CN108864343A - A kind of double-core (alpha-diimine) nickel/palladium alkene catalyst, preparation and application - Google Patents
A kind of double-core (alpha-diimine) nickel/palladium alkene catalyst, preparation and application Download PDFInfo
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- CN108864343A CN108864343A CN201710325709.2A CN201710325709A CN108864343A CN 108864343 A CN108864343 A CN 108864343A CN 201710325709 A CN201710325709 A CN 201710325709A CN 108864343 A CN108864343 A CN 108864343A
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- nickel
- diimine
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- -1 palladium alkene Chemical class 0.000 title claims abstract description 62
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 34
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims description 56
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 47
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 30
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 26
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 125000005594 diketone group Chemical group 0.000 claims description 13
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000003426 co-catalyst Substances 0.000 claims description 11
- 238000006482 condensation reaction Methods 0.000 claims description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 claims description 6
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001448 anilines Chemical class 0.000 claims description 3
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 46
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 229920000098 polyolefin Polymers 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000002902 bimodal effect Effects 0.000 abstract description 2
- 239000011982 enantioselective catalyst Substances 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 132
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 90
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 75
- 239000000047 product Substances 0.000 description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 45
- 239000012299 nitrogen atmosphere Substances 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 238000003756 stirring Methods 0.000 description 35
- 230000001376 precipitating effect Effects 0.000 description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 31
- 238000004090 dissolution Methods 0.000 description 30
- 238000001556 precipitation Methods 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 238000001816 cooling Methods 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- 230000000694 effects Effects 0.000 description 21
- 238000005406 washing Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 14
- 238000011049 filling Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 235000003140 Panax quinquefolius Nutrition 0.000 description 11
- 240000005373 Panax quinquefolius Species 0.000 description 11
- 238000010094 polymer processing Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 101150030514 GPC1 gene Proteins 0.000 description 8
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- VOBHRXKXNNPOFC-UHFFFAOYSA-N CCl.C1=CCCC=CCC1 Chemical compound CCl.C1=CCCC=CCC1 VOBHRXKXNNPOFC-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 0 **1C=C(*)C=C(*)C1N Chemical compound **1C=C(*)C=C(*)C1N 0.000 description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YRUODNOQCVIIQZ-BGERDNNASA-N (2S)-2,6-diamino-N-(1-diphenoxyphosphorylbutyl)hexanamide Chemical compound C=1C=CC=CC=1OP(=O)(C(NC(=O)[C@@H](N)CCCCN)CCC)OC1=CC=CC=C1 YRUODNOQCVIIQZ-BGERDNNASA-N 0.000 description 1
- CAOZDGNUUDFUGL-UHFFFAOYSA-N 1,3-di(propan-2-yl)-5-(trifluoromethyl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(F)(F)F)=C1 CAOZDGNUUDFUGL-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical class CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- FHEAFSAWXGUQGP-UHFFFAOYSA-N 2,6-ditert-butyl-4-nitroaniline Chemical compound CC(C)(C)C1=CC([N+]([O-])=O)=CC(C(C)(C)C)=C1N FHEAFSAWXGUQGP-UHFFFAOYSA-N 0.000 description 1
- HMUDLFJQDJVKKZ-UHFFFAOYSA-N 5,6-dimethyl-1,2-dihydroacenaphthylene Chemical compound C1CC2=CC=C(C)C3=C2C1=CC=C3C HMUDLFJQDJVKKZ-UHFFFAOYSA-N 0.000 description 1
- 125000006519 CCH3 Chemical group 0.000 description 1
- VULBLDOIBWZSEB-UHFFFAOYSA-N COC1=C2CCC=3C(=CC=C(C=C1)C32)OC Chemical compound COC1=C2CCC=3C(=CC=C(C=C1)C32)OC VULBLDOIBWZSEB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
-
- 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
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
- C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
-
- 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
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- 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
- C08F110/14—Monomers containing five or more carbon atoms
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to olefin catalytic polymerization technique fields, it is desirable to provide a kind of double-core (alpha-diimine) nickel/palladium alkene catalyst, preparation and application.The chemical structural formula of the catalyst is as shown in Formulas I or Formula II.The molecular structure of catalyst of the present invention is more diversified, the chain structure of polymerizate can be adjusted in wider range, the especially asymmetric catalyst of molecular structure, there are the different activated centres of two kinds of property, the molecular weight and/or the degree of branching of the polymer of each self-generating can be used for preparing bimodal distribution type polyolefin and other new structural polyolefine materials there are apparent difference.
