CN108912009B - Asymmetric diimine nickel catalyst and ligand, preparation method and application thereof - Google Patents
Asymmetric diimine nickel catalyst and ligand, preparation method and application thereof Download PDFInfo
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- CN108912009B CN108912009B CN201810555896.8A CN201810555896A CN108912009B CN 108912009 B CN108912009 B CN 108912009B CN 201810555896 A CN201810555896 A CN 201810555896A CN 108912009 B CN108912009 B CN 108912009B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003446 ligand Substances 0.000 title abstract description 33
- 229910000071 diazene Inorganic materials 0.000 title abstract description 25
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- 229920000098 polyolefin Polymers 0.000 claims abstract description 18
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 claims abstract description 15
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- -1 C1-C6Alkyl Chemical class 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 235000011054 acetic acid Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 21
- 239000005977 Ethylene Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 abstract description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical class C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 description 10
- 238000003780 insertion Methods 0.000 description 10
- 230000037431 insertion Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 239000012041 precatalyst Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- QAAHHTVIGAWDJK-UHFFFAOYSA-N 2-benzhydryl-4-methyl-6-(4-methylphenyl)aniline Chemical compound CC1=CC=C(C=C1)C2=C(C(=CC(=C2)C)C(C3=CC=CC=C3)C4=CC=CC=C4)N QAAHHTVIGAWDJK-UHFFFAOYSA-N 0.000 description 1
- XXMOABNUVYYSCY-UHFFFAOYSA-N 2-benzhydryl-4-methyl-6-phenylaniline Chemical compound CC1=CC(=C(C(=C1)C(C2=CC=CC=C2)C3=CC=CC=C3)N)C4=CC=CC=C4 XXMOABNUVYYSCY-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JAMQPOXCPBCRFC-UHFFFAOYSA-M C(CCC)[Ni]Br Chemical compound C(CCC)[Ni]Br JAMQPOXCPBCRFC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical class CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ZMZINYUKVRMNTG-UHFFFAOYSA-N acetic acid;formic acid Chemical compound OC=O.CC(O)=O ZMZINYUKVRMNTG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical class C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005021 gait Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to an asymmetric diimine nickel catalyst of the formula, a ligand, a preparation method and application thereof, wherein R1～R8And X is as defined herein. Such catalysts of the invention have high thermal stability and extremely high activity for ethylene polymerization, resulting in polyolefin materials with various degrees of branching and high molecular weight; furthermore, the catalyst of the present invention can be used for copolymerization of short-chain olefins such as propylene with methyl undecylenate.
Description
Technical Field
The invention relates to the field of catalysis and the field of synthetic polymer polyolefin materials, in particular to an asymmetric diimine nickel catalyst and a ligand, a preparation method and application thereof.
Background
Polyolefins are the most indispensable class of materials in daily life due to their extremely excellent properties and relatively low price. At present, the demand of polyolefin is quite remarkable, and due to the unique synthesis method, the research on the core catalyst in the synthesis of the polyolefin occupies a very important position.
Throughout the history of the development of the olefin polymerization industry, it has been found that the technological advances in the industry are not closely related to the discovery of new catalysts and the advancement of process technology. In the process of olefin polymerization, the catalyst often determines the polymerization behavior of the whole polymerization process, the state of the particles of the produced polymer, and the topology and product properties of the polymer. The research and development of the catalyst for olefin polymerization enable the polymerization varieties of the olefin to be richer and the performance to be more excellent, and the actual application field of the polymer is greatly widened.
A series of phosphine ligand based palladium and nickel catalysts have recently been shown to have this capability, and despite these advances, Brookhart type α -diimine catalysts remain a research hotspot in this field, extensive mechanistic studies reveal the unique chain walking characteristics of this type of catalyst, which involve β -hydrogen elimination and reinsertion.
Patent application CN 105152970a describes a highly sterically hindered diimine palladium catalyst with a symmetrical structure, and its ligand, preparation method and use. However, in this application, due to the symmetrical large steric hindrance structure of the ligand compound, the obtained catalyst has a low branching degree and a narrow molecular weight distribution with respect to the obtained polyolefin compound or copolymer, is inconvenient to process, and has a low insertion ratio with respect to the insertion of the polar monomer.
Brookhart et al (j.am. chem.soc.,1995,117,6414.), (j.am. chem.soc.,1996,118,11664.) in the last 90 th century reported for the first time that nickel and palladium diimine catalysts could be used in the production of high molecular weight polyethylene and in the production of polyolefins with polar functional groups. Since then, there has been a great enthusiasm for the polymerization studies of the diimine ligand catalysts. Despite these excellent properties, these catalysts tend to lack thermal stability, greatly limiting their industrial application. These catalysts decompose rapidly above 50 ℃ and produce low molecular weight polymers at high temperatures; another limitation is that the copolymerization activity of these catalysts is greatly reduced and the molecular weight of the copolymer is greatly reduced; in addition, the low melting point due to the high branching degree also limits some applications.
