CN109134302A - A kind of acenaphthene annulus has the application of the alpha-diimine and its derivative complex of hydroxyl in olefin polymerization - Google Patents
A kind of acenaphthene annulus has the application of the alpha-diimine and its derivative complex of hydroxyl in olefin polymerization Download PDFInfo
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- CN109134302A CN109134302A CN201811155533.1A CN201811155533A CN109134302A CN 109134302 A CN109134302 A CN 109134302A CN 201811155533 A CN201811155533 A CN 201811155533A CN 109134302 A CN109134302 A CN 109134302A
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- China
- Prior art keywords
- alpha
- diimine
- compound
- hydroxyl
- catalyst
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- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 75
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 32
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 22
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- -1 heterocyclic arene Chemical class 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 229940126062 Compound A Drugs 0.000 claims description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 3
- 238000012685 gas phase polymerization Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 2
- OCMNCWNTDDVHFK-UHFFFAOYSA-L dichloronickel;1,2-dimethoxyethane Chemical compound Cl[Ni]Cl.COCCOC OCMNCWNTDDVHFK-UHFFFAOYSA-L 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 2
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 230000037048 polymerization activity Effects 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000003426 co-catalyst Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- JBKFJFKSHGAYQG-UHFFFAOYSA-N OCC1=CC=C(C=C1)C1=CC=C2C(C(C=3C=CC=C1C32)=O)=O Chemical compound OCC1=CC=C(C=C1)C1=CC=C2C(C(C=3C=CC=C1C32)=O)=O JBKFJFKSHGAYQG-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- PHPQHHFMRUWUJG-UHFFFAOYSA-N 5-bromoacenaphthylene-1,2-dione Chemical compound C1=CC=C2C(Br)=CC=C3C(=O)C(=O)C1=C23 PHPQHHFMRUWUJG-UHFFFAOYSA-N 0.000 description 2
- XFZZDIHCNHYESF-UHFFFAOYSA-N 7-amino-1-bromo-4-phenyl-5,7,8,9-tetrahydrobenzo[7]annulen-6-one Chemical compound C=12CC(=O)C(N)CCC2=C(Br)C=CC=1C1=CC=CC=C1 XFZZDIHCNHYESF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- RAAMBBFGXIAMCU-UHFFFAOYSA-N OC1=CC=C(C=C1)C1=CC=C2C(C(C=3C=CC=C1C32)=O)=O Chemical compound OC1=CC=C(C=C1)C1=CC=C2C(C(C=3C=CC=C1C32)=O)=O RAAMBBFGXIAMCU-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000002466 imines Chemical group 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- RUVLYCMXZGNXPP-UHFFFAOYSA-N 3,4-dibromoacenaphthylene-1,2-dione Chemical compound C1=CC(C(C2=O)=O)=C3C2=C(Br)C(Br)=CC3=C1 RUVLYCMXZGNXPP-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- AOTASNMSEOHVJJ-UHFFFAOYSA-N CNC1=CC=CC=C1.FC1=CC=CC=C1 Chemical compound CNC1=CC=CC=C1.FC1=CC=CC=C1 AOTASNMSEOHVJJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- LHJCYYZDVRHRBR-UHFFFAOYSA-N [4-(hydroxymethyl)phenoxy]boronic acid Chemical compound OCC1=CC=C(OB(O)O)C=C1 LHJCYYZDVRHRBR-UHFFFAOYSA-N 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 241001477622 annulus group Species 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004674 formic acids Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
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- 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
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- 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
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- 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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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract
The present invention is that a kind of acenaphthene annulus has the application of the alpha-diimine and its derivative complex of hydroxyl in olefin polymerization.The acenaphthene annulus has the structural formula such as following formula I of the alpha-diimine of hydroxyl.Hydroxyl is had on the alpha-diimine ligand, alpha-diimine complex based on them can be copolymerized with catalyzed alkene homopolymerization, such as catalysis ethylene homo, norbornene homopolymerization, ethylene and norbornene copolymerization can be more importantly catalyzed, this is advantage not available for not hydroxyl alpha-diimine catalyst, is conducive to such rear transition catalyst in the application range of olefinic polymerization.Compared with the alpha-diimine catalyst thermal stability difference of classical Brookhart, for alpha-diimine complex of the only aniline with isopropyl that the present invention designs when polymerization temperature is at 80 DEG C, polymerization activity still can achieve 106G/molh or more, higher heat resistance are conducive to industrial applications.
Description
Technical field
The present invention relates to olefin catalytic field, specially a kind of acenaphthene annulus has the alpha-diimine and its derivative complex of hydroxyl
Application in olefin polymerization.
