CN115947882A - Preparation method of pyridine amido hafnium catalyst - Google Patents
Preparation method of pyridine amido hafnium catalyst Download PDFInfo
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- CN115947882A CN115947882A CN202310243295.4A CN202310243295A CN115947882A CN 115947882 A CN115947882 A CN 115947882A CN 202310243295 A CN202310243295 A CN 202310243295A CN 115947882 A CN115947882 A CN 115947882A
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 23
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract description 14
- 125000003368 amide group Chemical group 0.000 title abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 84
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- OIDRXSLJYDFQAZ-UHFFFAOYSA-N N[Hf].N1=CC=CC=C1 Chemical compound N[Hf].N1=CC=CC=C1 OIDRXSLJYDFQAZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 119
- 239000000047 product Substances 0.000 claims description 40
- 125000006413 ring segment Chemical group 0.000 claims description 40
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 238000001953 recrystallisation Methods 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 21
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 16
- 150000002576 ketones Chemical class 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- NFZPSWICTMSHLG-UHFFFAOYSA-N hafnium(4+) pyridin-2-ylazanide Chemical compound [Hf+4].[NH-]C1=CC=CC=N1.[NH-]C1=CC=CC=N1.[NH-]C1=CC=CC=N1.[NH-]C1=CC=CC=N1 NFZPSWICTMSHLG-UHFFFAOYSA-N 0.000 claims description 4
- YYCAWAQZKOZDEB-UHFFFAOYSA-N hafnium;pyridin-2-amine Chemical compound [Hf].NC1=CC=CC=N1 YYCAWAQZKOZDEB-UHFFFAOYSA-N 0.000 claims description 4
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 4
- FEEFWFYISQGDKK-UHFFFAOYSA-J hafnium(4+);tetrabromide Chemical compound Br[Hf](Br)(Br)Br FEEFWFYISQGDKK-UHFFFAOYSA-J 0.000 claims description 3
- QHEDSQMUHIMDOL-UHFFFAOYSA-J hafnium(4+);tetrafluoride Chemical compound F[Hf](F)(F)F QHEDSQMUHIMDOL-UHFFFAOYSA-J 0.000 claims description 3
- YCJQNNVSZNFWAH-UHFFFAOYSA-J hafnium(4+);tetraiodide Chemical compound I[Hf](I)(I)I YCJQNNVSZNFWAH-UHFFFAOYSA-J 0.000 claims description 3
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 3
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 claims description 3
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PSABUFWDVWCFDP-UHFFFAOYSA-N 2,2-dimethylheptane Chemical compound CCCCCC(C)(C)C PSABUFWDVWCFDP-UHFFFAOYSA-N 0.000 description 1
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 1
- SEEOMASXHIJCDV-UHFFFAOYSA-N 3-methyloctane Chemical compound CCCCCC(C)CC SEEOMASXHIJCDV-UHFFFAOYSA-N 0.000 description 1
- TYSIILFJZXHVPU-UHFFFAOYSA-N 5-methylnonane Chemical compound CCCCC(C)CCCC TYSIILFJZXHVPU-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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Classifications
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to a preparation method of a pyridine amino hafnium catalyst, which comprises the following steps: carrying out mixed reaction on the compound (1), the compound (2) and the compound (3) under the action of a molecular sieve catalyst to prepare a pyridine amido hafnium catalyst shown in a formula (4); the preparation method can directly prepare the pyridine amino hafnium catalyst shown in the formula (4) in one pot, and has simple steps and high yield.
Description
Technical Field
The invention relates to the technical field of compound synthesis, and particularly relates to a preparation method of a pyridine amido hafnium catalyst.
Background
Polyolefin is widely used due to its excellent mechanical properties, low cost and easy processing, and is one of the most productive synthetic polymer materials, and the polymerization process of olefin can be controlled by catalyst, so that the structure and performance of polyolefin can be accurately controlled, therefore it is also considered as the core technology of polyolefin industry.
The pyridine amino hafnium catalyst is an olefin polymerization catalyst with excellent performance, shows higher ethylene polymerization activity and thermal stability, can obtain linear polyethylene, has good copolymerization performance, and can be used for preparing a unique 'soft-hard alternating' olefin block copolymer material. However, the conventional preparation method of the pyridine amino hafnium catalyst involves multi-step reaction, flammable and easily decomposed intermediate products, or dangerous materials such as trimethylaluminum, etc., and is complex to operate and low in yield, which is not favorable for large-scale production.
Therefore, the conventional techniques still need to be improved.
Disclosure of Invention
Accordingly, there is a need for a method for preparing a hafnium pyridylamine catalyst with simple steps and high yield.