Description
Technical field
The invention belongs to olefin catalytic polymerization technique fields, and in particular to a kind of double-core (alpha-diimine) nickel/palladium alkene is urged
Agent and the preparation method and application thereof.
Background technique
Polyolefin is the basic material to involve the interests of the state and the people, and due to its excellent performance, the kind of multiplicity, Yi Jiyuan
Material is easy to get and the factors such as cheap, it is made to be widely used in each field such as work, agricultural and national defence.The exploitation of raw catelyst and
It is the key that the structure and performance for controlling polyolefin using being to push one of polyolefin industrial progress and the core drive of development.
(alpha-diimine) nickel/palladium catalyst can obtain branched polyethylene with catalyzed ethylene polymerization.Researcher urges such
Agent has carried out a large amount of research and improvement, is desirably to obtain the excellent catalyst system of catalytic performance, but most of both for list
(alpha-diimine) nickel/palladium catalyst of core, it is less to the research of double-core or multicore catalyst.
Chinese invention patent 200710070354.3,201210276244.3,201410024754.0 each provides double
Core (alpha-diimine) nickel/palladium catalyst.Since double-core (alpha-diimine) nickel/palladium catalyst contains there are two metal center, the two
There are special coordinating effects between activated centre, so that double-core (alpha-diimine) nickel/palladium catalyst is shown and monokaryon (α-two
Imines) the different catalytic performance of nickel/palladium catalyst, catalytic activity and polymer molecular weight can be improved.Chinese invention patent
200710070354.3 disclosing double-core as follows (alpha-diimine) Raney nickel.
R in structural formula1、R2、R3、R4Respectively methyl, ethyl or isopropyl；And R1=R1’、R2=R2’、R3=R3’、R4=
R4'；R5、R6Respectively H, methyl, ethyl, butyl, phenyl or trifluoromethyl；Or R5、R6Respectively methylene, sub- second
Base, butylidene, phenylene or trifluoromethyl phenylene and R5With R6It is connected to ring structure；X1、X2、X3And X4It is all Cl or Br.It should
The skeleton of catalyst is naphthalene and molecular structure is symmetrical.The molecular structure for thereby resulting in catalyst is single, and it is poly- to be catalyzed ethylene with it
The chain structure (such as molecular weight and the degree of branching) for closing the polyethylene of preparation is also relatively simple.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of double-core (Asia α-two
Amine) nickel/palladium alkene catalyst, preparation method and application.
In order to solve the technical problem, solution of the invention is：
A kind of double-core (alpha-diimine) nickel/palladium alkene catalyst is provided, chemical structural formula is as shown in Formulas I or Formula II：
In above formula, R1For methyl or isopropyl, R2For methyl or isopropyl, R3For H, methyl or by 2 R3Form camphyl or
Naphthalene and its derivative, R4For H, methyl or by 2 R4Form camphyl or naphthalene and its derivative, R5For methyl, tert-butyl, two
Phenyl methyl or isopropyl, R6For methyl, tert-butyl, diphenyl methyl or isopropyl, R7For H, methyl, tert-butyl, methoxyl group,
N, N- dimethyl-amino, Cl, Br, CF3Or NO2, R8For H, methyl, tert-butyl, methoxyl group, N, N- dimethyl-amino, Cl, Br,
CF3Or NO2；R7And R8When being simultaneously H, 2 R3With 2 R4It is not simultaneously naphthalene；X is Cl or Br.
