CN115947882B - Preparation method of pyridine amino hafnium catalyst - Google Patents
Preparation method of pyridine amino hafnium catalyst Download PDFInfo
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- CN115947882B CN115947882B CN202310243295.4A CN202310243295A CN115947882B CN 115947882 B CN115947882 B CN 115947882B CN 202310243295 A CN202310243295 A CN 202310243295A CN 115947882 B CN115947882 B CN 115947882B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- OIDRXSLJYDFQAZ-UHFFFAOYSA-N N[Hf].N1=CC=CC=C1 Chemical compound N[Hf].N1=CC=CC=C1 OIDRXSLJYDFQAZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 91
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- 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 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 114
- 125000004432 carbon atom Chemical group C* 0.000 claims description 57
- 125000000217 alkyl group Chemical group 0.000 claims description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 44
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 38
- 125000006413 ring segment Chemical group 0.000 claims description 37
- 238000001953 recrystallisation Methods 0.000 claims description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 19
- 150000002576 ketones Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- -1 hafnium pyridinium amine Chemical class 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 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
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 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
- YYCAWAQZKOZDEB-UHFFFAOYSA-N hafnium;pyridin-2-amine Chemical compound [Hf].NC1=CC=CC=N1 YYCAWAQZKOZDEB-UHFFFAOYSA-N 0.000 claims description 2
- 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 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
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- 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
- 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
- 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
- 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
- 239000013067 intermediate product Substances 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 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
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000543 intermediate Substances 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
- 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
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-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
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
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- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 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
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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Classifications
-
- 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 a mixing reaction on the compound (1), the compound (2) and the compound (3) under the action of a molecular sieve catalyst to prepare a pyridine amino 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, in particular to a preparation method of a pyridine amino hafnium catalyst.
Background
Polyolefin is widely used because of its excellent mechanical properties, low price and easy processing, and is one of the largest yield synthetic polymer materials, and the polymerization process of olefin can be regulated and controlled by catalyst, thus the structure and performance of polyolefin can be precisely controlled, so that it is also considered as a 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 olefin block copolymer material with alternating hardness. However, the traditional preparation method of the pyridine amino hafnium catalyst involves multi-step reaction, or involves inflammable and easily-decomposed intermediate products, or needs to use dangerous materials such as trimethylaluminum, and the like, so that the operation is complicated, the yield is low, and the large-scale production of the catalyst is not facilitated.
Accordingly, the conventional technology has yet to be improved.
Disclosure of Invention
Based on this, it is necessary to provide a method for producing a hafnium pyridinaminyl catalyst which is simple in steps and high in yield.
In one aspect of the present application, a method for preparing a hafnium pyridinamine-based catalyst is provided, comprising the steps of:
the compound (1), the compound (2) and the compound (3) are mixed to react 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 pyridine amino hafnium catalyst shown in the formula (4) are respectively as follows:
wherein R is 1 Each occurrence is independently selected from any one of H and alkyl with 1-15 carbon atoms, n 1 Any integer selected from 1 to 5;
R 2 each occurrence is independently selected from any one of H and alkyl with 1-15 carbon atoms, n 2 Any integer selected from 1 to 5;
R 3 each occurrence is independently selected from I - 、Br - And Cl - And F - Any one of them;
a is selected from-MgR 4 Or Li, R 4 Selected from any one of I, br and Cl.
In some embodiments, the mixing reaction is performed in an organic solvent, where 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 a substituted or unsubstituted aromatic hydrocarbon solvent with a ring atom number of 6-20, 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) - (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 unsubstituted aromatic hydrocarbon solvent with the ring number of 6-10 and an aromatic hydrocarbon solvent with the ring number of 6-10, wherein the aromatic hydrocarbon solvent is substituted by an alkyl group with the carbon number of 1-5;
(3) The ether solvent comprises at least one of a compound shown in a formula (5) and a compound shown in a formula (6):
wherein R is 5 Each occurrence of the alkyl is independently selected from the alkyl groups with 1-5 carbon atoms; n is n 3 Is any integer of 1 to 3;
(4) The ketone solvent is shown as a formula (7):
wherein R is 6 Each occurrence of the alkyl is independently selected from the alkyl groups with 1-5 carbon atoms;
(5) The volume-mass ratio of the organic solvent to the compound (1) is (9-20) mL to 1g.