In one aspect of the present application, a preparation method of a pyridylamine hafnium catalyst is provided, which includes the following steps:
the compound (1), the compound (2) and the compound (3) are mixed and reacted under the action of a molecular sieve catalyst,
preparing a pyridine amino hafnium catalyst shown in a formula (4);
the structures of the compound (1), the compound (2), the compound (3) and the hafnium pyridylamide catalyst represented by the formula (4) are respectively as follows:
wherein R is 1 Each occurrence is independently selected from any one of H and alkanyl with 1 to 15 carbon atoms, n 1 Any integer selected from 1~5;
R 2 each occurrence is independently selected from any one of H and alkanyl with 1 to 15 carbon atomsSeed, n 2 Any integer selected from 1~5;
R 3 each occurrence is independently selected from I - 、Br - And Cl - And F - Any one of the above;
a is selected from the formula-MgR 4 Or Li, R 4 Any one selected from I, br and Cl.
In some embodiments, the mixing reaction is performed in an organic solvent, and the organic solvent includes at least one of an ether solvent, a ketone solvent, and a substituted or unsubstituted aromatic hydrocarbon solvent having 6 to 20 ring atoms.
In some embodiments, the organic solvent includes a first solvent and a second solvent, the first solvent is an aromatic hydrocarbon solvent with 6 to 20 substituted or unsubstituted ring atoms, and the second solvent includes at least one of an ether solvent and a ketone solvent.
In some embodiments, the organic solvent satisfies at least one of the following conditions (1) to (5):
(1) The volume ratio of the first solvent to the second solvent is (3-5): 1;
(2) The first solvent comprises at least one of an aromatic hydrocarbon solvent with 6 to 10 unsubstituted ring atoms and an aromatic hydrocarbon solvent with 6 to 10 ring atoms substituted by alkyl with 1~5 carbon atoms;
(3) The ether solvent includes at least one of a compound represented by formula (5) and a compound represented by formula (6):
wherein R is 5 Each occurrence is independently selected from alkanyl having 1~5 carbon atoms; n is 3 Is any integer of 1~3;
(4) The ketone solvent is represented by formula (7):
wherein R is 6 Each occurrence is independently selected from alkanyl having 1~5 carbon atoms;
(5) The volume-mass ratio of the organic solvent to the compound (1) is (9-20) mL:1g.
In some of these embodiments, R 5 Each occurrence is independently selected from alkanyl having 1~4 carbon atoms; n is 3 Is 1~2;
R 6 each occurrence is independently selected from a linear alkyl group having a carbon number of 1~3.
In some embodiments, the molecular sieve catalyst satisfies at least one of the following conditions (6) to (7):
(6) The mass ratio of the molecular sieve catalyst to the compound (1) is 1 (8 to 15);
(7) The molecular sieve catalyst comprises at least one of an MCM-41 molecular sieve and a 4A molecular sieve;
the compound (1) satisfies at least one of the following conditions (8) to (10):
(8) n 1 is 1,R 1 Any one selected from the chain alkyl group having 1~5 carbon atoms;
(9) n 2 is 2,R 2 At each occurrence, is selected from any one of alkyl groups of 1~5 carbon atoms;
(10) Each R 1 And each R 2 Selected from the same group;
the compound (2) satisfies at least one of the following conditions (11) to (12):
(11) The compound (2) includes at least one of hafnium tetrachloride, hafnium tetrabromide, hafnium tetrafluoride, and hafnium tetraiodide;
(12) The molar ratio of the compound (2) to the compound (1) is (1 to 1.2) to 1;
the compound (3) satisfies at least one of the following conditions (13) to (14):
(13) The compound (3) includes at least one of methyl magnesium bromide, methyl magnesium chloride, methyl magnesium iodide, and methyl lithium;
(14) The molar ratio of the compound (3) to the compound (1) is (4.5-5): 1.
In some of these embodiments, the structure of compound (1) is as follows:
wherein i-Pr represents an isopropyl group.
In some embodiments, the temperature of the mixing reaction is 20-30 ℃, and the time is 12h-48h.
In some embodiments, the process for preparing the hafnium pyridine amino group catalyst represented by formula (4) further comprises the following steps:
removing the solvent from the product of the mixed reaction to produce a first concentrated product;
dissolving the first concentrated product in an aromatic hydrocarbon solvent with the number of substituted or unsubstituted ring atoms of 6 to 20, filtering, and concentrating the filtrate to prepare a second concentrated product;
dissolving the second concentrated product in a recrystallization solution to perform recrystallization treatment, thereby preparing the pyridylamine hafnium catalyst represented by the formula (4);
the recrystallization solution comprises at least one of alkanes with 5-10 carbon atoms.
In some embodiments, the recrystallization solution satisfies at least one of the following conditions (15) to (16):
(15) The volume ratio of the recrystallization solution to the second concentrated product is (5 to 10) to 1;
(16) The recrystallization solution includes at least one paraffin having a carbon number of 5~8.
Compared with the prior art, this application has following beneficial effect:
in the preparation method of the pyridylamine hafnium catalyst, the compound (1), the compound (2) and the compound (3) are subjected to mixed reaction under the action of the molecular sieve catalyst, so that the pyridylamine hafnium catalyst shown in the formula (4) can be prepared directly in one pot without using dangerous compounds such as trimethyl aluminum, butyl lithium and the like, and the preparation method is simple in steps and high in yield.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the hafnium pyridyl amide catalyst prepared in the example.