Background technique
As a kind of new olefine polymerization to grow up after traditional Ziegler-Natta and metallocene catalyst
Catalyst, the easy preparation of late transition metal catalyst of alpha-diimine nickel, palladium, Er Qieneng relatively low to the sensitivity of water oxygen
Enough catalysis only monomers prepare highly -branched or dissaving structure polymer, can be realized and are copolymerized with catalyzed alkene and polar monomer.
Therefore, their appearance causes the attention of many research groups immediately.Guan etc. (Angew.Chem.Int.Ed., 2004,43
(14),1821；Chem.Commun., 2010,46 (42), 7879) report has synthesized a series of cyclophane skeleton structures
Alpha-diimine palladium catalyst, relative to the such catalyst reported in the past, they are showed in addition to good heat resistance.Wu Qing etc.
(Macromolecules, 2009,42 (20), 7789) also design has synthesized the different alpha-diimine nickel catalysis of a variety of skeleton structures
Agent shows that the biggish catalyst activity of carbon skeleton steric hindrance is higher, reaches 106G PE/molNih, and in 80 DEG C of also tables
Reveal preferable catalytic activity.And what Long seminar (ACS Catal.2014,4,2501-2504) design synthesized contains big position
The alpha-diimine Raney nickel of benzhydril substituent is hindered, or even very high activity can be kept when temperature reaches 90 DEG C, is opened up
Excellent thermal stability is shown.Although it is equal ethylene can be catalyzed in addition, alpha-diimine nickel catalysis ethylene is that have activity well
It is poly-, norbornene homopolymerization, but there are no the document report of catalysis ethylene and norbornene copolymerization.Experiment discovery, has been reported
Alpha-diimine Raney nickel do not have catalysis ethylene and norbornene copolymerized ability.Currently, sold in the market based on second
Alkene and addition polymer-cyclic olefine copolymer (COC) of norbornene are mainly to be prepared by metallocene catalysis, this is
Weakness one of of the alpha-diimine Raney nickel relative to metallocene catalyst.
Summary of the invention
The purpose of the present invention is to provide alpha-diimines and its derivative complex that a kind of acenaphthene annulus has hydroxyl.The α-two is sub-
Hydroxyl is had on the acenaphthene ring of amine, the presence of hydroxyl enables alpha-diimine complex and co-catalyst based on them to act on, point
Ion pair from activated centre, can be improved catalytic activity and thermal stability.
The technical scheme adopted by the invention is that:
A kind of acenaphthene annulus has the alpha-diimine compound of hydroxyl, it is characterized in that the alpha-diimine structural formula of compound
Are as follows:
Wherein, R is substituted base or unsubstituted C6-C60Aryl, C6-C60One of heterocyclic arene base；Ar
To have the following structure one of group:
Wherein, n=1,2,3,4,5,6 or 7；R' is C1-C20Alkyl.
The acenaphthene annulus has the preparation method of the alpha-diimine compound of hydroxyl, it is characterized in that acenaphthene ring shown in formula I
The preparation method of alpha-diimine compound with hydroxyl, comprising the following steps:
At 40-120 DEG C, by the alpha-diimine as shown in compound A, as shown in compound B have hydroxyl fragrance
Boron compound, inorganic carbonate, palladium catalyst react 1-48 hours in the mixture of organic solvent and water, are made such as Formulas I institute
The alpha-diimine compound with hydroxyl shown；
Wherein, the alpha-diimine as shown in compound A with such as compound B shown in have hydroxyl fragrant boron compound
Molar ratio is 1:1-1:2, and the molar ratio of the alpha-diimine as shown in compound A and inorganic carbonate is 1:2-1:5, such as compound
The molar ratio of alpha-diimine and palladium catalyst shown in A is 1:0.001-1:0.5；The palladium catalyst is four (triphenyl phosphorus)
Palladium or bis- (dibenzalacetone) palladiums.Inorganic carbonate is potassium carbonate, sodium carbonate or cesium carbonate.
The compound A is as follows:
Wherein, R is substituted base or unsubstituted C6-C60Aryl, C6-C60One of heterocyclic arene base；
The compound B is as follows:
Wherein, R " is hydrogen or C1-C15Alkyl or two R " be connected and constitute naphthenic base.Ar is to have the following structure base
One of group:
Wherein, n=1,2,3,4,5,6 or 7；R' is C1-C20Alkyl.