In some of these embodiments, R 5 Each occurrence of the alkyl is independently selected from the alkyl groups with 1-4 carbon atoms; n is n 3 Is any integer of 1 to 2;
R 6 each occurrence is independently selected from straight-chain alkyl groups with 1-3 carbon atoms.
In some embodiments, the molecular sieve catalyst satisfies at least one of the following conditions (6) - (7):
(6) The mass ratio of the molecular sieve catalyst to the compound (1) is 1 (8-15);
(7) The molecular sieve catalyst comprises at least one of an MCM-41 molecular sieve and a 4A molecular sieve;
the compound (1) meets at least one of the following conditions (8) - (10):
(8) n 1 is 1, R 1 Any one selected from alkyl groups having 1 to 5 carbon atoms;
(9) n 2 is 2, R 2 Each occurrence of the alkyl groups is selected from any one of the alkyl groups with 1-5 carbon atoms;
(10) Each R is 1 And each R 2 Selected from the same groups;
the compound (2) meets at least one of the following conditions (11) - (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 (1-1.2): 1;
the compound (3) meets at least one of the following conditions (13) - (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 isopropyl.
In some embodiments, the temperature of the mixing reaction is 20-30 ℃ and the time is 12-48 h.
In some embodiments, the process for preparing the pyridine amino hafnium catalyst represented by formula (4) further includes the following steps:
removing the solvent from the mixed reaction product to prepare a first concentrated product;
dissolving the first concentrated product in a substituted or unsubstituted aromatic hydrocarbon solvent with the ring atom number of 6-20, filtering, and concentrating the filtrate to prepare a second concentrated product;
dissolving the second concentrated product in a recrystallization solution to perform recrystallization treatment to prepare the pyridine amino hafnium catalyst shown in the formula (4);
the recrystallization solution comprises at least one alkane with the carbon number of 5-10.
In some embodiments, the recrystallization solution satisfies at least one of the following conditions (15) - (16):
(15) The volume ratio of the recrystallization solution to the second concentrated product is (5-10): 1;
(16) The recrystallization solution comprises at least one alkane with the carbon number of 5-8.
Compared with the prior art, the application has the following beneficial effects:
in the preparation method of the pyridine amino hafnium catalyst, the compound (1), the compound (2) and the compound (3) are mixed to react under the action of a molecular sieve catalyst, and the pyridine amino hafnium catalyst shown in the formula (4) can be directly prepared in one pot without using dangerous compounds such as trimethylaluminum, butyllithium and the like, so that the steps are simple and the yield is high.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a hafnium pyridinium amine based catalyst prepared in the examples.
Detailed Description
The present application is described in further detail below in connection with specific embodiments. 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 application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present application, the term "alkyl" refers to a group formed by the loss of one hydrogen from an alkane, e.g., methyl group formed by the loss of one hydrogen from methane, including cycloalkyl and alkanyl.
The term "alkanyl" refers to an alkane in which the carbon atoms are all joined by a single carbon-carbon bond and are not cyclic, and the remaining valences are all hydrogen-bonded to form a group upon loss of one hydrogen, including straight chain alkanyl and branched alkanyl. Similarly, a "cycloalkyl" aryl refers to a group in which the carbon atoms are all joined by a single carbon-carbon bond and are partially cyclic, and the remaining bonds are all formed by the loss of one hydrogen from an alkane formed by combining the remaining bonds with hydrogen.
In the present application, the "alkane 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 refers to a group formed by losing one hydrogen from an alkane having 2 to 15 carbon atoms (i.e., a C1-15 alkane), and specific examples include a group formed by losing one hydrogen from 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, and non-limiting examples of "C1-15 alkane" include methane, ethane, n-propane, isopropyl, n-butane, isobutane, 2-ethylbutane, 3-dimethylbutane, n-pentane, isopentane, neopentane, 1-methylpentane, 3-methylpentane, 2-ethylpentane, 4-methyl-2-pentane, n-hexane, 1-methylhexane, 2-ethylhexane, 2-butylhexane, n-heptane, 1-methylheptane, 2-ethylheptane, n-heptane, n-nonane, n-2-ethylheptane, n-heptane.