Detailed Description
The present application will be described in further detail with reference to specific examples. This application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In this application, the term "alkyl" refers to a group formed upon loss of one hydrogen from an alkane, for example methane, to form a methyl group upon loss of one hydrogen, and includes cycloalkyl and alkanyl.
The term "alkanyl" refers to a group formed by an alkane in which carbon atoms are all connected by a single carbon-carbon bond and are not cyclic and the remaining bonds have bonds to hydrogen, and which is formed by losing one hydrogen, and includes straight-chain alkanyl groups and branched-chain alkanyl groups. Similarly, "cycloalkyl" aryl means a group formed by an alkane in which carbon atoms are all connected by a carbon-carbon single bond and part of the carbon atoms form a ring, and the remaining bonds are all bonded to hydrogen, and one hydrogen is lost.
In the present application, the "alkylene subunit having 1 to 15 carbon atoms" may have 1 to 15 carbon atoms, including 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or 15, and refer to a group formed by an alkane having 2 to 15 carbon atoms (i.e., a C1 to 15 alkane) which loses one hydrogen, and specific examples thereof include a group formed by a C1 alkane, a C2 alkane, a C3 alkane, a C4 alkane, a C5 alkane, a C6 alkane, a C7 alkane, a C8 alkane, a C9 alkane, or a C13 alkane which loses one hydrogen, non-limiting examples of "C1-15 alkanes" include methane, ethane, n-propane, iso-propane, n-butane, iso-butane, 2-ethylbutane, 3-dimethylbutane, n-pentane, iso-pentane, neopentane, 1-methylpentane, 3-methylpentane, 2-ethylpentane, 4-methyl-2-pentane, n-hexane, 1-methylhexane, 2-ethylhexane, 2-butylhexane, n-heptane, 1-methylheptane, 2,2-dimethylheptane, 2-ethylheptane, n-octane, n-nonane, n-decane.
In this application, when no attachment site is indicated in a group, it means that an optional attachment site in the group is used as an attachment site.
In the present application, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position of the ring, e.g.
Wherein R is attached to any substitutable site of the phenyl ring.
In the present application, the "number of ring atoms" means the number of atoms bonded to a ring, and when the ring is substituted with a substituent, the atoms included in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified, and for example, the number of ring atoms of cyclohexane is 6, the number of ring atoms of benzene ring is 6, the number of ring atoms of naphthalene ring is 10, and the number of ring atoms of thiophene is 5.
In the present application, "substituted or unsubstituted" means that the defined group may or may not be substituted, and when substituted, if the attachment site of the substituent is not specified in the group, it means that the attachment site may be any attachable site on the substituted group.
In the traditional preparation method of the pyridine amino hafnium catalyst, multi-step reaction is involved, flammable and easily-decomposed intermediate products are involved, or dangerous materials such as trimethylaluminum and the like are required to be used, for example, in a technical scheme, a ligand substrate is firstly reacted with butyllithium to prepare a ligand lithium compound, then the ligand lithium compound is subjected to reflux reaction with hafnium tetrachloride, and finally the ligand lithium compound is reacted with a Grignard reagent to obtain a final catalyst.
In another technical scheme, a ligand substrate is adopted to react with tetra (dimethylamino) hafnium to obtain a dimethylamino intermediate, and then trimethyl aluminum is methylated to obtain the pyridylamine hafnium catalyst.
Based on this, the technicians in this application, after a lot of creative experiments in long-term synthesis research and related production processes, obtain the preparation method of the pyridine amino hafnium catalyst with simple steps and high yield in this application.
In one embodiment of the present application, a method for preparing a hafnium pyridine amino catalyst is provided, which includes the following step S10.
Step S10: and (3) carrying out mixed reaction on the compound (1), the compound (2) and the compound (3) under the action of a molecular sieve catalyst to prepare the pyridylamine hafnium catalyst shown in the formula (4).
The structures of the pyridylamine hafnium catalysts represented by the compounds (1), (2), (3) and (4) are as follows:
wherein R is 1 Each occurrence is independently selected from H and any one of alkanyl with 1 to 15 carbon atoms, and n 1 Any integer selected from 1~5;
R 2 each occurrence is independently selected from any one of H and alkanyl with 1 to 15 carbon atoms, n 2 Any integer selected from 1~5;
R 3 each occurrence is independently selected from I - 、Br - And Cl - And F - Any one of the above;
a is selected from the formula-MgR 4 Or Li, R 4 Any one selected from I, br and Cl.
In the preparation method of the pyridine amino hafnium catalyst, the compound (1), the compound (2) and the compound (3) are mixed and reacted under the action of the molecular sieve catalyst, and the pyridine amino hafnium catalyst shown in the formula (4) can be prepared directly in one pot without using dangerous compounds such as trimethyl aluminum, butyl lithium and the like, so that the steps are simple and the yield is high.
n 1 Each occurrence is independently selected from 1, 2, 3, 4 or 5.
n 2 For each occurrence, is identically selected from 1, 2, 3, 4 or 5.
