x P-CMP catalyst according to claim 2, wherein: in the step (1), the molar ratio of the 5,10,15, 20-tetra (4-bromophenyl) porphyrin to the transition metal salt MX is 1:25-30, the heating reaction temperature is 140-160 ℃, and the reaction time is 8-14 h.
4. The method for preparing a mesoporous polymer M x P-CMP catalyst according to claim 2, wherein: the [ p-Br ] in step (2)] 4 PM, 1, 4-phenyldiboronic acid, K 2 CO 3 And the molar ratio of the tetra (triphenylphosphine) palladium is 1:2-10:6-10:0.05-0.15; the temperature of the stirring reaction is 100-180 ℃ and the time is 18-36 h.
5. Use of a mesoporous polymeric M x P-CMP catalyst according to claim 1, for the preparation of oxo-isophorone, comprising the steps of: in the presence of organic base, using polymer M-P-CMP catalyst and using molecular oxygen or oxygen-enriched gas to make beta-isophorone produce oxidation reaction to prepare oxo isophorone.
6. The use of a mesoporous polymeric M x P-CMP catalyst according to claim 5, for the preparation of oxo-isophorone, characterized in that: the organic base is one or more than two of pyridine, 4-methylpyridine, 2-methylpyridine, aniline, methylimidazole or diphenylamine.
7. The use of a mesoporous polymeric M x P-CMP catalyst according to claim 5, for the preparation of oxo-isophorone, characterized in that: the molecular oxygen or oxygen-enriched gas is oxygen or air.
8. The use of a mesoporous polymeric M x P-CMP catalyst according to claim 5, for the preparation of oxo-isophorone, characterized in that: the mass ratio of the beta-isophorone to the M-P-CMP catalyst to the organic base is 1:0.001-0.05:0.025-40.
9. The use of a mesoporous polymeric M x P-CMP catalyst according to claim 5, for the preparation of oxo-isophorone, characterized in that: the temperature of the oxidation reaction is 50-85 ℃.
10. The use of a mesoporous polymeric M x P-CMP catalyst according to claim 5, for the preparation of oxo-isophorone, characterized in that: the polymer M-P-CMP catalyst can be recycled, and the specific recycling process is as follows: after the reaction is finished, stopping stirring, cooling at room temperature and standing for 3-8 hours, collecting a precipitate through centrifugation, cleaning with water, tetrahydrofuran, methanol and acetone, performing Soxhlet extraction by taking tetrahydrofuran, methanol and acetone as solvents, and performing vacuum drying to obtain a solid, namely the recovered M-P-CMP catalyst, and continuing to be used for the beta-isophorone oxidation reaction.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898985A (en) * | 1987-10-06 | 1990-02-06 | Soda Aromatic Company, Limited | Process for preparing 3,5,5-trimethylcyclohexa-2-en-1,4-dione |
| CN101327451A (en) * | 2007-06-24 | 2008-12-24 | 山东理工大学 | Uses of planar polymerized phthalocyanine or porphyrin transition metal complexes |
| CN106632832A (en) * | 2016-08-29 | 2017-05-10 | 扬州工业职业技术学院 | Polymer catalyst used for synthesizing isophorone and preparation method of polymer catalyst |
| CN116854569A (en) * | 2023-05-30 | 2023-10-10 | 江苏宏邦化工科技有限公司 | Method for preparing oxo-isophorone by taking 3, 5-trimethyl-4-hydroxy-2-cyclohexene-1-one as raw material |
-
2022
- 2022-12-21 CN CN202211645499.2A patent/CN116116464A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898985A (en) * | 1987-10-06 | 1990-02-06 | Soda Aromatic Company, Limited | Process for preparing 3,5,5-trimethylcyclohexa-2-en-1,4-dione |
| CN101327451A (en) * | 2007-06-24 | 2008-12-24 | 山东理工大学 | Uses of planar polymerized phthalocyanine or porphyrin transition metal complexes |
| CN106632832A (en) * | 2016-08-29 | 2017-05-10 | 扬州工业职业技术学院 | Polymer catalyst used for synthesizing isophorone and preparation method of polymer catalyst |
| CN116854569A (en) * | 2023-05-30 | 2023-10-10 | 江苏宏邦化工科技有限公司 | Method for preparing oxo-isophorone by taking 3, 5-trimethyl-4-hydroxy-2-cyclohexene-1-one as raw material |
Non-Patent Citations (1)
| Title |
|---|
| LONG CHEN ET AL.: "CMPs as Scaffolds for Constructing Porous Catalytic Frameworks: A Built-in Heterogeneous Catalyst with High Activity and Selectivity Based on Nanoporous Metalloporphyrin Polymers", 《J. AM. CHEM. SOC》, vol. 132, 10 June 2010 (2010-06-10), pages 9138 - 9143 * |
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