In this application, where no attachment site is indicated in a group, an optionally attachable site in the group is meant as an attachment site.
In the present application, a single bond to a substituent extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.g
R in (C) is connected with any substitutable site of benzene ring.
In the present application, "number of ring atoms" means the number of atoms bonded to form a ring, and when the ring is substituted with a substituent, the atoms contained 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 a benzene ring is 6, the number of ring atoms of a 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, the attachment site of the substituent is not indicated in the group, and 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, the preparation method either involves multi-step reaction or involves inflammable and easily-decomposed intermediate products, or dangerous materials such as trimethylaluminum are needed, for example, in a technical scheme, ligand substrates are reacted with butyl lithium to prepare ligand lithiate, then the ligand lithiate is reacted with hafnium tetrachloride in a reflux way, and finally the ligand lithiate is reacted with Grignard reagent to obtain the final catalyst.
In another technical scheme, ligand substrates are adopted to react with tetra (dimethylamino) hafnium, a dimethylamino intermediate is obtained first, and then trimethylaluminum is used for methylation to obtain the pyridine amino hafnium catalyst, and the intermediate involved in the process is inflammable and easily decomposed, trimethylaluminum is needed, inflammable and explosive, and the yield is low.
Based on the above, in the long-term synthesis research and the production process, the technical personnel of the application obtain the preparation method of the pyridine amino hafnium catalyst with simple steps and high yield after a large number of creative experiments.
In one embodiment of the present application, a method for preparing a hafnium pyridinaminyl catalyst is provided, including the following step S10.
Step S10: and (3) carrying out a mixing reaction on the compound (1), the compound (2) and the compound (3) under the action of a molecular sieve catalyst to prepare the pyridine amino hafnium catalyst shown in the formula (4).
The structures of the pyridine amino hafnium catalysts shown in the compound (1), the compound (2), the compound (3) and the formula (4) are respectively as follows:
wherein R is 1 Each occurrence is independently selected from any one of H and alkyl with 1-15 carbon atoms, n 1 Any integer selected from 1 to 5;
R 2 each occurrence is independently selected from any one of H and alkyl with 1-15 carbon atoms, n 2 Any integer selected from 1 to 5;
R 3 each occurrence is independently selected from I - 、Br - And Cl - And F - Any one of them;
a is selected from-MgR 4 Or Li, R 4 Selected from any one of 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 to react under the action of a molecular sieve catalyst, and the pyridine amino hafnium catalyst shown in the formula (4) can be directly prepared in one pot without using dangerous compounds such as trimethylaluminum, butyllithium 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 Each occurrence is identically selected from 1, 2, 3, 4 or 5.
When R is 1 Are all selected from H or R 2 When selected from H, means that the group on which it resides is phenyl.
In some embodiments, the mixing reaction is performed in an organic solvent, where 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.
The substituted or unsubstituted aromatic hydrocarbon solvent with the ring number of 6-20 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 the possibly related reaction intermediate 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 unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms, and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the organic solvent includes at least one of an ether solvent, a ketone solvent, an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms, and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the organic solvent includes at least one of an ether solvent, a ketone solvent, an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms, and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the organic solvent includes at least one of an ether solvent, a ketone solvent, an unsubstituted aromatic hydrocarbon solvent having 6 to 8 ring atoms, and an aromatic hydrocarbon solvent having 6 to 8 ring atoms substituted with an alkyl group having 1 to 4 carbon atoms.
In some embodiments, the organic solvent includes at least one of an ether solvent, a ketone solvent, benzene, and a phenyl solvent substituted with an alkyl group having 1 to 5 carbon atoms.
In some of these embodiments, an alkanyl having 1 to 5 carbon atoms includes, but is not limited to: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl.
In some of these embodiments, phenyl solvents substituted with an alkanyl group having 1 to 5 carbon atoms include, but are not limited to: at least one of toluene and xylene.
In some embodiments, the ether solvent comprises at least one of a compound represented by formula (5) and a compound represented by formula (6):
wherein R is 5 Each occurrence of the alkyl is independently selected from the alkyl groups with 1-5 carbon atoms; n is n 3 Is any integer of 1 to 3.
n 3 1, 2 or 3; in some of these embodiments, n 3 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 Each occurrence of which is independently selected from an alkanyl group having 1 to 4 carbon atoms.