The preparation method of the alpha-diimine as shown in compound A, it is characterized in that described as shown in compound A
The preparation method of alpha-diimine, comprising the following steps:
At 40-120 DEG C, by 5- bromine band acenaphthenequinone, R-NH2It is small that 1-48 is reacted in organic solvent with catalyst organic acid
When, the alpha-diimine compound with hydroxyl shown in formula I is made；
Wherein, 5- bromine band acenaphthenequinone and R-NH2Molar ratio be 1:2-1:4,5- bromine rubs with acenaphthenequinone and organic acid catalyst
You are than being 1:0.001-1:0.5；The organic acid catalyst is formic acid, acetic acid, p-methyl benzenesulfonic acid or camphorsulfonic acid；It is described
Organic solvent be methylene chloride, chloroform, 1,2- dichloroethanes, tetrahydrofuran, 1,4- dioxane, benzene, toluene, chlorobenzene or
Their mixture；Compound R-the NH2Middle R is substituted base or unsubstituted C6-C60Aryl, C6-C60It is miscellaneous
One of cyclophane alkyl.
A kind of alpha-diimine metal complex, it is characterized in that the metal complex is had the α-two of hydroxyl by the acenaphthene annulus
Group with imine moiety and late transition metal reactant salt are made, wherein the late transition metal salt is nickel salt, palladium salt, platinum salt, molysite
Or cobalt salt；
The preparation method of the alpha-diimine metal complex, it is characterized in that the following steps are included: in a nitrogen atmosphere
Reactor in, the late transition metal salt is added to the alpha-diimine compound solution that the acenaphthene annulus has hydroxyl
Reaction in (concentration 0.01-0.1mmol/mL), wherein late transition metal salt and alpha-diimine compound equimolar amounts；Room temperature
Under be stirred to react 1-48 hours, be concentrated under reduced pressure reaction solution to 1st/1/10th to 50 of original solution volume, add dense
Ten times of contracting liquid product precipitate to fiftyfold precipitating reagent, filter, after solid is washed with precipitating reagent, vacuum drying obtains alpha-diimine
Metal complex；
Wherein, the solvent in the alpha-diimine compound solution is C1-C20Chloralkane, C1-C20Chloro virtue
Fragrant hydrocarbon, C1-C20Aromatic hydrocarbon or C1-C20One of oxygen-containing alkane or a variety of mixed solvents；The precipitating reagent is C5-C20
Alkane or C5-C20One of cycloalkane or a variety of mixtures.
The preparation method of the alpha-diimine metal complex, it is characterized in that the solution of the alpha-diimine compound
Middle solvent is methylene chloride, chloroform, 1,2- dichloroethanes, chlorobenzene, dichloro-benzenes, toluene, tetrahydrofuran and 1,4- dioxy six
One of ring or a variety of mixed solvents；
The precipitating reagent is one of pentane, n-hexane, normal heptane, normal octane and hexamethylene or a variety of mixing
Object；
The late transition metal salt is preferably (DME) NiBr2、(DME)NiCl2、(COD)PdClCH3、(PhCN)2PdCl2
Or (COD) PdMe (NCMe).
A kind of application of alpha-diimine metal complex, it is characterized in that the alpha-diimine metal complex is as main reminder
Agent is applied to the polymerisation in solution of the liquid-phase bulk polymerization or olefinic monomer of the gas-phase polymerization or olefinic monomer of ethylene or propylene
In.
The application of the alpha-diimine metal complex, it is characterized in that the alpha-diimine metal complex is as master
Catalyst is applied in olefin polymerization, including following reaction condition: polymeric reaction temperature is -20-120 DEG C；Olefinic monomer is gas
Pressure is 0.1-10MPa when body；Olefinic monomer be specially ethylene, propylene, 1- butylene, 1- amylene, 4-methyl-1-pentene, 1- oneself
Alkene, 1- heptene, 1- octene, 1- decene, norbornene, vinyl norbornene, ethylidene norbornene, bicyclopentadiene, 1,
One of 4- butadiene, styrene, α-methylstyrene and divinylbenzene are a variety of.
When the olefinic monomer carries out polymerisation in solution, solvent is anhydrous toluene, dimethylbenzene, chlorobenzene, methylene chloride, two
Chloroethanes, n-hexane or normal heptane；Olefinic monomer additional amount is 0.1-10mol in every liter of solvent；Major catalyst additional amount be 1 ×
10-5-1×10-3The major catalyst solvent of mol/L, in terms of the molal quantity of major catalyst contains the molal quantity of metal by it；Co-catalysis
The molar ratio of metal is 10-4000:1 in agent and major catalyst；The co-catalyst is alkyl aluminum, alkylaluminoxane or boronation
Object, preferably AlEt2Cl、AlEtCl2、Al2Et3Cl3、Al2Me2Cl4、AlEt3、Al(i-Bu)3、MAO、EAO、MMAO、B(C6F5)4、
NaBAF or B (C6H3(CF3)2)4One of.