Long et al (J.Am.chem.Soc.2013,135(44),16316-16319) find that the polyolefin obtained by polymerizing the nickel diimine catalyst of the diphenyl substituted methylaniline derivative at 100 ℃ is suitable for industrial gas phase regulation polymerization (80-100 ℃), but the application of the polyolefin is limited by the low yield (8.6%) of the synthetic ligand; the yield of the acenaphthenequinone derivative synthesized by the modified synthesis steps is still only 10% (ACS Catal.2014,4, 2501-2504).
Menglong Gao et al ("Ethylene polymerization by 2, 3-diiminylbutyrylamide pre-catalysts for catalyst removal from benzyl sulfides", Journal of organic Chemistry,798(2015) p401-407) propose a 2, 3-diiminobutylkl nickel bromide precatalyst with a benzhydryl group for Ethylene polymerization. However, in the described precatalyst, both groups in the benzene para-position are benzhydryl groups which significantly increase the steric hindrance of the overall catalyst, which also presents the problems mentioned above in CN 105152970a, namely that the obtained catalyst has a low degree of branching and a narrow molecular weight distribution for the obtained polyolefin compound or copolymer, is inconvenient to process, and the insertion is low for the insertion of polar monomers, due to the large steric hindrance structure of the ligand compound.
Markus Schmid et al ("New C2v-and Chiral C2-symmetry olefin Polymerization Catalysts Based on Nickel (II) and Palladium (II) diimine Polymerization Catalysts 2,6-Diphenyl amine polymers: Synthesis, structural catalysis, and First Insight Polymerization Properties", Organometallics,20(2001) p2321-2330) proposed a 2, 3-diimine butyl Nickel bromide precatalyst with an aromatic group for ethylene Polymerization. However, in the precatalyst described, the groups in both ortho positions to the benzene are aromatic groups, which is very low in activity but allows to obtain polyolefins with very low branching and high melting points at room temperature, i.e. due to the structure of the ortho aromatic groups, the obtained catalyst has a high melting point and a narrow molecular weight distribution for the obtained polyolefin compound, is not easy to process and has a low insertion rate for the insertion of polar monomers.
Jennifer L.Rhinehart et al ("A Robust Ni (II) α -diene Catalyst for high hTimePerure Ethylene Polymerization", Journal of The American chemical society, Vol.135, p.16316-16319) describe complexes 2 a-b:
(wherein R is Me), which can be used as a catalyst for the polymerization of olefins. However, on the one handAs is apparent from the structure thereof, the catalyst also has the problem in CN 105152970a mentioned above, that is, the obtained catalyst is narrow in molecular weight distribution for the obtained polyolefin compound due to the large steric hindrance structure of the ligand compound, inconvenient to process, while not involving the insertion ratio of the polar monomer at all; on the other hand, the catalyst itself has a very low synthesis yield of the ligand compound, and accordingly the catalyst has a necessarily low synthesis yield, which is a vital problem as well known to those skilled in the art, and thus has no practical value.
Despite decades of research work, the research associated with the α -diimine nickel catalyst has presented significant challenges, particularly in the areas of (1) effectively inhibiting the chain gait process to achieve regio-controlled α -olefin polymerization and (2) copolymerization of olefins with polar monomers.
Disclosure of Invention
In view of this, the object of the present invention is to provide a class of asymmetric α -diimine ligands and corresponding ni (ii) catalysts, which have high thermal stability and extremely high activity for ethylene polymerization, resulting in polyolefin materials with various degrees of branching and high molecular weight, and methods of preparation and use thereof.
In one aspect, the present invention provides a compound of formula (I):
wherein R is1、R3、R4And R6Independently of one another are hydrogen, C1-C6Alkyl, halogen or halogeno C1-C6An alkyl group; r2And R5Independently of one another are hydrogen, C1-C6Alkyl, halogen, halogeno C1-C6Alkyl, nitro, C1-C6Alkoxy, N-di (C)1-C6Alkyl) amino or trifluoromethyl; and R is7And R8Independently of one another are hydrogen, C1-C6Alkyl, halogenHalogen substituted C1-C6Alkyl, nitro, C1-C6Alkoxy, N-di (C)1-C6Alkyl) amino or trifluoromethyl.
In another aspect, the present invention provides a process for the preparation of a compound of formula (I) as described above, said process comprising:
reacting a diketone compound of formula a with an amine compound of formula B and C and a zinc halide of formula D in an organic acid solvent at 60-120 ℃ for 0.5-6h to form a compound of formula E;
then reacting the compound of formula E with an aqueous solution of a weak acid salt in an organic polar solvent for 0.2-5h at room temperature to form the compound of formula (I),
wherein R is1、R2、R3、R4、R5、R6、R7And R8As defined above, and each X is independently halogen.
In a preferred embodiment, the organic acid is formic acid, acetic acid, propionic acid or a mixture thereof, and the organic polar solvent is dichloromethane, chloroform, chlorobenzene, dichloroethane or a mixture thereof.
In another aspect, the present invention provides a complex of formula (II):
wherein R is1、R2、R3、R4、R5、R6、R7And R8As defined above, Ph represents phenyl and each X is independently halogen.