The present invention also provides the method for preparing double-core above-mentioned (alpha-diimine) nickel/palladium alkene catalyst, including it is following
Step：
(1) aniline is added drop-wise to progress ketoamine condensation reaction in equimolar diketone, obtains compound C1；Wherein, aniline
In include substituent R 5 and R7, include substituent R 3 in diketone；
(2) aniline is added drop-wise to progress ketoamine condensation reaction in equimolar diketone, obtains compound C2；Wherein, aniline
In include substituent R 6 and R8, include substituent R 4 in diketone；
(3) compound C1 is added drop-wise in equimolar 4,4'- methylene bis- (the disubstituted aniline of 2,6-) and carries out ketoamine contracting
Reaction is closed, compound C3 is obtained：
(4) compound C3 and equimolar compound C2 is subjected to ketoamine condensation reaction, obtains ligand L：
(5) under conditions of anhydrous and oxygen-free, by ligand L respectively with (DME) NiBr2、NiCl2·6H2O or (COD)
PdCH3Cl complexing, obtains double-core described in Formulas I or Formula II (alpha-diimine) nickel/palladium alkene catalyst.
Invention further provides a kind of double-core (alpha-diimine) nickel/palladium alkene catalyst composition, the composition is removed
Comprising except double-core above-mentioned (alpha-diimine) nickel/palladium alkene catalyst, also including the second component co-catalyst；The co-catalysis
Agent is Li (Et2O)2.8B(C6F5)4, it is methylaluminoxane, aluminium diethyl monochloride, any in ethyl aluminum dichloride or sesquialter aluminium ethide
It is a kind of.
Further include chain shuttling agent in the composition in the present invention, is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, two fourths
Any one in base magnesium, dimethyl magnesium or diethyl zinc.
Invention further provides the double-core (alpha-diimine) nickel/palladium alkene catalyst compositions to prepare poly- second
Application in alkene, polypropylene or ethylene and alpha olefin copolymer.
Inventive principle description：
(1) when the molecular structure of catalyst is symmetrical, when the skeleton of catalyst is not naphthalene or skeleton is naphthalene, replace
Base R7And R8It is not H；(2)R7And R8It can be different substituent groups, to prepare asymmetric double-core (alpha-diimine) nickel/palladium
Alkene catalyst.The skeleton and substituent R of catalyst7And R8Size will affect the steric hindrance around Ni metal center, from
And influence the molecular weight of polymer；And the skeleton and substituent R of catalyst7And R8In frared spectra or Draw electronic effect meeting
The electronegativity for influencing Ni metal center, to influence the degree of branching of polymer.Therefore, can by change catalyst skeleton with
And substituent R7And R8Type adjust the diversity of catalyst molecule structure, to realize the sanction to polymerizate chain structure
It cuts.
Compared with prior art, the beneficial effects of the present invention are：
The molecular structure of catalyst of the present invention is more diversified, and the link of polymerizate can be adjusted in wider range
Structure (such as molecular weight and the degree of branching), the especially asymmetric catalyst of molecular structure, there are the different activated centre of two kinds of property,
The molecular weight and/or the degree of branching of the polymer of each self-generating can be used for preparing bimodal distribution type polyene there are apparent difference
Hydrocarbon and other new structural polyolefine materials.