Beneficial effects of the present invention: alpha-diimine and its derivative complex that a kind of acenaphthene annulus has hydroxyl are provided.The α-two
Hydroxyl is had on imine ligand, the alpha-diimine complex based on them can be copolymerized with catalyzed alkene homopolymerization, such as catalysis ethylene
Homopolymerization, norbornene homopolymerization, it is often more important that ethylene and norbornene copolymerization can be catalyzed, this is not hydroxyl alpha-diimine
Advantage not available for catalyst, this advantage are conducive to expand such rear transition catalyst in the application range of olefinic polymerization.
Compared with the alpha-diimine catalyst thermal stability of classical Brookhart poor (just losing catalytic activity at 60 DEG C), such as present invention
Aniline on isopropyl alpha-diimine complex when reaction temperature is at 80 DEG C polymerization activity still can achieve 106g/
Molh or more, high temperature resistance is good, and application industrially may be implemented.It present invention can be suitably applied to existing catalyst alkene
Gas phase polymerization apparatus, ontology or the polymerisation in solution device of hydrocarbon.
Specific embodiment
The present invention is described further with reference to embodiments.It should be noted that following embodiments cannot function as pair
The limitation of the scope of the present invention, any improvement made on the basis of the present invention is all without prejudice to spirit of the invention.
One, the synthesis of alpha-diimine compound
The alpha-diimine compound can be made by following steps:
(1) compound A is made in 5- bromo acenaphthenequinone and aromatic amine reaction response；
(2) the compound A as prepared by step (1) reacts to obtain compound I with the fragrant boron compound with hydroxyl.
Reaction route is as follows:
Embodiment 1
Bis- (2,6- diisopropyl) the benzene imines I1 of 5- (4- hydroxymethyl phenyl) acenaphthenequinone are (i.e. such as the structure of Compound I, wherein Ar
=p-methylphenyl, R=(2,6- diisopropyl) phenyl) synthesis:
Its preparation route is as follows:
The synthesis of bis- (2,6- diisopropyl) the benzene imines a1 of bis- bromo acenaphthenequinone of 5-:
5- bromo acenaphthenequinone (2.09g, 8mmol) is added into the reaction flask of 250mL, 2,6-DIPA (3.36g,
19mmol) and the anhydrous methanol of 150mL, and 10 drop anhydrous formic acids, the mixture back flow reaction 48 hours are instilled.Thin layer chromatography chases after
Track reaction, until raw material fully reacting filters to obtain brown-red solid, which mentions after reaction mixture is cooling
It is pure, obtain 4.27g yellow solid a1, yield 92%.1H NMR(400MHz,CDCl3): δ 8.10 (d, J=8.4Hz, 1H),
7.61 (d, J=7.7Hz, 1H), 7.47 (t, J=7.9Hz, 1H), 7.30-7.27 (m, 6H), 6.67 (d, J=7.2Hz, 1H),
6.45 (d, J=7.7Hz, 1H), 3.07-2.91 (m, 4H), 1.23 (d, J=6.8Hz, 12H), 0.98-0.95 (m, 12H) .MS
(ESI):m/z 579(M+H).
The synthesis of bis- (2,6- diisopropyl) the benzene imines I1 of 5- (4- hydroxymethyl phenyl) acenaphthenequinone:
By compound a 1 (2.32g, 4mmol), 4- methylol phenyl boric acid (0.76g, 5mmol), tetrakis triphenylphosphine palladium
(0.46g, 0.4mmol), Anhydrous potassium carbonate (1.66g, 12mmol), 100mL toluene and 50mL water are added in two-mouth bottle, and argon gas is protected
Shield, is heated to reflux 10h.It after being cooled to room temperature, is extracted with dichloromethane, after organic phase anhydrous sodium sulfate drying, filtering is drained
Solvent obtains 2.31g yellow solid I1, yield 95% finally by column column layer chromatography separating-purifying.1H NMR(400MHz,
CDCl3): δ 7.98 (d, J=8.4Hz, 1H), 7.49 (s, 4H), 7.35-7.27 (m, 5H), 6.70-6.65 (m, 2H), 4.79
(s, 2H), 3.08-3.05 (m, 4H), 1.25 (d, J=6.6Hz, 12H), 1.02-0.98 (m, 12H) .MS (ESI): m/z 607
(M+H).