In another aspect, the present invention provides a process for preparing a complex of formula (II),
the method comprises the following steps:
reacting a compound of formula (I) as defined above with a compound of formula DMENiX in an organic solvent at ambient temperature2The nickel precursor compound of (a) is reacted,
wherein DME represents ethylene glycol dimethyl ether, and R1、R2、R3、R4、R5、R6、R7、R8And X is as defined above.
In a preferred embodiment, each X is independently Cl or Br.
In another aspect, the present invention provides a method of preparing a polyolefin compound, the method comprising: the complex of the formula (II) is used as a catalyst to catalyze and polymerize low-carbon olefins. Preferably, the lower olefin is C2-4An olefin, more preferably ethylene or propylene.
In another aspect, the present invention provides a polyolefin compound prepared according to the above process, characterized in that the polyolefin compound has a number of methyl groups corresponding to 1000 methylene groups of 50 to 250 and a molecular weight of 20000-.
In another aspect, the present invention provides a method of preparing a copolymer of a lower olefin and methyl undecylenate, the method comprising: the complex of the formula (II) is used as a catalyst to catalyze and polymerize low-carbon olefin and methyl acrylate. Preferably, the lower olefin is C2-4An olefin, more preferably ethylene.
In another aspect, the present invention provides a copolymer prepared according to the above method, characterized in that the copolymer has a number of methyl groups corresponding to 1000 methylene groups of 60 to 250, an insertion ratio of 0.4 to 4.0%, and a molecular weight of 60000g/mol of 10000-.
The asymmetric diimine compound of the formula (I) is used as a ligand to form an asymmetric diimine nickel complex catalyst of the formula (II), and the catalyst has high activity for olefin polymerization and produces polyethylene with proper branching degree and high molecular weight; furthermore, the catalyst of the present invention can be used for the copolymerization of ethylene with methyl undecylenate. The polyethylene and methyl undecylenate copolymer obtained by the invention is a solid macromolecule, the branching degree of the obtained polymer is moderate, and the branching degree of methyl in 1000 methylene groups is 60-250.
Drawings
FIG. 1 shows a schematic single crystal structure of an asymmetric diimine ligand nickel catalyst prepared in accordance with example 5 of this invention, wherein N1 and N2 represent the 1 st and 2 nd nitrogen atoms in the ligand structure, respectively; br1 and Br2 represent bromine atoms in the ligand structure; ni1 represents a nickel atom in the ligand structure; c1 and C2 represent the 1 st and 2 nd carbon atoms in the ligand structure, where the remaining 3 rd to 66 th carbon atoms (C3-C66) in the ligand structure are not indicated on the figure (all hydrogen atoms are also not shown).
FIG. 2 shows the hydrogen NMR spectra of polyethylene prepared according to example 7 of the present invention, with NMR measurements using a Bruker400MHz NMR spectrometer.
FIG. 3 shows the NMR spectra of PP-methylundecenoate copolymer prepared according to example 8 of the present invention, with NMR measurement using a Bruker400MHz NMR spectrometer.
Detailed Description
The invention hopes that wider molecular weight distribution can be brought by the asymmetric structure, so that high polymers with more excellent physical properties can be obtained, and meanwhile, the asymmetric structure is hoped to effectively improve the copolymerization of polar monomers. Based on the method, the asymmetric diimine nickel catalyst with improved catalytic activity for the polymerization of low-carbon olefin or the copolymerization of the low-carbon olefin and methyl undecylenate is obtained by changing the spatial position of a ligand compound of the catalyst, namely reducing the steric hindrance on one side of the ligand compound, so that high molecules with proper branching degree and wider distribution can be obtained, and meanwhile, the insertion ratio of polar monomers is improved.
The nickel catalyst structure of the present invention is asymmetric because of the groups on both sides of the aniline (i.e., one side of the substituted aryl group, the other side of the substituted aryl group is a bulky steric group structure).
The inventor of the invention has made extensive and intensive studies to prepare a novel ligand compound, a catalyst complex and a catalytic system by changing the catalyst structure, thereby catalyzing low-carbon olefins such as ethylene and propylene with high activity to directly obtain olefins such as polyethylene with high molecular weight and moderate branching degree; the catalyst can also catalyze the copolymerization of low-carbon olefin such as propylene and methyl undecylenate to obtain a copolymer with the branching degree of 60-250.
One aspect of the present invention provides a method for synthesizing a class of ligands (i.e., compounds of formula (I)) having different steric hindrance structures with high yield (up to 80% or more) to synthesize a target nickel catalyst; on the other hand, the nickel diimine catalyst based on the ligand shows excellent stability and activity in the process of polymerization and copolymerization of olefin.
Wherein R is1、R3、R4And R6Independently of one another are hydrogen, C1-C6Alkyl, halogen or halogeno C1-C6An alkyl group; r2And R5Independently of one another are hydrogen, C1-C6Alkyl, halogen, halogeno C1-C6Alkyl, nitro, C1-C6Alkoxy, N-di (C)1-C6Alkyl) amino or trifluoromethyl; and R is7And R8Independently of one another are hydrogen, C1-C6Alkyl, halogen, halogeno C1-C6Alkyl, nitro, C1-C6Alkoxy, N-di (C)1-C6Alkyl) amino or trifluoromethyl.