Specific embodiment
In the present invention, the method for preparing double-core (alpha-diimine) nickel/palladium alkene catalyst includes the following steps：
(1) aniline is added drop-wise to progress ketoamine condensation reaction in equimolar diketone, obtains compound C1；Wherein, aniline
In include substituent R 5 and R7, include substituent R 3 in diketone；
(2) aniline is added drop-wise to progress ketoamine condensation reaction in equimolar diketone, obtains compound C2；Wherein, aniline
In include substituent R 6 and R8, include substituent R 4 in diketone；
(3) compound C1 is added drop-wise in equimolar 4,4'- methylene bis- (the disubstituted aniline of 2,6-) and carries out ketoamine contracting
Reaction is closed, compound C3 is obtained：
(4) compound C3 and equimolar compound C2 is subjected to ketoamine condensation reaction, obtains ligand L：
(5) under conditions of anhydrous and oxygen-free, by ligand L respectively with (DME) NiBr2、NiCl2·6H2O or (COD)
PdCH3Cl complexing, obtains double-core described in Formulas I or Formula II (alpha-diimine) nickel/palladium alkene catalyst：
In above formula, R1For methyl or isopropyl, R2For methyl or isopropyl, R3For H, methyl or by 2 R3Form camphyl or
Naphthalene and its derivative, R4For H, methyl or by 2 R4Form camphyl or naphthalene and its derivative, R5For methyl, tert-butyl, two
Phenyl methyl or isopropyl, R6For methyl, tert-butyl, diphenyl methyl or isopropyl, R7For H, methyl, tert-butyl, methoxyl group,
N, N- dimethyl-amino, Cl, Br, CF3Or NO2, R8For H, methyl, tert-butyl, methoxyl group, N, N- dimethyl-amino, Cl, Br,
CF3Or NO2；R7And R8When being simultaneously H, 2 R3With 2 R4It is not simultaneously naphthalene；X is Cl or Br.
Ketoamine condensation reaction and complexation reaction involved in above-mentioned catalyst synthesis processes are that the classics in document are anti-
It answers, the response parameters such as the input amount of reactant and reaction condition are all general in its synthesis process, are the art sections
It grinds well known to worker.Below by way of specific embodiment, the present invention is described further, but the present invention is not limited to
Lower embodiment.The method is conventional method unless otherwise instructed, and the raw material unless otherwise instructed can be from open quotient
Industry approach and obtain.
The synthesized reference document Chem.Eur.J.2002 of 4- substituent group -2,6- diisopropyl aniline according to the present invention,
8(13):2848 and Organometallics, 2005,24 (6)：1145 carry out.
One, the preparation of ligand
Embodiment 1
The synthesis of ligand L 1
The chemical structural formula of ligand L 1 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, after dissolution two hours, 2mmol 4- nitro -2,6-DIPA (is dissolved in advance for stirring
In 20mL acetonitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 ×
50mL normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product C1-10.515g, yield 75%.
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, stirs, after dissolution two hours, by 2mmol 4- (N, N- dimethyl) amino -2,6-DIPA
(being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.Product C1-1'0.562g is obtained, is produced
Rate is 78%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 0.5mmol C1-1
(being dissolved in 10mL ethyl alcohol in advance) is added dropwise in three-necked flask.0.5mmol C1-1'(is dissolved in 10mL in advance after 24 hours
In ethyl alcohol) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 × 50mL
Normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product ligand L 10.428g, yield 80%.1H-NMR
(400MHz,CDCl3,δin ppm):8.32~8.38 (m, 8H, Py-H), 8.01 (s, 2H, Ar-H), 7.79 (s, 4H, Py-H),
6.99(s,4H,Ar-H),6.57(s,2H,Ar-H),3.96(s,2H,CH2), 3.06 (s, 6H, N (CH3)2),2.87(sept,
8H,CH(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2)。
Elem.Anal.Calcd.For C73H78N6O2:C, 81.87%；H, 7.29%；N, 7.85%.Found:C,
81.81%；H, 7.22%；N, 7.89%.