Embodiment 2
Bis- [2,4- dimethyl -6- two (4- fluorobenzene) methyl] the benzene imines I2 of 5- (4- hydroxy phenyl) acenaphthenequinone are (i.e. such as I chemical combination
The structure of object, wherein Ar=is to phenyl, R=[2,4- dimethyl -6- two (4- fluorobenzene) methyl] phenyl) synthesis:
Its preparation route is as follows:
The preparation of compound I2 is identical as compound I1 preparation process in embodiment 1, wherein using 2,4- dimethyl -6- two
(4- fluorobenzene) methylaniline replaces the 2,6-DIPA in embodiment 1, and toluene replaces the dichloromethane in embodiment 1
Alkane, p-methyl benzenesulfonic acid replace the formic acid in embodiment 1, and 4- hydroxyl benzpinacol borate replaces the 4- hydroxyl first in embodiment 1
Base phenyl boric acid, bis- (dibenzalacetone) palladiums replace the tetrakis triphenylphosphine palladium in embodiment 1, and natrium carbonicum calcinatum replaces embodiment
Anhydrous potassium carbonate in 1.The yield of compound I2 is 86%.1H NMR(400MHz,CDCl3): δ 7.76 (d, J=8.5Hz,
1H), 7.30 (d, J=8.2Hz, 2H), 7.13-6.90 (m, 14H), 6.81-6.78 (m, 4H), 6.62 (d, J=5.6Hz, 2H),
6.37-6.32 (m, 2H), 6.06-6.01 (m, 4H), 5.67 (s, 2H), 2.33 (s, 6H), 2.29 (d, J=6.0Hz, 6H) .MS
(ESI):m/z 885(M+H).
Embodiment 3
Bis- [(the benzhydryl) -4- of 2,6- bis- methoxyl group] the benzene imines I3 of 5- (4- hydroxymethyl phenyl) acenaphthenequinone are (i.e. such as Compound I
Structure, wherein Ar=p-methylphenyl, R=[2,6- bis- (benzhydryl) -4- methoxyl group] phenyl) synthesis:
Its preparation route is as follows:
The preparation of compound I3 is identical as compound I1 preparation process in embodiment 1, wherein using 2,6- benzhydryl -6-
Aminoanisole replaces the 2,6-DIPA in embodiment 1, and toluene replaces the methylene chloride in embodiment 1, to methyl
Benzene sulfonic acid replaces the formic acid in embodiment 1, and Carbon Dioxide caesium replaces the Anhydrous potassium carbonate in embodiment 1.The yield of compound I3
It is 79%.1H NMR(400MHz,CDCl3): δ 7.66 (d, J=8.4Hz, 1H), 7.57 (d, J=7.9Hz, 2H), 7.41 (d, J
=7.9Hz, 2H), 7.21-7.12 (m, 20H), 6.96-6.91 (m, 9H), 6.76-6.61 (m, 17H), 6.34 (d, J=
7.1Hz, 1H), 6.08 (d, J=7.3Hz, 1H), 5.80 (s, 2H), 5.74 (s, 2H), 4.86 (s, 2H), 3.69 (s, 3H),
3.68(s,3H).MS(ESI):m/z 1164(M+H).
Two, the synthesis of alpha-diimine metal complex
Embodiment 4
The synthesis of bis- (2,6- diisopropyl) the benzene imines nickelous bromides (NiI1) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone
Argon gas is protected and the compound I1 (0.61g, 1mmol) that embodiment 1 obtains is added into reaction flask, 1,2- dimethoxy
Ethane nickelous bromide (DME) NiBr2(0.309g, 1mmol), methylene chloride 50mL are stirred at room temperature 24 hours.Then it is concentrated under reduced pressure anti-
It answers liquid to 5mL, 50mL n-hexane is added and is settled out red brown solid.It filters, after solid is washed with n-hexane, vacuum drying is obtained
Complex NiI1 0.788g, yield: 96%.The elemental analysis of complex NiI1, C43H46Br2N2NiO theoretical value: C
62.58%, H 5.62%, N 3.39%.Experiment value: C 62.61%, H 5.59%, N 3.37%.ICP measurement, Ni
7.09%.
Embodiment 5
Bis- [2,4- dimethyl -6- two (4- fluorobenzene) methyl] the benzene imines nickelous bromides (NiI2) of 5- (4- hydroxy phenyl) acenaphthenequinone
Synthesis
Complex NiI2 is identical as complex NiI1 preparation process in embodiment 4, wherein changing using as made from embodiment 2
Object I2 is closed instead of the I1 in embodiment 4.The yield of complex NiI2 is 97%.The elemental analysis of complex NiI2,
C60H44Br2F4N2NiO theoretical value: C 65.31%, H 4.02%, N 2.54%；Experiment value: C 65.29%, H 4.03%, N
2.56%.ICP measurement, Ni 5.33%.
Embodiment 6
Bis- [(the benzhydryl) -4- of 2,6- bis- methoxyl group] the benzene imines nickelous bromides (NiI3) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone
Synthesis
Complex NiI3 is identical as complex NiI1 preparation process in embodiment 4, wherein changing using as made from embodiment 3
Object I3 is closed instead of the I1 in embodiment 4.The yield of complex NiI3 is 95%.The elemental analysis of complex NiI3,
C85H66Br2N2NiO3Theoretical value: C 73.88%, H 4.81%, N 2.03%；Experiment value: C 73.89%, H 4.79%, N
2.05%.ICP measurement, Ni 4.26%.