Preferably, R1、R3、R4And R6Is H and R2And R5Independently of one another, methyl, and R7And R8Independently of one another, phenyl, p-tolyl, p-tert-butylphenyl or 2-naphthyl。
The present inventors have intensively studied to find that a target ligand can be obtained in high yield by employing different temperatures of two stages in the reaction process, in which a diketone compound such as acenaphthoquinone is first reacted with the above amine compounds of formulae B and C and the compound of formula D in an organic acid solvent such as acetic acid in a low temperature stage (60 to 90 ℃, e.g., 80 ℃), to form an intermediate compound of formula E; followed by hydrolysis reaction with an aqueous solution of a weak acid salt such as potassium oxalate, sodium oxalate, potassium acetate, sodium acetate, potassium carbonate, sodium carbonate, etc. in an organic polar solvent at room temperature stage (30 ℃ C. when toluene is used, for example).
Specifically, in one embodiment, the present invention provides a process for preparing a compound of formula (I), comprising:
reacting the diketone compound of formula a, the amine compound of formulae B and C, and the zinc halide D in an organic acid solvent, such as acetic acid, at 60-90 ℃, such as 80 ℃, for 0.5-6h, such as 1h, in an organic acid solvent, such as acetic acid, to form the compound of formula E;
the solid product E is then reacted in an organic polar solvent such as dichloromethane with an aqueous solution of a weak acid salt such as potassium oxalate at room temperature, e.g. 30 ℃ for 0.2 to 5h, preferably 0.5h, to form the compound of formula (I),
wherein R is1、R2、R3、R4、R5、R6、R7And R8Is as defined above, and each X is independently a halogen, such as chlorine, bromine, or iodine.
For this reaction, if the formula (B) and the formula (C) as the starting materials are the same amine compound in structure (i.e., R)1、R2、R3And R4、R5、R6Are respectively the sameSubstituents), then during the reaction, one equivalent of a diketone such as acenaphthenequinone and two equivalents of an amine compound, and an equivalent of a zinc halide (e.g., zinc chloride) are mixed in a reaction vessel such as a bottle shaped like a eggplant, heated at a temperature of, for example, 80 ℃ for a reaction of, for example, 0.5 hour, cooled and filtered, washed with, for example, ethyl ether five times and dried; the resulting solid is then dissolved in an organic solvent such as dichloromethane, and an appropriate amount of a weak acid salt such as an aqueous solution of sodium oxalate is added and reacted at, for example, 30 ℃ for, for example, 0.5 hour. And if the formula (B) and the formula (C) as the starting materials are amine compounds different in structure (i.e., R)1、R2、R3And R4、R5、R6Respectively, are not completely the same substituent), one equivalent of acenaphthenequinone and one equivalent of one of the amine compounds (e.g., the amine compound of formula (B), and an equivalent of zinc halide (e.g., zinc chloride) are first mixed in a bottle shaped like a eggplant, and heated at a low temperature, e.g., 80℃, for a reaction, e.g., 0.5 hour, after which the other amine compound (e.g., the amine compound of formula (C)) is added and heated at a low temperature, e.g., 80℃, for a reaction, e.g., 0.5 hour, cooled, filtered, washed with ether five times and dried. Then, the obtained solid was dissolved in methylene chloride, and an appropriate amount of potassium oxalate solution was added to react at 30 ℃ for 0.5 hour. Extracting, spin-drying and drying. The yields of the various ligands of the invention were all above 75% by calculation.
Another aspect of the invention relates to unsymmetrically sterically hindered diimine complexes of formula (II) (i.e., the nickel catalysts of this invention),
wherein R is1、R2、R3、R4、R5、R6、R7And R8Is as defined above; herein, Ph represents an aryl group; and each X is independently halogen, preferably X is independently chlorine or bromine.
In the present invention, the method for synthesizing the asymmetric diimine complex comprises:
the ligand compound of formula (I) above is reacted with a compound of formula DME in an organic solvent such as dichloromethaneNiX2Wherein DME represents glyme and X is as defined above.
Preferably, the palladium precursor compound is dmeenicl2Or DMENiBr2。
In addition, the invention also relates to the application of the nickel catalyst, which is used for catalyzing the polymerization reaction of low-carbon olefin such as ethylene and propylene or the copolymerization reaction of low-carbon olefin such as ethylene and methyl undecylenate, and the catalyst shows higher stability and activity.
Preferably, the lower olefin is C2～4Olefins, including but not limited to ethylene, propylene, butylene, or any combination thereof. Preferably, the lower olefin is ethylene or propylene. In addition, the lower olefins herein may also be C6-12Aryl substituted lower olefins as described above.
The high molecular polymer or copolymer obtained by the above method has an appropriate degree of branching; specifically, in this context, the degree of branching refers to the number of branched methyl groups corresponding to 1000 carbons in the polymer or copolymer being 50 to 250 and 60 to 250, respectively.
Preferably, a cocatalyst, such as MAO (methylaluminoxane), is also present in the catalytic reaction, preferably at a temperature of 20-80 ℃. Preferably, in the above catalytic reaction, the pressure of ethylene is 1 to 10 atmospheres and the pressure of propylene is 1 to 5 atmospheres.