ESI-MS:m/z 1071.0([M+H]+)
Embodiment 2
The synthesis of ligand L 2
The chemical structural formula of ligand L 2 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, by 2mmol 2,3- diacetyl is added to the three-necked flask for filling 80mL acetonitrile
In, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 2mmol 4- trifluoromethyl -2,6- diisopropyl benzene
Amine (being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product
Precipitation.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.Product C1-2 0.353g is obtained,
Yield is 72%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 2mmol 2,3- diacetyl is added to the three-necked flask for filling 80mL acetonitrile
In, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 2mmol 4- (N, N- dimethyl) amino -2,6- bis-
Isopropyl aniline (being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, it is naturally cold
But, product Precipitation.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.Obtain product C1-2'
0.428g, yield 82%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 0.5mmol C1-2
(being dissolved in 10mL ethyl alcohol in advance) is added dropwise in three-necked flask.0.5mmol C1-2'(is dissolved in 10mL in advance after 24 hours
In ethyl alcohol) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 × 50mL
Normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product ligand L 20.388g, yield 85%.1H-NMR
(400MHz,CDCl3,δin ppm):7.38(s,2H,Ar-H),6.99(s,4H,Ar-H),6.57(s,2H,Ar-H),3.96
(s,2H,CH2), 3.06 (s, 6H, N (CH3)2),2.87(sept,8H,CH(CH3)2),2.07(s,12H,CCH3), 0.86~
1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C58H78N5F3:C, 76.40%；H, 8.56%；N, 7.68%.Found:C,
76.45%；H, 8.51%；N, 7.62%.
ESI-MS:m/z 912.0([M+H]+)
Embodiment 3
The synthesis of ligand L 3
The chemical structural formula of ligand L 3 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol glyoxal is added in the three-necked flask for filling 80mL acetonitrile, half is small
Shi Hou, is added 15mL acetic acid, and after dissolution two hours, the bromo- 2,6-DIPA of 2mmol 4- (is dissolved in advance for stirring
In 20mL acetonitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 ×
50mL normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product C1-30.326g, yield 75%.
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol glyoxal is added in the three-necked flask for filling 80mL acetonitrile, half is small
15mL acetic acid is added in Shi Hou, stirs, after dissolution two hours, by 2mmol 4- (N, N- dimethyl) amino -2,6- diisopropyl benzene
Amine (being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product
Precipitation.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.Product C1-3'0.368g is obtained,
Yield is 79%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 0.5mmol C1-3
(being dissolved in 10mL ethyl alcohol in advance) is added dropwise in three-necked flask.0.5mmol C1-3'(is dissolved in 10mL in advance after 24 hours
In ethyl alcohol) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 × 50mL
Normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product ligand L 30.364g, yield 85%.1H-NMR
(400MHz,CDCl3,δin ppm):7.50(d,4H,NC-H),7.27(s,2H,Ar-H),6.99(s,4H,Ar-H),6.57
(s,2H,Ar-H),3.96(s,2H,CH2), 3.06 (s, 6H, N (CH3)2),2.87(sept,8H,CH(CH3)2), 0.86~1.26
(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C53H70N5Br:C, 74.30%；H, 8.18%；N, 8.18%.Found:C,
74.36%；H, 8.11%；N, 8.13%.
ESI-MS:m/z 857.0([M+H]+)
Embodiment 4
The synthesis of ligand L 4
The chemical structural formula of ligand L 4 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, after dissolution two hours, the chloro- 2,6-DIPA of 2mmol 4- (is dissolved in advance for stirring
In 20mL acetonitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 ×
50mL normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product C1-40.586g, yield 78%.
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, stirs, after dissolution two hours, by 2mmol 4- (N, N- dimethyl) amino -2,6- dimethylaniline
(being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.Product C1-4'0.531g is obtained, is produced
Rate is 81%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6- dimethylanilines), which is added to, to be filled
In the three-necked flask of 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 0.5mmol C1-4
(being dissolved in 10mL ethyl alcohol in advance) is added dropwise in three-necked flask.0.5mmol C1-4'(is dissolved in 10mL in advance after 24 hours
In ethyl alcohol) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 × 50mL
Normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain 4 0.357g of product ligand L, yield 80%.1H-NMR
(400MHz,CDCl3,δin ppm):8.32~8.38 (m, 8H, Py-H), 7.79 (s, 4H, Py-H), 7.32 (s, 2H, Ar-H),
6.91(s,4H,Ar-H),6.49(s,,2H,Ar-H),3.96(s,2H,CH2), 3.06 (s, 6H, N (CH3)2),2.34(s,18H,
CH3), 0.86~1.26 (dd, 12H, CH (CH3)2)。
Elem.Anal.Calcd.For C61H54N5Cl:C, 82.11%；H, 6.06%；N, 7.85%.Found:C,
82.14%；H, 6.08%；N, 7.82%.