Embodiment 7
The synthesis of bis- (2,6- diisopropyl) the benzene imines palladium chlorides (PdI1) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone:
In a nitrogen atmosphere, ligand i 1 (0.61g, 1mmol) made from embodiment 1, (PhCN) are added into reaction flask2PdCl2(0.384g, 1mmol), methylene chloride 60mL are stirred at room temperature 24 hours.Then reaction solution is concentrated under reduced pressure to 5mL, is added
50mL n-hexane is settled out red brown solid.It filters, after solid is washed with n-hexane, vacuum drying obtains complex PdI1
0.765g, yield: 96%.The elemental analysis of complex PdI1, C43H46Cl2N2OPd theoretical value: C 65.86%, H 5.91%,
N3.57%；Experiment value: C 65.87%, H 5.90%, N 3.56%.ICP measurement, Pd 13.56%.
Embodiment 8
The synthesis of bis- (2,6- diisopropyl) the benzene imines palladium chlorides (PdI3) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone:
Complex PdI3 is identical as complex PdI1 preparation process in embodiment 7, wherein changing using as made from embodiment 3
Object I3 is closed instead of the I1 in embodiment 7.The yield of complex PdI3 is 92%.The elemental analysis of complex PdI3,
C85H66Br2N2O3Pd theoretical value: C 71.41%, H 4.65%, N 1.96%；Experiment value: C 71.89%, H 4.59%, N
1.02%.ICP measurement, Pd, 7.42%.
Three, olefin polymerization
Embodiment 9
NiI1 is as major catalyst catalyzed ethylene polymerization
It is re-filled with addition 50mL dry toluene in the 250mL reaction kettle of ethylene three times to through nitrogen displacement, is heated to 80 DEG C
And constant temperature, 5 μm of ol are separately added by the co-catalyst AlEt of 4 gained complex NiI1,1.0mol/L of embodiment2Cl 5mL, (is helped
Catalyst and major catalyst molar ratio are 1000:1), stirring, which is passed through ethylene, to be made to keep pressure 0.5MPa, polymerization time in reactor
It is 1 hour.Be added 10mL concentration expressed in percentage by volume be 10% acidic ethanol (i.e. volume ratio is 37% concentrated hydrochloric acid: dehydrated alcohol=
1:9) produced to reaction terminating with water, ethanol washing, filtered polymeric, then drying 8 hours in 60 DEG C of vacuum ovens
Object polyethylene 6.9g.The catalytic activity of NiI1 is 1.4 × 106(activity is by polymerizate quality/(in catalyst golden by g/molh
The amount of category substance × per hour) be calculated).Polymer Mw (weight average molecular weight) is 6.8 × 105G/mol, MWD (molecular weight point
Cloth) it is 1.7 (GPC is measured).13The polymer branching degree of C NMR measurement is 82/1000 carbon atom.
Embodiment 10
NiI1 is catalyzed norbornene polymerization as major catalyst
50mL dry toluene is added into the 250mL reaction kettle after nitrogen displacement three times, heats and constant temperature is to 60 DEG C, point
Not Jia Ru 3g norbornene, 5 μm of ol by the co-catalyst MAO of embodiment 4 resulting complex NiI1,1mol/L, (5mL is helped and is urged
Agent and major catalyst molar ratio are 2000:1), polymerization time is 1 hour, and it is 10% that 10mL concentration expressed in percentage by volume, which is then added,
Acidic ethanol filter out polymer to reaction terminating, and with after water, ethanol washing, then dry 8 in 60 DEG C of vacuum ovens
Hour, obtain solid polymer product 2.8g.The catalytic activity of NiI1 is 5.6 × 105g/mol·h.Polymer Mw be 3.2 ×
105G/mol, MWD 2.1.
Embodiment 11
Copolymerization of the NiI1 as major catalyst catalysis ethylene and norbornene
50mL dry toluene is added into the 250mL reaction kettle for being re-filled with ethylene after nitrogen displacement three times, heats and permanent
Temperature to 60 DEG C, be separately added into 3g norbornene, 5 μm of ol by embodiment 4 resulting complex NiI1,1mol/L co-catalyst
MAO (5mL, co-catalyst and major catalyst molar ratio are 1000:1), stirring, which is passed through ethylene, to be made to keep pressure in reactor
0.5MPa, polymerization time are 1 hour, the acidic ethanol that then addition 10mL concentration expressed in percentage by volume is 10% to reaction terminating, mistake
Filter out polymer, and with after water, ethanol washing, then in 60 DEG C of vacuum ovens it is 8 hours dry, obtain solid polymer product
2.0g.The catalytic activity of NiI1 is 4.0 × 105g/mol·h.Polymer Mw is 2.6 × 105G/mol, MWD 2.2.13C NMR
The content for measuring norbornene in polymer is 55%.