In another preferred embodiment, the reaction solvent is dichloromethane, toluene, chlorobenzene or a combination thereof, it is understood that within the scope of the present invention, the above-mentioned features of the present invention and the features specifically described below (e.g., in the examples) can be combined with each other to form new or preferred embodiments. For reasons of space, they will not be described in detail.
Examples
The following examples illustrate the details of the invention and the data presented include the synthesis of ligands, the synthesis of metal compounds, olefin polymerization or copolymerization processes wherein the synthesis of the complex, the polymerization process is carried out in the absence of water and oxygen, all sensitive materials are stored in a glove box, all solvents are rigorously dried to remove water, olefin gas is purified by a water and oxygen removal column, and methyl undecylenate is purified by water and oxygen removal vacuum distillation. All the raw materials were purchased and used without specific mention.
The silica gel column separation uses 200-mesh and 300-mesh silica gel, and the nuclear magnetism detection uses a Bruker400MHz nuclear magnetism instrument. The elemental analysis was determined by the chemical and physical center of the university of science and technology in China. Molecular weight and molecular weight distribution were determined by high temperature GPC. Mass spectrometry was performed using ThermoLTQ Orbitrap XL (ESI)+) Or P-SIMS-Gly of Bruker Daltonics Inc (EI)+) The single crystal X-ray Diffraction analysis adopts an Oxford Diffraction Gemini S Ultra CCD single crystal Diffraction instrument, Cu K α
And (5) irradiating at room temperature. The reagent raw materials used in the examples were purchased from Aldrich (analytical grade) unless otherwise specified, and were used as they were without treatment if not otherwise specified.
Methylene chloride (AR, dichloromethane), beijing chemical plant,
after molecular sieve pre-drying, in N2Adding calcium hydride for reflux under protection, and evaporating before use;
toluene (AR, tolumene), beijing chemical plant,
after molecular sieve pre-drying, in N2Adding metal sodium under protection for reflux, and steaming out before use;
zinc chloride (zinc chloride), beijing chemical plant, used directly;
cyclohexane (AR, cyclohexane), Beijing chemical plant,
after molecular sieve pre-drying, in N2Adding metal sodium under protection for reflux, and steaming out before use;
o-dichlorobenzene (AR, o-dichlorobenzene), Beijing chemical plant,
adding calcium hydride for reflux after the molecular sieve is pre-dried under the protection of N2, and steaming out before use;
acetic acid (formic acid), AR (88%), beijing chemical plant, used directly;
ethylene (ethylene), polymer grade, used as is, untreated;
propylene (propene), polymer grade, used as received
High purity N2(high-purity reagent) used without treatment;
ethanol (ethanol), analytically pure, Tianjin reagent II factory, directly used;
methanol (methanol), industrial products, Tianjin reagent, etc., directly used;
hydrochloric acid-methanol solution (hydrochloric acid-methanol solution), 2%, self-prepared;
all solvents were analytically pure reagents and were used without treatment.
Example 1: synthesis of N, N-di [ (2-benzhydryl-4-methyl-6-phenyl) phenyl ] acenaphthenequinonyl-2, 3-diimine
To a eggplant-shaped bottle (equipped with a thermometer, a reflux condenser and a stirrer) containing 50ml of acetic acid were added 0.7 g of 2-benzhydryl-4-methyl-6-phenylaniline, 0.18 g of acenaphthenequinone and 140 mg of zinc chloride at room temperature, and the mixture was heated to 80 ℃ by an oil bath and reacted for 0.5 hour. Then, it was cooled, filtered, washed with ether five times, and dried. Then, all solids were dissolved in 20 ml of dichloromethane, 5 ml of saturated aqueous potassium oxalate solution was added, and the mixture was rapidly stirred at 30 ℃ for 0.5 hour, then extracted three times with 10 ml of dichloromethane, dried over magnesium sulfate, filtered, and the solution was spin-dried with a rotary evaporator to obtain the solid, which was washed three times with 20 ml of methanol and dried in vacuo to obtain 0.7 g of a solid with a yield of 83%.