In some of these embodiments, R 5 Each occurrence is identically selected from the group consisting of alkanyl groups having 1 to 4 carbon atoms.
Specific examples of the "alkyl group having 1 to 4 carbon atoms" include: any one of methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
In some of these embodiments, the compound of formula (5) includes at least one of methyl ether, ethyl ether, butyl ether, and methyl tert-butyl ether.
In some of these embodiments, the ketone solvent is as shown in formula (7):
R 6 each occurrence of which is independently selected from an alkanyl group having 1 to 5 carbon atoms.
In some of these embodiments, R 6 Each occurrence is independently selected from carbon atomsA linear alkyl group or branched alkyl group having a number of 1 to 5.
In some of these embodiments, R 6 Each occurrence is independently selected from straight-chain alkyl groups with 1-3 carbon atoms.
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 solvent comprises 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 tertiary 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 a substituted or unsubstituted aromatic hydrocarbon solvent with a ring number of 6-20, and the second solvent includes at least one of an ether solvent and a ketone solvent.
Further studies by the skilled person in this application have found that: when the specific first solvent and the specific second solvent are mixed to be used as the reaction solvent, the raw materials and the products can have better solubility, the reaction is prone to be carried out under the homogeneous phase condition, the reaction efficiency can be further improved, and the yield of the products is 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 performed in a specific organic solvent environment, and the reaction efficiency is further improved.
In the above "(3-5): 1", the values of the ratio include the minimum and maximum values of the range, and each value between such minimum and maximum values, and specific examples include, but are not limited to, the point values in the examples and the following point values: 3:1, 3.5:1, 4:1, 4.5:1, 5:1; or a range of any two values.
In some embodiments, the first solvent includes at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the first solvent includes at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the first solvent includes at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the first solvent includes at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 8 ring atoms and an aromatic hydrocarbon solvent having 6 to 8 ring atoms substituted with an alkyl group having 1 to 4 carbon atoms.
In some embodiments, the first solvent includes at least one of benzene and a phenyl solvent substituted with an alkyl group having 1 to 5 carbon atoms.
In some of these embodiments, an alkanyl having 1 to 5 carbon atoms includes, but is not limited to: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl.
In some of these embodiments, phenyl solvents substituted with an alkanyl group having 1 to 5 carbon atoms include, but are 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 types of the ether solvents and the ketone solvents are as described above, and are not described in detail herein.
In some of these embodiments, the second solvent includes at least one of the compound represented by formula (5), the compound represented by formula (6), and the compound represented by formula (7) described above.
In some of these embodiments, the second solvent includes any one of the compound represented by formula (5), the compound represented by formula (6), and the compound represented by formula (7) described above.
The compound represented by formula (5), the compound represented by formula (6) and the compound represented by formula (7) are as described above, and are not described in detail herein.
In some of these embodiments, the second compound comprises at least one of methyl ether, ethyl ether, butyl ether, methyl tertiary 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 (9-20) mL 1g.
In the above "(9-20) mL:1g", 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 point values in the embodiments and the following point values: 9mL:1g, 10mL:1g, 11mL:1g, 12mL:1g, 13mL:1g, 14mL:1g, 15mL:1g, 16mL:1g, 17mL:1g, 18mL:1g, 19mL:1g, 20mL:1g; or a range of any two values.
In some of these embodiments, in compound (1), n 1 Is 1, R 1 Any one selected from alkyl groups having 1 to 5 carbon atoms.
In some of these embodiments, R 1 All of which are the same and are selected from any of alkyl groups having 1 to 4 carbon atoms.
In some of these embodiments, R 1 All of which are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.
In some of these embodiments, n 2 Is 2, R 2 Each occurrence is selected from any one of alkyl groups having 1 to 5 carbon atoms.
In some of these embodiments, R 2 Each occurrence is selected from any one of alkyl groups having 1 to 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 groups.
In some of these embodiments, the structure of compound (1) is as follows:
wherein i-Pr represents isopropyl.
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 compound (2) to compound (1) is (1-1.2): 1.
The reaction efficiency can be further improved by controlling the molar ratio of the compound (2) to the compound (1).
In the above (1-1.2): 1″, 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 point values in the embodiments and the following point values: 1:1, 1.1:1, 1.2:1; or a range of any two values.