When R is in the specification 1 Are all selected from H or R 2 When both are selected from H, it means that the group on which they are located is phenyl.
In some embodiments, the mixing reaction is performed in an organic solvent, and the organic solvent includes at least one of an ether solvent, a ketone solvent, and a substituted or unsubstituted aromatic hydrocarbon solvent with 6 to 20 ring atoms.
The aromatic hydrocarbon solvent with 6 to 20 ring atoms of substituted or unsubstituted has better solubility to the raw material compound (1) and the product, and the ether solvent and the ketone solvent can increase the solubility of the compound (2) and a reaction intermediate possibly involved in the mixed reaction process, so that the reaction efficiency can be improved.
In some embodiments, the organic solvent includes at least one of an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent having 6 to 10 unsubstituted ring atoms, and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1~5 carbon atoms.
In some embodiments, the organic solvent includes at least one of an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent having 6 to 10 unsubstituted ring atoms, and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with a chain alkyl group having 1~5 carbon atoms.
In some embodiments, the organic solvent includes at least one of an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent having 6 to 10 unsubstituted ring atoms, and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with a chain alkyl group having 1~5 carbon atoms.
In some of these embodiments, the organic solvent comprises at least one of an ether solvent, a ketone solvent, an unsubstituted aromatic hydrocarbon solvent having a ring atom number of 6~8, and an aromatic hydrocarbon solvent having a ring atom number of 6~8 substituted with a chain alkyl group having a carbon atom number of 1~4.
In some of these embodiments, the organic solvent comprises at least one of an ether solvent, a ketone solvent, benzene, and a phenyl solvent substituted with an alkanyl group having a carbon number of 1~5.
In some of these embodiments, alkanyl with a carbon number of 1~5 includes, but is not limited to: any one of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In some of these embodiments, phenyl solvents substituted with an alkanyl group having a carbon number of 1~5 include, but are not limited to: at least one of toluene and xylene.
In some embodiments, the ethereal solvent comprises at least one of a compound of formula (5) and a compound of formula (6):
wherein R is 5 Each occurrence is independently selected from alkanyl having 1~5 carbon atoms; n is 3 Is 1~3.
n 3 Is 1, 2 or 3; in some of these embodiments, n 3 Is 1 or 2.
In some embodiments, the compound of formula (6) comprises at least one of ethylene glycol dimethyl ether and triethylene glycol dimethyl ether.
In some of these embodiments, R 5 Independently at each occurrence, is selected from the number of carbon atomsIs 1~4 alkanyl.
In some of these embodiments, R 5 For each occurrence, are identically selected from alkanyl having a carbon number of 1~4.
Specific examples of the "alkanyl group having 1~4 as the carbon number" include: any one of methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
In some of these embodiments, the compound of formula (5) comprises at least one of methyl ether, ethyl ether, butyl ether, and methyl tert-butyl ether.
In some of these embodiments, the ketone solvent is of formula (7):
R 6 each occurrence is independently selected from alkanyl having 1~5 carbon atoms.
In some of these embodiments, R 6 Each occurrence is independently selected from a linear or branched alkyl group having a carbon number of 1~5.
In some of these embodiments, R 6 Each occurrence is independently selected from a linear alkyl group having a carbon number of 1~3.
In some of these embodiments, R 6 Each occurrence is independently selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
In some of these embodiments, R 6 Each occurrence is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
In some of these embodiments, the ketone-based solvent includes at least one of acetone, 2-butanone.
In some of these embodiments, the organic solvent comprises at least one of benzene, toluene, xylene, methyl ether, diethyl ether, butyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, acetone, and 2-butanone.
In some embodiments, the organic solvent includes a first solvent and a second solvent, the first solvent is an aromatic hydrocarbon solvent with 6 to 20 substituted or unsubstituted ring atoms, and the second solvent includes at least one of an ether solvent and a ketone solvent.
The skilled person in the present application further studies found that: when the specific first solvent and the specific second solvent are mixed to be used as the solvent for reaction, the raw materials and the product have better solubility, so that the reaction tends to be carried out under a homogeneous condition, the reaction efficiency can be further improved, and the product yield can be improved.
In some embodiments, the volume ratio of the first solvent to the second solvent is (3-5): 1.
The volume ratio of the first solvent to the second solvent is further regulated, so that the reaction is carried out in a specific organic solvent environment, and the reaction efficiency is further improved.
In the above "(3-5): 1", the ratio includes the minimum and maximum values of the range, and each value between the minimum and maximum values, and specific examples include, but are not limited to, the following point values in the examples: 3:1, 3.5; or any two numerical ranges.
In some embodiments, the first solvent includes at least one of an aromatic hydrocarbon solvent with 6 to 10 unsubstituted ring atoms and an aromatic hydrocarbon solvent with 6 to 10 ring atoms substituted by an alkyl group with 1~5 carbon atoms.