1H NMR(400MHz,CDCl3) δ 7.62(d, J ═ 7.7Hz,4H, aryl-H), 7.36(d, J ═ 8.2Hz,2H, aryl-H), 7.29(d, J ═ 7.2Hz,2H, aryl-H), 7.25(s,1H, aryl-H), 7.24-7.18 (m,2H, aryl-H), 7.12(d, J ═ 10.2Hz,6H, aryl-H), 7.08(d, J ═ 6.2Hz,3H, aryl-H), 6.97-6.83 (m,6H, aryl-H), 6.22-6.02 (m,6H, aryl-H), 5.95-5.75 (m,6H, aryl-H), 5.46(s,2H, CHPh), CHPh2),2.38(s,1H,CH3).13C NMR(101MHz,CDCl3)δ162.69(s,N＝C),145.57(s),143.99(s),140.71(s),140.33(s),139.94(s),133.65(s),133.27(s),131.34(s),129.76(s),129.70(s),129.57(s),129.47(s),129.45(s),129.29(s),129.17(s),128.10(s),127.94(s),127.47(s),127.09(s),127.05(s),126.63(s),125.84(s),124.71(s),122.58(s),51.78(s,CHPh2),21.27(s,CH3,CH3) HRMS (m/z) calculation of C64H49N2845.3896, found to be 845.3890[ M + H ]]+。
Example 2: synthesis of N, N-bis [ (2-benzhydryl-4-methyl-6-p-tolyl) phenyl ] acenaphthenequinonyl-2, 3-diimine
Similarly to example 1, 0.72 g of 2-benzhydryl-4-methyl-6-p-tolylaniline, 0.18 g of acenaphthenequinone, and 140 mg of zinc chloride were added to a eggplant-shaped bottle (equipped with a thermometer, a reflux condenser, and a stirrer) containing 50ml of acetic acid at room temperature, and the mixture was heated to 80 ℃ by an oil bath and reacted for 0.5 hour. Then, it was cooled, filtered, washed with ether five times, and dried. Then, all solids were dissolved in 20 ml dichloromethane, 5 ml saturated aqueous sodium oxalate solution was added, and rapid stirring was carried out at 30 ℃ for 0.5 hour, followed by extraction three times with 10 ml dichloromethane, drying over magnesium sulfate, filtration, and spin-drying of the solution to obtain the solid, which was washed three times with 20 ml methanol and dried under vacuum to obtain 0.72 g solid with a yield of 83%.
1H NMR(400MHz,CDCl3) δ 7.51(d, J ═ 8.0Hz,4H, aryl-H), 7.35(d, J ═ 8.2Hz,2H, aryl-H), 7.29(d, J ═ 7.2Hz,3H, aryl-H), 7.24-7.16 (m,2H, aryl-H), 7.12(d, J ═ 7.5Hz,3H, aryl-H), 7.07(s,2H, aryl-H), 6.92(d, J ═ 8.2Hz, 4H, aryl-H), 7.35(d, J ═ 8.2Hz,2H, aryl-H), 7.6.16 (d, J ═ 7.5Hz6.8Hz,4H, aryl-H), 6.90-6.84 (m,2H, aryl-H), 6.12(d, J ═ 7.1Hz,4H, aryl-H), 6.07(d, J ═ 7.1Hz,2H, aryl-H), 5.90(dq, J ═ 14.1,6.9Hz,5H, aryl-H), 5.48(s,2H, CHPh2),2.38(s,6H,CH3),1.81(s,6H,CH3).13C NMR(101MHz,CDCl3)δ162.50(s,N＝C),145.70(s),144.14(s),140.85(s),139.86(s),137.30(s),136.70(s),133.67(s),133.18(s),131.33(s),129.55(s),129.50(s),129.36(s),129.20(s),128.78(s),127.90(s),127.36(s),126.98(s),126.60(s),125.80(s),124.73(s),122.53(s),51.72(s,CHPh2),21.28(s,CH3),20.71(s,CH3) HRMS (m/z) calculation of C66H53N2873.4209, found to be 873.4202[ M + H ]]+。
Example 3: synthesis of N, N-di [ (2-benzhydryl-4-methyl-6-p-tert-butylphenyl) phenyl ] acenaphthenequinone-2, 3-diimine
Similarly to example 1, to a eggplant-shaped bottle (equipped with a thermometer, a reflux condenser and a stirrer) containing 50ml of acetic acid were added 0.81 g of 2-benzhydryl-4-methyl-6-p-tert-butylphenylaniline, 0.18 g of acenaphthenequinone and 140 mg of zinc chloride at room temperature, and the mixture was heated to 80 ℃ by an oil bath and reacted for 0.5 hour. Then, it was cooled, filtered, washed with ether five times, and dried. Then, all solids were dissolved in 20 ml dichloromethane, 5 ml saturated aqueous potassium oxalate solution was added, and rapid stirring was carried out at 30 ℃ for 0.5 hour, followed by extraction three times with 10 ml dichloromethane, drying over magnesium sulfate, filtration, and spin-drying of the solution to obtain the solid, which was washed three times with 20 ml methanol and dried under vacuum to obtain 0.75 g solid with a yield of 78%.
1H NMR(400MHz,CDCl3) δ 7.63(d, J ═ 8.5Hz,4H, aryl-H), 7.32(d, J ═ 8.1Hz,3H, aryl-H), 7.25-7.14 (m,9H, aryl-H), 7.09(d, J ═ 7.5Hz,6H, aryl-H), 6.88(t, J ═ 7.7Hz,4H, aryl-H), 6.12(d, J ═ 7.1Hz,2H, aryl-H), 6.06-5.97 (m,3H, aryl-H), 5.75(d, J ═ 3.5Hz,5H, aryl-H), 5.46(s,2H, CHPh), CHPh2),2.37(s,6H,CH3),0.78(s,18H,C(CH3)3).13C NMR(101MHz,CDCl3)δ162.45(s,N＝C),149.70(s),145.57(s),143.71(s),140.46(s),137.35(s),133.56(s),133.03(s),131.35(s),129.74(s),129.56(s),129.23(s),129.04(s),127.88(s),127.22(s),127.06(s),126.52(s),125.76(s),125.13(s),124.45(s),122.45(s),52.02(s,CHPh2),34.06(s,C(CH3)3),30.86(s,C(CH3)3),21.27(s,CH3) HRMS (m/z) calculation of C72H65N2957.5148, found to be 957.5142[ M + H ]]+。
Example 4: nickel complex (A)PhN^N)NiBr2Synthesis of (2)
To a flask (equipped with a stirrer) containing 20 ml of dichloromethane was added 844.7 mg of the aryl ligand prepared in example 1 (i.e., N-bis [ (2-benzhydryl-4-methyl-6-phenyl) phenyl ] at room temperature]Acenaphthenequinone alkyl-2, 3-diimine), and 305.5 mg of DMENiBr was added2. After stirring at room temperature for 1 day, the solution turned turbid from clear, and a red precipitate appeared. Filtration under reduced pressure and vacuum drying gave an orange solid in 54% yield. FIG. 1 shows a single crystal structure schematic of a bulky hindered diamine ligand palladium catalyst prepared in an example of the present invention.