ESI-MS:m/z 892.5([M+H]+)
Embodiment 5
The synthesis of ligand L 5
The chemical structural formula of ligand L 5 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, after dissolution two hours, 2mmol 4- nitro -2,6- di-tert-butyl aniline (is dissolved in advance for stirring
In 20mL acetonitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 ×
50mL normal heptane washing precipitating, after 70 DEG C, vacuum drying 48 hours.Obtain product C1-50.645g, yield 75%.
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, after dissolution two hours, 2mmol 4- methoxyl group -2,6- di-tert-butyl aniline (is dissolved in advance for stirring
In 20mL acetonitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5
× 50mL normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product C1-5'0.664g, yield 80%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 0.5mmol C1-5
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.0.5mmol C1-5'(is dissolved in 20mL in advance after 24 hours
In ethyl alcohol) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 × 50mL
Normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product ligand L 50.458g, yield 80%.1H-NMR
(400MHz,CDCl3,δin ppm):8.32~8.38 (m, 8H, Py-H), 7.79 (s, 4H, Py-H), 7.52 (s, 2H, Ar-H),
7.04(s,2H,Ar-H),6.99(s,4H,Ar-H),3.96(s,2H,CH2), 3.83 (s, 3H, OCH3),2.87(sept,4H,CH
(CH3)2),1.35(s,36H,C(CH3)3), 0.86~1.26 (dd, 24H, CH (CH3)2)。
Elem.Anal.Calcd.For C78H89N5O3:C, 81.82%；H, 7.78%；N, 6.12%.Found:C,
81.88%；H, 7.71%；N, 6.16%.
ESI-MS:m/z 1144.0([M+H]+)
Embodiment 6
The synthesis of ligand L 6
The chemical structural formula of ligand L 6 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, stirs, after dissolution two hours, 2mmol 4- trifluoromethyl -2,6-DIPA is (molten in advance
Solution is in 20mL acetonitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.
Wash precipitating with 5 × 50mL normal heptane, after 70 DEG C, vacuum drying 48 hours.Obtain product C1-6 0.695g, yield 85%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 1mmol C1-6
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.6 0.476g of product ligand L is obtained,
Yield is 85%.1H-NMR(400MHz,CDCl3,δin ppm):8.32~8.38 (m, 8H, Py-H), 7.79 (s, 4H, Py-H),
7.38(s,4H,Ar-H),6.99(s,4H,Ar-H),3.96(s,2H,CH2),2.87(sept,8H,CH(CH3)2), 0.86~
1.26(dd,48H,CH(CH3)2)。
Elem.Anal.Calcd.For C73H72N4F6:C, 78.35%；H, 6.44%；N, 6.26%.Found:C,
78.31%；H, 6.37%；N, 6.22%.
ESI-MS:m/z 1119.0([M+H]+)
Embodiment 7
The synthesis of ligand L 7
The chemical structural formula of ligand L 7 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol glyoxal is added in the three-necked flask for filling 80mL acetonitrile, half is small
Shi Hou, is added 15mL acetic acid, and 2mmol 2,6-DIPA after dissolution two hours, (is dissolved in 20mL second by stirring in advance
In nitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.Just with 5 × 50mL
Heptane wash precipitating, after 70 DEG C, vacuum drying 48 hours.Obtain product C1-7 0.369g, yield 75%.