In some of the embodiments, the first solvent includes at least one of an aromatic hydrocarbon solvent with 6 to 10 unsubstituted ring atoms and an aromatic hydrocarbon solvent with 6 to 10 ring atoms substituted by a chain alkyl with 1~5 carbon atoms.
In some of the embodiments, the first solvent includes at least one of an aromatic hydrocarbon solvent with 6 to 10 unsubstituted ring atoms and an aromatic hydrocarbon solvent with 6 to 10 ring atoms substituted by a chain alkyl with 1~5 carbon atoms.
In some of these embodiments, the first solvent comprises at least one of an aromatic hydrocarbon solvent with a ring number of 6~8 unsubstituted and an aromatic hydrocarbon solvent with a ring number of 6~8 substituted with a chain alkyl group with a carbon number of 1~4.
In some of these embodiments, the first solvent comprises at least one of benzene and a phenyl solvent substituted with an alkanyl group having a carbon number of 1~5.
In some of these embodiments, alkanyl with a carbon number of 1~5 includes, but is not limited to: any one of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In some of these embodiments, the phenyl solvent substituted with an alkanyl group having a carbon number of 1~5 includes, but is not limited to: at least one of toluene and xylene.
In some of these embodiments, the first solvent comprises at least one of benzene, toluene, xylene.
The kinds of ether solvents and ketone solvents are as described above and will not be described in detail herein.
In some embodiments, the second solvent comprises at least one of the compounds represented by formula (5), formula (6), and formula (7) described above.
In some embodiments, the second solvent comprises any one of the compounds represented by formula (5), formula (6), and formula (7) described above.
The compound represented by the formula (5), the compound represented by the formula (6) and the compound represented by the formula (7) are as described above and will not be described in detail.
In some of these embodiments, the second compound comprises at least one of methyl ether, ethyl ether, butyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, acetone, and 2-butanone.
In some embodiments, the volume-to-mass ratio of the organic solvent to the compound (1) is (9 to 20) mL:1g.
In the above "(9 to 20) mL:1g", the values of the ratio include the minimum and maximum values of the range, and each value between the minimum and maximum values, and specific examples include, but are not limited to, the following values in the examples: 1g, 10ml; or any two numerical ranges.
In some of these embodiments, in compound (1), n 1 Is 1,R 1 Any one selected from the chain alkyl group having 1~5 carbon atoms.
In some of these embodiments, R 1 Are all selected from any one of alkyl groups having 1~4 carbon atoms.
In some of these embodiments, R 1 Are all selected from any one of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In some of these embodiments, n 2 Is 2,R 2 At each occurrence, is selected from any one of the chain alkyl groups of 1~5.
In some of these embodiments, R 2 Each occurrence is equally selected from any one of the alkanyl groups having 1~4 carbon atoms.
In some of these embodiments, R 2 Each occurrence is identically selected from any one of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In some of these embodiments, R 1 And each R 2 Selected from the same group.
In some of these embodiments, the structure of compound (1) is shown below:
wherein i-Pr represents an isopropyl group.
In some of these embodiments, compound (2) comprises at least one of hafnium tetrachloride, hafnium tetrabromide, hafnium tetrafluoride, and hafnium tetraiodide.
In some embodiments, the molar ratio of the compound (2) to the compound (1) is (1 to 1.2): 1.
By controlling the molar ratio of the compound (2) to the compound (1), the reaction efficiency can be further improved.
In the above "(1 to 1.2): 1", the ratio includes the minimum and maximum values of the range and each value between the minimum and maximum values, and specific examples include, but are not limited to, the following values in the examples: 1:1, 1.1: 1, 1.2: 1; or any two numerical ranges.
In some of these embodiments, compound (3) comprises at least one of methylmagnesium bromide, methylmagnesium chloride, methylmagnesium iodide, and methyllithium.
In some embodiments, the molar ratio of the compound (3) to the compound (1) is (4.5 to 5): 1.
In the above "(4.5-5): 1", the value of the ratio includes the minimum value and the maximum value of the range, and each value between the minimum value and the maximum value, and specific examples include, but are not limited to, the following values in the embodiments: 4.5:1, 4.6: 1, 4.7: 1, 4.8: 1, 4.9: 1, 5:1; or any two numerical ranges.
In some embodiments, the temperature of the mixing reaction is 20 ℃ to 30 ℃ and the time is 12h to 48h.
The conditions of the mixed reaction are adjusted, so that side reaction is avoided while higher reaction efficiency is kept, and the yield of the product is further improved.
The preparation scheme of the application can realize higher yield under the milder temperature condition.
In the above "20 ℃ to 30 ℃, the values of the ratio include the minimum value and the maximum value of the range, and each value between the minimum value and the maximum value, and specific examples include, but are not limited to, the following point values in the embodiments: 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C, 30 deg.C; or any two numerical ranges.
In the above "12h to 48h", the ratio includes the minimum and maximum values of the range, and each value between the minimum and maximum values, and specific examples include, but are not limited to, the following values: 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h, 48 h; or any two numerical ranges.