Elemental analysis, theoretical calculation: c64H48Br2N2Ni C, 72.27; h, 4.55; n, 2.63; actually measuring C, 72.21; h, 4.59; and N, 2.28. Mass Spectrometry MALDI-TOF-MS (m/z): theory C64H48BrN2981.2354, found 981.2040[ M-Br ]]+。
Example 5: nickel complex (A)TolN^N)NiBr2Synthesis of (2)
Analogously to example 4, a flask (equipped with stirrer) containing 20 ml of dichloromethane was charged at room temperature873.2 mg of the aryl ligand prepared in example 2 (i.e., N-bis [ (2-benzhydryl-4-methyl-6-p-tolyl) phenyl)]Acenaphthenequinone alkyl-2, 3-diimine), and 305.5 mg of DMENiBr was added2. After stirring at room temperature for 1 day, the solution turned turbid from clear, and a red precipitate appeared. Filtration under reduced pressure and vacuum drying gave an orange solid in 64% yield.
Elemental analysis, theoretical calculation: c66H52Br2N2Ni is C, 72.62; h, 4.80; n, 2.57; actually measuring C, 72.41; h, 4.69; and N, 2.18. Mass Spectrometry MALDI-TOF-MS (m/z) calculation of C66H52BrN21009.2667, found 1009.2381[ M-Br ]]+。
Example 6: nickel complex (A)TBuN^N)NiBr2Synthesis of (2)
In analogy to example 4, in a flask (equipped with stirrer) containing 20 ml of dichloromethane was added 956.2 mg of the aryl ligand prepared in example 2 (i.e. N, N-bis [ (2-benzhydryl-4-methyl-6-p-tolyl) phenyl group) at room temperature]Acenaphthenequinone alkyl-2, 3-diimine), and 305.5 mg of DMENiBr was added2. After stirring at room temperature for 1 day, the solution turned turbid from clear, and a red precipitate appeared. Filtration under reduced pressure and vacuum drying gave an orange solid in 66% yield.
Elemental analysis, theoretical calculation: c72H64Br2N2Ni C, 73.55; h, 5.49; n, 2.38; actually measuring C, 73.21; h, 4.98; and N, 2.42. Mass Spectrometry MALDI-TOF-MS (m/z): theory C72H64BrN21093.3606, found 1093.3084[ M-Br ]]+。
Example 7: use of catalysts for ethylene polymerization
In a glove box, 48mL of toluene and 35mg of methylaluminoxane were added under a nitrogen atmosphere to a 350mL autoclave (with magnetic stirring, oil bath heating, and thermometer). Then, vacuum was applied by freezing with liquid nitrogen, ethylene was charged three times to and fro, the reaction temperature was adjusted to 30 ℃, and a solution of 1mg of the palladium catalyst prepared in example 4 dissolved in 2ml of dichloromethane was injected thereto. After the valve was closed and the ethylene pressure was adjusted to 9 atm, the reaction was carried out for 30 minutes. The reaction was stopped, the reactor was opened, 5% by volume of methanol hydrochloride solution was added thereto to terminate the polymerization, the polymer was spin-dried and washed three times with pure methanol, and dried at 50 ℃ to obtain 4.4 g of a semi-crystalline polyethylene having a number of methyl groups corresponding to 1000 methylene groups of 60 and a molecular weight of 57800 g/mol.
Figure 2 shows the nmr hydrogen spectrum of a polyethylene polymer prepared according to an example of the invention. It can be seen therein that the resulting polyethylene has a suitable degree of branching.
Example 8: application of catalyzing copolymerization of propylene and methyl undecylenate
In a glove box, 48mL of toluene, 175mg of methylaluminoxane and 0.2mL of methyl undecylenate were added to a 350mL autoclave (with magnetic stirring, oil bath heating and thermometer) under nitrogen. Then, vacuum was applied by freezing with liquid nitrogen, propylene was charged three times, the reaction temperature was adjusted to 30 ℃ and a solution of 5.9mg of the palladium catalyst prepared in example 6 dissolved in 2ml of dichloromethane was injected thereto. After the valve was closed and the propylene pressure was adjusted to 6 atm, the reaction was carried out for 120 minutes. The reaction was stopped, the reaction vessel was opened, 5% (by volume) methanol hydrochloride solution was added thereto to terminate the polymerization, and the polymer was spin-dried, washed three times with pure methanol, and dried at 50 ℃ to obtain 0.4 g of a semicrystalline polypropylene copolymer having a number of methyl groups corresponding to 1000 methylene groups of 154 and a molecular weight of 110000 g/mol. FIG. 3 shows a NMR spectrum of a copolymer of propylene and methyl undecylenate prepared according to an example of the present invention.