In some of these embodiments, compound (3) comprises at least one of methyl magnesium bromide, methyl magnesium chloride, methyl magnesium iodide, and methyl lithium.
In some embodiments, the molar ratio of compound (3) to compound (1) is (4.5-5): 1.
In the above "(4.5-5): 1", 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 point values in the embodiments and the following point values: 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1; or a range of any two values.
In some embodiments, the temperature of the mixing reaction is 20-30 ℃ and the time is 12-48 h.
The conditions of the mixed reaction are regulated, and side reactions are avoided while the higher reaction efficiency is maintained, so that the yield of the product is further improved.
According to the preparation scheme, higher yield can be realized under milder temperature conditions.
In the foregoing "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 point values in the embodiments and the following point values: 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃; or a range of any two values.
In the above "12h to 48h", 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 point values in the embodiments and the following point 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 a range of any two values.
In some embodiments, the mass ratio of the molecular sieve catalyst to the compound (1) is 1 (8-15).
In the above "1 (8-15)", 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 point values in the embodiments and the following point values: 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15; or a range of any two values.
The molecular sieve catalyst comprises a natural molecular sieve and an artificial synthetic molecular sieve, wherein the natural molecular sieve is mainly crystalline silicate or aluminosilicate, and silicon oxygen tetrahedron or aluminum oxygen tetrahedron are connected through oxygen bridge bonds to form a pore canal and a cavity system with molecular size of the molecular sieve, so that the molecular sieve catalyst has the characteristic of sieving molecules, researchers find out the molecular sieve of phosphoaluminate type with the deep research of molecular sieve synthesis and application, and the framework elements of the molecular sieve, such as silicon, aluminum or phosphorus, 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 of the molecular sieve can be more than 2 nm, so that the molecular sieve can be divided into a silicon aluminum molecular sieve, a phosphorus aluminum molecular sieve and a framework heteroatom molecular sieve according to the framework element composition, such as A type potassium A (3A), sodium A (4A) and calcium A (5A); x type is calcium X (10X) and sodium X (13X); y is sodium Y, calcium Y, etc.; further, there are other kinds of molecular sieves, such as MCM-41 molecular sieves, which are prepared by using a quaternary ammonium salt of a supramolecular surfactant as a template for the porous silicate, depending on the template 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 pyridine amino hafnium catalyst shown in the formula (4) further includes the following steps S11 to S13.
Step S11, removing the solvent in the mixed reaction product to prepare a first concentrated product.
The solvent in the product of the mixing reaction may be removed using methods commonly used in the art, including but not limited to: and (5) distilling under reduced pressure.
And S12, dissolving the first concentrated product in a substituted or unsubstituted aromatic hydrocarbon solvent with the ring number of 6-20, filtering, and concentrating the filtrate to prepare a second concentrated product.
The target product of the pyridine amino hafnium catalyst shown in the formula (4) is easy to dissolve in a substituted or unsubstituted aromatic hydrocarbon solvent with the ring atom number of 6-20, and other raw materials and intermediate products are difficult to dissolve in the substituted or unsubstituted aromatic hydrocarbon solvent with the ring atom number of 6-20, so that the target product, other raw materials and byproducts can be subjected to preliminary separation after filtration.
In some embodiments, the first concentrated product is dissolved in at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the first concentrated product is dissolved in at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the first concentrated product is dissolved in at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 10 ring atoms and an aromatic hydrocarbon solvent having 6 to 10 ring atoms substituted with an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the first concentrated product is dissolved in at least one of an unsubstituted aromatic hydrocarbon solvent having 6 to 8 ring atoms and an aromatic hydrocarbon solvent having 6 to 8 ring atoms substituted with an alkyl group having 1 to 4 carbon atoms.
In some embodiments, the first concentrated product is dissolved in at least one of benzene and a phenyl solvent substituted with an alkyl group having 1 to 5 carbon atoms.
In some of these embodiments, an alkanyl having 1 to 5 carbon atoms includes, but is not limited to: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl.
In some of these embodiments, phenyl solvents substituted with an alkanyl group having 1 to 5 carbon atoms include, but are not limited to: at least one of toluene and xylene.
In some of these embodiments, the first concentrated product described above is dissolved in at least one of benzene, toluene, xylene.