In some of the examples, the mass ratio of the molecular sieve catalyst to the compound (1) is 1 (8 to 15).
In the above "1 (8 to 15)", values of the ratio include a minimum value and a maximum value of the range, and each value between the minimum value and the maximum value, and specific examples include, but are not limited to, the following point values in the embodiments: 1:8, 1:9, 1; or any two numerical ranges.
The molecular sieve catalyst comprises a natural molecular sieve and an artificially synthesized molecular sieve, wherein the natural molecular sieve is mainly crystalline silicate or aluminosilicate, and is formed into a pore canal and cavity system with the molecular size of the molecular sieve by connecting silicon-oxygen tetrahedron or aluminum-oxygen tetrahedron through oxygen bridge bonds, so that the molecular sieve has the characteristic of sieving molecules, and then researchers find the phosphoaluminate molecular sieve along with the deepening of molecular sieve synthesis and application research, and framework elements of silicon, aluminum or phosphorus of the molecular sieve can Be replaced by B, ga, fe, cr, ge, ti, V, mn, co, zn, be, cu and the like, and the pore canal and cavity size can reach more than 2 nm, so the molecular sieve can Be divided into the silicoaluminate molecular sieve, the phosphoaluminate molecular sieve and the framework heteroatom molecular sieve according to the framework element composition, such as A type A, potassium A (3A), sodium A (4A) and calcium A (5A); x type is calcium X (10X), sodium X (13X); y type is sodium Y, calcium Y, etc.; further, other types, such as MCM-41 molecular sieves prepared by using supramolecular surfactant quaternary ammonium salt as a template agent of porous silicate, are available according to the template agent used in the preparation.
In some of these embodiments, the molecular sieve catalyst comprises at least one of an MCM-41 molecular sieve and a 4A molecular sieve.
In some embodiments, the process for preparing the hafnium pyridylamine catalyst represented by formula (4) further comprises the following steps S11 to S13.
And S11, removing the solvent in the product of the mixed reaction to prepare a first concentrated product.
The solvent in the product of the mixed reaction can be removed by methods commonly used in the art for removing solvents, including but not limited to: and (5) distilling under reduced pressure.
And S12, dissolving the first concentrated product into a substituted or unsubstituted aromatic hydrocarbon solvent with the ring atom number of 6-20, filtering, concentrating the filtrate, and preparing a second concentrated product.
The target product of the pyridine amido hafnium catalyst shown in the formula (4) is easily dissolved in the substituted or unsubstituted aromatic hydrocarbon solvent with the ring atomic number of 6-20, and other raw materials and intermediate products are hardly dissolved in the substituted or unsubstituted aromatic hydrocarbon solvent with the ring atomic number of 6-20, so that the target product, other raw materials and byproducts can be preliminarily separated after filtration.
In some embodiments, the first concentrated product is dissolved in at least one of an unsubstituted aromatic hydrocarbon solvent with 6 to 10 ring atoms and an aromatic hydrocarbon solvent with 6 to 10 ring atoms substituted by an alkyl group with 1~5 carbon atoms.
In some embodiments, the first concentrated product is dissolved in at least one of an unsubstituted aromatic hydrocarbon solvent with a ring atom number of 6 to 10 and an aromatic hydrocarbon solvent with a ring atom number of 6 to 10 substituted by a chain alkyl group with a carbon atom number of 1~5.
In some embodiments, the first concentrated product is dissolved in at least one of an unsubstituted aromatic hydrocarbon solvent with a ring atom number of 6 to 10 and an aromatic hydrocarbon solvent with a ring atom number of 6 to 10 substituted by a chain alkyl group with a carbon atom number of 1~5.
In some of these examples, the first concentrated product is dissolved in at least one of an aromatic hydrocarbon solvent having a ring number of 6~8 unsubstituted and an aromatic hydrocarbon solvent having a ring number of 6~8 substituted with an alkanyl group having a carbon number of 1~4.
In some of these embodiments, the first concentrated product is dissolved in at least one of benzene and a phenyl solvent substituted with an alkanyl group having 1~5 carbon atoms.
In some of these embodiments, alkanyl with a carbon number of 1~5 includes, but is not limited to: any one of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In some of these embodiments, phenyl solvents substituted with an alkanyl group having a carbon number of 1~5 include, but are not limited to: at least one of toluene and xylene.
In some of these embodiments, the first concentrated product is dissolved in at least one of benzene, toluene, xylene.
The concentration treatment is intended to remove most of the solvent, and the method used may be a concentration method commonly used in the art, including but not limited to: evaporation, distillation under reduced pressure, and the like.
S13, dissolving the second concentrated product into a recrystallization solution for recrystallization to prepare a pyridylamine hafnium catalyst shown in a formula (4); the recrystallization solution contains at least one of alkanes with 5 to 10 carbon atoms.
The skilled person in the present application further studies found that: the solubility of the target product in the specific recrystallization solvent changes with the temperature change, so the specific recrystallization solvent is adopted to further purify the target product on the premise of reducing the loss.