In addition, the following table 1 shows the polymerization effects of different electron effect catalysts prepared in the examples of the present invention at different temperatures.
Table 1: effect of temperature on ethylene polymerizationa。
aConditions are as follows: 1 micromole of catalyst, 600 equivalents of methylaluminoxane, 2 milliliters of dichloromethane, 48 milliliters of toluene and 9 atmospheric ethylene react for 0.5 hour;
bactivity: 106Grams per mole of catalyst per hour;
cPDI: molecular weight (M)n) And the distribution thereof, determined by GPC in trichlorobenzene as solvent at 150 ℃ using polystyrene as standard;
db ═ number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectroscopy.
From table 1, it can be seen that the catalysts prepared in examples 4, 5 and 6 of the present invention all catalytically produced polyethylene at high pressure with high activity, particularly the catalyst prepared in example 4 reached the highest activity at 30 degrees, and the catalyst prepared in example 6 reached the highest activity at 70 degrees (the conventional catalyst deactivated at this temperature); meanwhile, compared with the conventional catalyst, the catalyst prepared in the embodiments 4, 5 and 6 of the invention can be polymerized to obtain a high molecular polymer with a large molecular weight and a proper branching degree.
TABLE 2 polymerization and copolymerization of propylene with different steric effect catalystsa。
aPolymerization conditions: total volume of toluene and methyl undecylenate: 43 ml, 5. mu. mol catalyst.
bThe activity unit is 103Grams per mole of catalyst per hour.
cPDI: molecular weight (M)n) And their distribution, determined by GPC using universal calibration.
d(XUA): the insertion ratio of the polar monomer was measured by nuclear magnetic resonance spectroscopy.
eB ═ number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectroscopy.
fMethyl undecylenate concentration: the concentration of experiment 4 was 0.02 mol per liter and the concentration of experiment 5 was 0.04 mol per liter.
-: indicating that no detection was performed.
It can be seen from table 2 that the catalysts prepared in examples 4, 5 and 6 of the present invention all catalytically produced polypropylene at a pressure with a higher activity, and the catalyst prepared in example 6 reached 0.8% when the concentration of methyl undecylenate reached 0.04 mol/l.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. A compound of formula (I):
wherein R is1、R3、R4And R6Independently of one another are hydrogen, C1-C6Alkyl, halogen or halogeno C1-C6An alkyl group; r2And R5Independently of one another are hydrogen, C1-C6Alkyl, halogen, halogeno C1-C6Alkyl, nitro, C1-C6Alkoxy, N-di (C)1-C6Alkyl) amino or trifluoromethyl; and R is7And R8Independently of one another are hydrogen, C1-C6Alkyl, halogen, halogeno C1-C6Alkyl, nitro, C1-C6Alkoxy, N-di (C)1-C6Alkyl) amino or trifluoromethyl.
2. A process for the preparation of a compound of formula (I) as claimed in claim 1, which process comprises:
reacting a diketone compound of formula a with an amine compound of formula B and C and a zinc halide of formula D in an organic acid solvent at 60-120 ℃ for 0.5-6h to form a compound of formula E;
then reacting the compound of formula E with an aqueous solution of a weak acid salt in an organic polar solvent for 0.2-5h at room temperature to form the compound of formula (I),
wherein R is1、R2、R3、R4、R5、R6、R7And R8As defined in claim 1, and each X is independently halogen.
3. The method according to claim 2, wherein the organic acid is formic acid, acetic acid, propionic acid or a mixture thereof, and the organic polar solvent is dichloromethane, chloroform, chlorobenzene, dichloroethane or a mixture thereof.
4. A complex of formula (II):
wherein R is1、R2、R3、R4、R5、R6、R7And R8As defined in claim 1, Ph represents phenyl and each X is independently halogen.
5. A process for preparing a complex of formula (II),
the method comprises the following steps:
reacting a compound of formula (I) according to claim 1 with a compound of formula DMENiX in an organic solvent at ambient temperature2The nickel precursor compound of (a) is reacted,
wherein DME represents ethylene glycol dimethyl ether, and R1、R2、R3、R4、R5、R6、R7、R8And X is as defined in claim 4.
6. The method of claim 5, wherein each X is independently Cl or Br.
7. A method of preparing a polyolefin compound, the method comprising:
catalytic polymerization of lower olefins using the complex of formula (II) according to claim 4 as catalyst, wherein the lower olefin is C2-4An olefin.
8. A process for preparing a copolymer of a lower olefin and methyl undecylenate, the process comprising:
catalytic polymerization of lower olefins with methyl undecylenate using the complex of formula (II) according to claim 4 as catalyst, wherein the lower olefin is C2-4An olefin.
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