Embodiment 12
NiI2 is as major catalyst catalyzed ethylene polymerization
Vinyl polymerization condition and concrete operations are the same as embodiment 9.Wherein, n-hexane replaces the toluene in embodiment 9, main reminder
Agent replaces the NiI1 in embodiment 9 with the NiI2 prepared by embodiment 5.The catalytic activity of NiI2 is 5.8 × 105g/mol·
h.Polymer Mw is 8.2 × 105G/mol, MWD 1.3.13The polymer branching degree of C NMR measurement is 56/1000 carbon atom.
Embodiment 13
NiI3 is catalyzed 1- butylene and ethylene copolymer as major catalyst
Solvent is dry toluene, and 1- butylene and ethylene pressure ratio are 0.5, makes to keep pressure 1MPa in reactor, reaction temperature
Degree is 80 DEG C, the NiI3 that major catalyst is prepared with embodiment 6, cocatalyst B (C6F5)4(mole of co-catalyst and major catalyst
Than for 800:1), with embodiment 9, polymerization time is 1.5 hours for concrete operations.Its activity is 6.5 × 105G/molh, polymerization
Object Mw is 3.9 × 105G/mol, MWD 2.0.
Embodiment 14
PdI1 is catalyzed 1- hexene oligomerization as major catalyst
50mL dry toluene is added in through nitrogen displacement 250mL reaction kettle three times, be separately added into 5mL 1- hexene, 5
μm ol is by the resulting PdI1 of embodiment 7, co-catalyst Al2Et3Cl3(molar ratio of co-catalyst and major catalyst is 800:1),
Stirring is warming up to 40 DEG C, and polymerization time is 2 hours, and the acidic ethanol of 10mL 10% is then added to reaction terminating, with water, second
Alcohol washing, filtered polymeric, then drying 8 hours in 60 DEG C of vacuum ovens, obtain product polyhexene 4.5g.Its activity is
8.9×105G/molh, polymer Mw are 3.3 × 105G/mol, MWD 2.8.
Embodiment 15
PdI3 is as major catalyst catalyzed ethylene polymerization
The NiI1 in embodiment 9 is replaced with complex PdI3 prepared by embodiment 8, being passed through ethylene makes to keep pressure in reactor
Power 2MPa, co-catalyst are B (C6F5)4(molar ratio of co-catalyst and major catalyst is 100:1), operates with embodiment 9.Its
Activity is 8.7 × 106G/molh, polymer Mw are 6.0 × 105G/mol, MWD 2.3, polymer branching degree are 124/1000
A carbon atom.
By embodiment 9- embodiment 11 as can be seen that the alpha-diimine metal complex NiI1 with hydroxyl can be catalyzed
Ethylene homo, norbornene homopolymerization and ethylene and norbornene copolymerization.And aniline exists with the complex NiI1 of isopropyl
Under 80 DEG C of polymerization temperatures, still there is good catalytic activity.
Unaccomplished matter of the present invention is well-known technique.
Claims (8)
1. a kind of acenaphthene annulus has the alpha-diimine compound of hydroxyl, it is characterized in that the alpha-diimine structural formula of compound are as follows:
Wherein, R is substituted base or unsubstituted C6-C60Aryl, C6-C60One of heterocyclic arene base；Ar is tool
Just like one of flowering structure group:
Wherein, n=1,2,3,4,5,6 or 7；R' is C1-C20Alkyl.
2. acenaphthene annulus as described in claim 1 has the preparation method of the alpha-diimine compound of hydroxyl, it is characterized in that such as Formulas I institute
The preparation method of the alpha-diimine compound with hydroxyl shown, comprising the following steps:
At 40-120 DEG C, by the alpha-diimine as shown in compound A, as shown in compound B have hydroxyl fragrant boronation
It closes object, inorganic carbonate, palladium catalyst to react 1-48 hours in the mixture of organic solvent and water, be made shown in formula I
Alpha-diimine compound with hydroxyl；
Wherein, mole of the alpha-diimine as shown in compound A and the fragrant boron compound as shown in compound B with hydroxyl
Than for 1:1-1:2, the molar ratio of the alpha-diimine as shown in compound A and inorganic carbonate is 1:2-1:5, such as compound A institute
The molar ratio of the alpha-diimine and palladium catalyst that show is 1:0.001-1:0.5；The palladium catalyst is four (triphenyl phosphorus) palladiums
Or bis- (dibenzalacetone) palladiums.Inorganic carbonate is potassium carbonate, sodium carbonate or cesium carbonate.