In some of these embodiments, the volume ratio of the recrystallized solution to the second concentrated product is (5 to 10): 1.
And adjusting the volume ratio of the recrystallization solution to the second concentrated product to further improve the recrystallization efficiency.
In the above "(5 to 10): 1", the ratio includes the minimum and maximum values of the range and each value between the minimum and maximum values, and specific examples include, but are not limited to, the following values in the examples: 5:1, 6:1, 7:1, 8:1, 9:1, 10; or any two numerical ranges.
In some of these embodiments, the recrystallization solution includes at least one paraffin having a carbon number of 5~8.
In some of these embodiments, the recrystallization solution includes at least one of the linear alkanes having a carbon number of 5~8.
In some of these embodiments, the recrystallization solution includes at least one of n-pentane, n-hexane, n-heptane, and n-octane.
While the present application will be described in conjunction with specific embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
The following are specific examples.
Example 1
The synthesis route of the pyridine amido hafnium catalyst is as follows:
the method comprises the following specific steps:
under a nitrogen atmosphere, a 100mL solvent storage bottle (Schlenk) was charged with a starting material (2) hafnium tetrachloride (2.56 g, 8 mmol), MCM-41 molecular sieve (0.37 g), starting material (1) N- [2,6-bis (1-methyl) phenyl ] -R- [2- (1-methyl) phenyl ] -6- (1-phenyl) -2-pyridineethamine, name of Chinese: 2- [ N- (2,6-diisopropylphenylamino) -o-isopropylphenylmethyl ] -6- (1-naphthyl) -pyridine (3.99 g, 7.8 mmol), anhydrous toluene 30 mL, anhydrous ether 8mL, charging a solution of raw material (3) methylmagnesium bromide in ether (12 mL, 3M) with a syringe at room temperature (20 ℃ C. -30 ℃ C.), and then reacting at room temperature (20 ℃ C. -30 ℃ C.) for 12 hours; and after the reaction is finished, carrying out reduced pressure distillation to remove the solvent to obtain a first concentrated product, adding anhydrous toluene 50 mL into the first concentrated product, filtering, concentrating the filtrate to obtain a second concentrated product of 10mL, adding the second concentrated product into 100mL n-pentane for recrystallization, filtering and drying to obtain a yellow product, namely the pyridylamine hafnium catalyst (5.2 g), wherein the structure is shown in the upper line.
The prepared pyridine amido hafnium catalyst is subjected to nuclear magnetic hydrogen spectrum test, and the results are as follows:
1 HNMR ( C 6 D 6 : deuterated benzene), delta: 8.60 (1H, d), 8.24 (1H, m), 7.83 (1H, d), 7.71 (1H, m), 7.51 (1H, d), 7.01-7.39 (9H, m), 6.83 (1H, d), 6.57 (1H, s), 6.55 (1H, d), 3.83 (1H, m), 3.38 (1H, m), 2,90 (1H, m), 1.37 (6H, m), 1.14 (6H, m), 0.96 (3H, s), 0.70 (6H, d), 0.39 (3H, d)。
the nuclear magnetic spectrum is shown in FIG. 1.
The results show that: the target product is successfully prepared by adopting the method.
The yield of the pyridylamine hafnium catalyst was calculated using the following formula:
yield = moles of pyridylamine hafnium catalyst/moles of raw material (1) × 100%.
The main condition parameters, yield and purity results are shown in Table 1.
Example 2~7
Example 2~7 is the same as example 1 except for the parameters in table 1 and other conditions not shown in table 1 are the same as example 1.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that no MCM-41 molecular sieve was added to the reaction step, and the results are shown in Table 1.
The main condition parameters and yield results of each example and comparative example are shown in Table 1, wherein "M" represents the number of moles of the substance, "M" represents the mass of the substance, and "V" represents the volume of the substance.
TABLE 1
"/" indicates that the condition is not present.
Analysis of the data in Table 1: according to the preparation method of the pyridylamine hafnium catalyst, the compound (1), the compound (2) and the compound (3) are subjected to mixed reaction under the action of the molecular sieve catalyst, dangerous compounds such as trimethyl aluminum and butyl lithium are not needed, the pyridylamine hafnium catalyst shown in the formula (4) can be prepared directly in one pot, the steps are simple, the yield is high, and the yield of the pyridylamine hafnium catalyst is greatly reduced in the absence of the catalyst in the comparative example 1.
Further, in example 1, the yield of the reaction can be further improved by adjusting the solution used for the reaction as compared with example 7.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present application shall be subject to the appended claims, and the description can be used to interpret the contents of the claims.