The purpose of the above concentration treatment is 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 in a recrystallization solution to perform recrystallization treatment to prepare a pyridine amino hafnium catalyst shown in a formula (4); the recrystallization solution comprises at least one alkane with 5-10 carbon atoms.
Further studies by the skilled person in this application have found that: the solubility of the target product in the specific recrystallization solvent changes along with the change of temperature, so that the target product is further purified by adopting the specific recrystallization solvent on the premise of reducing the loss.
In some embodiments, the volume ratio of the recrystallization solution to the second concentrated product is (5-10): 1.
And adjusting the volume ratio of the recrystallization solution to the second concentrated product to further improve the recrystallization efficiency.
In the above "(5-10): 1", 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 point values in the embodiments and the following point values: 5:1, 6:1, 7:1, 8:1, 9:1, 10:1; or a range of any two values.
In some of these embodiments, the recrystallization solution includes at least one of paraffins having 5 to 8 carbon atoms.
In some embodiments, the recrystallization solution includes at least one of linear alkanes having 5 to 8 carbon atoms.
In some of these embodiments, the recrystallization solution includes at least one of n-pentane, n-hexane, n-heptane, n-octane.
The present application will be described in connection with specific embodiments, but is not limited thereto, and it is to be understood that the appended claims outline the scope of the application, and those skilled in the art, guided by the concepts herein provided, will recognize certain changes made to the embodiments of the application that will be covered by the spirit and scope of the claims of the application.
The following are specific examples.
Example 1
The synthesis of the pyridine amino hafnium catalyst comprises the following synthetic route:
the method comprises the following specific steps:
raw material (2) hafnium tetrachloride (2.56 g, 8 mmol), MCM-41 molecular sieve (0.37 g), raw material (1) N- [2,6-bis (1-methyl) phenyl ] -R- [2- (1-methyl) phenyl ] -6- (1-nanowire) -2-pyridinemethanamine, chinese name: 2- [ N- (2, 6-diisopropylphenylamino) -o-isopropylphenyl methyl ] -6- (1-naphthyl) -pyridine (3.99 g, 7.8 mmol), anhydrous toluene 30 mL, anhydrous diethyl ether 8mL, adding diethyl ether solution of raw material (3) methyl magnesium bromide (12 mL, 3M) by syringe at room temperature (20 ℃ to 30 ℃) and then reacting at room temperature (20 ℃ to 30 ℃) for 12 hours; after the reaction, the solvent is distilled off under reduced pressure to obtain a first concentrated product, anhydrous toluene 50 mL is added into the first concentrated product, the first concentrated product is filtered, filtrate is taken for concentration treatment to obtain a second concentrated product of 10mL, the second concentrated product is added into 100mL n-pentane for recrystallization, and the yellow product of pyridine amino hafnium catalyst (5.2 g) is obtained after filtration and drying, and the structure is shown in the above route.
Nuclear magnetic hydrogen spectrum test is carried out on the prepared pyridine amino hafnium catalyst, and the result is as follows:
1 HNMR ( C 6 D 6 : deuterated benzene) δ: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 figure 1.
The results show that: by adopting the method, the target product is successfully prepared.
The yield of the hafnium pyridinaminyl catalyst was calculated using the following formula:
yield = moles of hafnium pyridinaminyl catalyst per moles of starting material (1) ×100%.
The main parameters and the yield and purity are shown in Table 1.
Examples 2 to 7
Examples 2 to 7 are the same as example 1, except that the parameters shown in Table 1 are set forth, and other conditions not shown in Table 1 are the same as example 1.
Comparative example 1
Comparative example 1 was essentially the same as example 1 except that no MCM-41 molecular sieve was added during the reaction step, and the specific results are set forth 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 this condition is not present.
Analysis of table 1 data: in the preparation method of the pyridine amino hafnium catalyst, the compound (1), the compound (2) and the compound (3) are subjected to mixed reaction under the action of a 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 trimethylaluminum, butyllithium and the like, so that the steps are simple, the yield is high, and the yield of the comparative example 1 is greatly reduced under the condition that no catalyst exists.