The compound A is as follows:
Wherein, R is substituted base or unsubstituted C6-C60Aryl, C6-C60One of heterocyclic arene base；
The compound B is as follows:
Wherein, R " is hydrogen or C1-C15Alkyl or two R " be connected and constitute naphthenic base.Ar is to have the following structure in group
One kind:
Wherein, n=1,2,3,4,5,6 or 7；R' is C1-C20Alkyl.
3. the preparation method of the alpha-diimine as claimed in claim 2 as shown in compound A, it is characterized in that described such as chemical combination
The preparation method of alpha-diimine shown in object A, comprising the following steps:
At 40-120 DEG C, by 5- bromine band acenaphthenequinone, R-NH2It reacts 1-48 hours, is made in organic solvent with organic acid catalyst
Alpha-diimine compound with hydroxyl shown in formula I；
Wherein, 5- bromine band acenaphthenequinone and R-NH2Molar ratio be 1:2-1:4, molar ratio of the 5- bromine with acenaphthenequinone and organic acid catalyst be
1:0.001-1:0.5；The organic acid catalyst is formic acid, acetic acid, p-methyl benzenesulfonic acid or camphorsulfonic acid；Described is organic
Solvent is methylene chloride, chloroform, 1,2- dichloroethanes, tetrahydrofuran, 1,4- dioxane, benzene, toluene, chlorobenzene or theirs is mixed
Close object；Compound R-the NH2Middle R is substituted base or unsubstituted C6-C60Aryl, C6-C60Heterocyclic arene base
One of.
4. a kind of alpha-diimine metal complex, it is characterized in that the metal complex is had by acenaphthene annulus as described in claim 1
The alpha-diimine compound of hydroxyl and late transition metal reactant salt are made, wherein the late transition metal salt be nickel salt, palladium salt,
One of platinum salt, molysite or cobalt salt.
5. the preparation method of alpha-diimine metal complex as claimed in claim 4, it is characterized in that the following steps are included: in nitrogen
In reactor under gas atmosphere, it is 0.01-0.1mmol/mL such as claim 1 that the late transition metal salt, which is added to concentration,
It is reacted in the alpha-diimine compound solution with hydroxyl, wherein late transition metal salt and alpha-diimine compound etc.
Mole；Be stirred to react at room temperature 1-48 hours, be concentrated under reduced pressure reaction solution to original solution volume 1/10th to 50/
One, it adds ten times of the volume of the concentrated liquid and is precipitated to fiftyfold precipitating reagent, filtered, after solid is washed with precipitating reagent, vacuum drying
Obtain alpha-diimine metal complex；
Wherein, solvent is C in the solution of the alpha-diimine compound1-C20Chloralkane, C1-C20Chlorination aromatic hydrocarbon,
C1-C20Aromatic hydrocarbon or C1-C20One of oxygen-containing alkane or a variety of mixed solvents；The precipitating reagent is C5-C20Alkane
Hydrocarbon or C5-C20One of cycloalkane or a variety of mixtures.
6. the preparation method of alpha-diimine metal complex as claimed in claim 5, it is characterized in that the alpha-diimine
Close object solution in solvent be methylene chloride, chloroform, 1,2- dichloroethanes, chlorobenzene, dichloro-benzenes, toluene, tetrahydrofuran and
One of 1,4- dioxane or a variety of mixed solvents；
The precipitating reagent is one of pentane, n-hexane, normal heptane, normal octane and hexamethylene or a variety of mixtures；
The late transition metal salt is preferably (DME) NiBr2、(DME)NiCl2、(COD)PdClCH3、(PhCN)2PdCl2Or
(COD)PdMe(NCMe)。
7. a kind of application of alpha-diimine metal complex, it is characterized in that alpha-diimine metal combination as claimed in claim 4
Object is applied to the gas-phase polymerization of ethylene or propylene or the liquid-phase bulk polymerization or olefinic monomer of olefinic monomer as major catalyst
In polymerisation in solution.
8. the application of alpha-diimine metal complex as claimed in claim 7, it is characterized in that α-two as claimed in claim 4
Imine metal complex as major catalyst application in olefin polymerization, including following reaction condition: polymeric reaction temperature is-
20-120℃；Pressure is 0.1-10MPa when olefinic monomer is gas；Olefinic monomer is specially ethylene, propylene, 1- butylene, 1- penta
Alkene, 4-methyl-1-pentene, 1- hexene, 1- heptene, 1- octene, 1- decene, norbornene, vinyl norbornene, ethylidene drop
One of bornylene, bicyclopentadiene, 1,4- butadiene, styrene, α-methylstyrene and divinylbenzene are a variety of.
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| CN114853947A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Composite catalyst and application thereof |
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