Claims (10)
1. The preparation method of the pyridine amino hafnium catalyst is characterized by comprising the following steps of:
the compound (1), the compound (2) and the compound (3) are mixed and reacted under the action of a molecular sieve catalyst,
preparing a pyridylamine hafnium catalyst shown in a formula (4);
the structures of the compound (1), the compound (2), the compound (3) and the hafnium pyridylamide catalyst represented by the formula (4) are respectively as follows:
wherein R is 1 In each of the occurrences of the first and second images,each independently selected from H and any one of alkanyl with 1 to 15 carbon atoms, n 1 Any integer selected from 1~5;
R 2 each occurrence is independently selected from any one of H and alkanyl with 1 to 15 carbon atoms, n 2 Any integer selected from 1~5;
R 3 each occurrence is independently selected from I - 、Br - And Cl - And F - Any one of the above;
a is selected from the formula-MgR 4 Or Li, R 4 Any one selected from I, br and Cl.
2. The method according to claim 1, wherein the mixing reaction is performed in an organic solvent, and the organic solvent comprises at least one of an ether solvent, a ketone solvent, and a substituted or unsubstituted aromatic hydrocarbon solvent having 6 to 20 ring atoms.
3. The method according to claim 2, wherein the organic solvent comprises a first solvent and a second solvent, the first solvent is an aromatic hydrocarbon solvent with 6 to 20 ring atoms which may be substituted or unsubstituted, and the second solvent comprises at least one of an ether solvent and a ketone solvent.
4. The method for preparing the hafnium pyridylamine catalyst according to claim 3, wherein the organic solvent satisfies at least one of the following conditions (1) to (5):
(1) The volume ratio of the first solvent to the second solvent is (3-5): 1;
(2) The first solvent comprises at least one of an aromatic hydrocarbon solvent with 6 to 10 unsubstituted ring atoms and an aromatic hydrocarbon solvent with 6 to 10 ring atoms substituted by alkyl with 1~5 carbon atoms;
(3) The ether solvent includes at least one of a compound represented by formula (5) and a compound represented by formula (6):
wherein R is 5 Each occurrence is independently selected from alkanyl having 1~5 carbon atoms; n is 3 Is 1~3;
(4) The ketone solvent is represented by formula (7):
wherein R is 6 Each occurrence is independently selected from alkanyl having 1~5 carbon atoms;
(5) The volume-mass ratio of the organic solvent to the compound (1) is (9-20) mL:1g.
5. The method of claim 4, wherein R is selected from the group consisting of 5 Each occurrence is independently selected from alkanyl having 1~4 carbon atoms; n is 3 Is 1~2;
R 6 each occurrence is independently selected from a linear alkyl group having a carbon number of 1~3.
6. The method for preparing the hafnium pyridine amino group catalyst according to any one of claims 1~5, wherein the molecular sieve catalyst satisfies at least one of the following conditions (6) to (7):
(6) The mass ratio of the molecular sieve catalyst to the compound (1) is 1 (8 to 15);
(7) The molecular sieve catalyst comprises at least one of an MCM-41 molecular sieve and a 4A molecular sieve;
the compound (1) satisfies at least one of the following conditions (8) to (10):
(8) n 1 is 1,R 1 Any one selected from the chain alkyl group having 1~5 carbon atoms;
(9) n 2 is the number of 2, and the number of the second,R 2 at each occurrence, is selected from any one of alkyl groups of 1~5 carbon atoms;
(10) Each R 1 And each R 2 Are selected from the same group;
the compound (2) satisfies at least one of the following conditions (11) to (12):
(11) The compound (2) includes at least one of hafnium tetrachloride, hafnium tetrabromide, hafnium tetrafluoride, and hafnium tetraiodide;
(12) The molar ratio of the compound (2) to the compound (1) is (1 to 1.2) to 1;
the compound (3) satisfies at least one of the following conditions (13) to (14):
(13) The compound (3) includes at least one of methyl magnesium bromide, methyl magnesium chloride, methyl magnesium iodide, and methyl lithium;
(14) The molar ratio of the compound (3) to the compound (1) is (4.5-5): 1.
7. The method of claim 1~5 wherein said compound (1) has the structure:
wherein i-Pr represents an isopropyl group.
8. The method for preparing the hafnium pyridine amino group catalyst according to the 1~5, wherein the temperature of the mixing reaction is 20 ℃ to 30 ℃ and the time is 12h to 48h.
9. The method of claim 1~5 wherein the process of preparing the hafnium pyridyl amide catalyst of formula (4) further comprises the steps of:
removing the solvent from the product of the mixed reaction to produce a first concentrated product;
dissolving the first concentrated product in an aromatic hydrocarbon solvent with the number of substituted or unsubstituted ring atoms of 6 to 20, filtering, and concentrating the filtrate to prepare a second concentrated product;
dissolving the second concentrated product in a recrystallization solution to perform recrystallization treatment, thereby preparing the pyridylamine hafnium catalyst represented by the formula (4);
the recrystallization solution comprises at least one of alkanes with 5-10 carbon atoms.
10. The method of preparing the hafnium pyridylamine catalyst according to claim 9, wherein the recrystallization solution satisfies at least one of the following conditions (15) to (16):
(15) The volume ratio of the recrystallization solution to the second concentrated product is (5 to 10) to 1;
(16) The recrystallization solution includes at least one paraffin having a carbon number of 5~8.
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