Further, in example 1, the yield of the reaction was further improved by adjusting the solution used in the reaction as compared with example 7.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples represent only a few embodiments of the present application, which are described in more detail and detail, but are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. The scope of the application is, therefore, indicated by the appended claims, and the description may 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:
the compound (1), the compound (2) and the compound (3) are mixed to react 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 pyridine amino hafnium catalyst shown in the formula (4) are respectively as follows:
R 2 each occurrence is independently selected from any one of H and alkyl with 1-15 carbon atoms, n 2 Any integer selected from 1 to 5;
R 3 each occurrence is independently selected from I - 、Br - And Cl - And F - Any one of them;
a is selected from-MgR 4 Or Li, R 4 Any one selected from I, br and Cl;
the mixing reaction is carried out in an organic solvent, the organic solvent comprises a first solvent and a second solvent, and the volume ratio of the first solvent to the second solvent is (3-5) 1; the first solvent comprises at least one of an unsubstituted aromatic hydrocarbon solvent with the ring number of 6-10 and an aromatic hydrocarbon solvent with the ring number of 6-10, which is substituted by an alkyl group with the carbon number of 1-5, and the second solvent comprises at least one of an ether solvent and a ketone solvent;
the ether solvent comprises at least one of a compound shown in a formula (5) and a compound shown in a formula (6):
the ketone solvent is shown as a formula (7):
wherein R is 6 Each occurrence of which is independently selected from an alkanyl group having 1 to 5 carbon atoms.
2. The method for producing a hafnium pyridinium amido catalyst according to claim 1, wherein the volume/mass ratio of the organic solvent to the compound (1) is (9-20) mL/1 g.
3. The method for preparing a pyridine amino hafnium catalyst according to claim 1, wherein R 5 Each occurrence of the alkyl is independently selected from the alkyl groups with 1-4 carbon atoms; n is n 3 Is any integer of 1 to 2;
R 6 each occurrence is independently selected from straight-chain alkyl groups with 1-3 carbon atoms.
4. The method for preparing a hafnium pyridinium amine based catalyst of claim 1, wherein the compound of formula (5) comprises at least one of methyl ether, diethyl ether, butyl ether and methyl t-butyl ether.
5. The method for preparing a pyridine amino hafnium catalyst according to claim 1, wherein the ketone solvent comprises at least one of acetone and 2-butanone.
6. The method for preparing a pyridine amino hafnium catalyst according to any one of claims 1 to 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 (8-15);
(7) The molecular sieve catalyst comprises at least one of an MCM-41 molecular sieve and a 4A molecular sieve;
the compound (1) meets at least one of the following conditions (8) - (10):
(8) n 1 is 1, R 1 Any one selected from alkyl groups having 1 to 5 carbon atoms;
(9) n 2 is 2, R 2 Each occurrence of the alkyl groups is selected from any one of the alkyl groups with 1-5 carbon atoms;
(10) Each R is 1 And each R 2 Selected from the same groups;
the compound (2) meets at least one of the following conditions (11) - (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 (1-1.2): 1;
the compound (3) meets at least one of the following conditions (13) - (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 for preparing a pyridine amino hafnium catalyst according to any one of claims 1 to 5, wherein the structure of the compound (1) is as follows:
8. The method for preparing a pyridine amino hafnium catalyst according to any one of claims 1 to 5, wherein the temperature of the mixing reaction is 20 ℃ to 30 ℃ and the time is 12h to 48h.
9. The method for preparing a hafnium pyridinaminyl catalyst according to any one of claims 1 to 5, further comprising the steps of:
removing the solvent from the mixed reaction product to prepare a first concentrated product;
dissolving the first concentrated product in a substituted or unsubstituted aromatic hydrocarbon solvent with the ring atom number of 6-20, filtering, and concentrating the filtrate to prepare a second concentrated product;
dissolving the second concentrated product in a recrystallization solution to perform recrystallization treatment to prepare the pyridine amino hafnium catalyst shown in the formula (4);
the recrystallization solution comprises at least one alkane with the carbon number of 5-10.
10. The method for preparing a hafnium pyridinamine-based catalyst according to claim 9, wherein the recrystallization solution satisfies at least one of the following conditions (15) - (16):
(15) The volume ratio of the recrystallization solution to the second concentrated product is (5-10): 1;
(16) The recrystallization solution comprises at least one alkane with the carbon number of 5-8.
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