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol acenaphthenequinone is added in the three-necked flask for filling 80mL acetonitrile, half an hour
Afterwards, 15mL acetic acid is added, 2mmol 2,6-DIPA after dissolution two hours, (is dissolved in 20mL acetonitrile by stirring in advance
In) be added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 × 50mL positive heptan
Alkane washing precipitating, after 70 DEG C, vacuum drying 48 hours.Obtain product C1-7 ' 0.552g, yield 81%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 0.5mmol C1-7
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.0.5mmol C1-7 ' (is dissolved in 20mL in advance after 24 hours
In ethyl alcohol) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.With 5 × 50mL
Normal heptane washing precipitating, after be dried in vacuo 48 hours at 70 DEG C.Obtain product ligand L 70.356g, yield 83%.1H-NMR
(400MHz,CDCl3,δin ppm):8.32~8.38 (m, 4H, Py-H), 7.79 (s, 2H, Py-H), 7.51 (s, 2H, Ar-H),
7.50(d,2H,CH),7.12(s,4H,Ar-H),6.99(s,4H,Ar-H),3.96(s,2H,CH2),2.87(sept,8H,CH
(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2)。
Elem.Anal.Calcd.For C61H68N4:C, 85.41%；H, 7.94%；N, 6.54%.Found:C,
85.45%；H, 7.91%；N, 6.59%.
ESI-MS:m/z 857.0([M+H]+)
Embodiment 8
The synthesis of ligand L 8
The chemical structural formula of ligand L 8 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, by 2mmol 5,6- dihydro cyclopenta [f, g] acenaphthene -1,2- diketone, which is added to, to be filled
In the three-necked flask of 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 2mmol 2,6- bis- is different
Propyl aniline (being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, it is naturally cold
But, product Precipitation.Wash precipitating with 5 × 50mL normal heptane, after 70 DEG C, vacuum drying 48 hours.Obtain product C1-8
0.609g, yield 83%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 1mmol C1-8
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.8 0.424g of product ligand L is obtained,
Yield is 82%.1H-NMR(400MHz,CDCl3,δin ppm):8.32(s,4H,Py-H),7.64(s,4H,Py-H),7.51
(s,2H,Ar-H),7.12(s,4H,Ar-H),6.99(s,4H,Ar-H),3.96(s,2H,CH2),3.52(t,8H,CH2),2.87
(sept,8H,CH(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2)。
Elem.Anal.Calcd.For C75H78N4:C, 86.96%；H, 7.54%；N, 5.41%.Found:C,
87.02%；H, 7.48%；N, 5.46%.
ESI-MS:m/z 1035.0([M+H]+)
Embodiment 9
The synthesis of ligand L 9
The chemical structural formula of ligand L 9 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol camphorquinone is added in the three-necked flask for filling 80mL acetonitrile, half is small
Shi Hou, is added 15mL acetic acid, and 2mmol 2,6-DIPA after dissolution two hours, (is dissolved in 20mL second by stirring in advance
In nitrile) it is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product Precipitation.Just with 5 × 50mL
Heptane wash precipitating, after 70 DEG C, vacuum drying 48 hours.Obtain product C1-9 0.358g, yield 55%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 1mmol C1-9
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.9 0.417g of product ligand L is obtained,
Yield is 85%.1H-NMR(400MHz,CDCl3,δin ppm):7.51(s,2H,Ar-H),7.12(s,4H,Ar-H),6.99
(s,4H,Ar-H),3.96(s,2H,CH2),2.87(sept,8H,CH(CH3)2), 1.24~1.49 (m, 32H, Camph-H),
0.86~1.20 (dd, 48H, CH (CH3)2)。
Elem.Anal.Calcd.For C69H96N4:C, 84.40%；H, 9.79%；N, 5.71%.Found:C,
84.42%；H, 9.76%；N, 5.73%.
ESI-MS:m/z 981.0([M+H]+)
Embodiment 10
The synthesis of ligand L 10
The chemical structural formula of ligand L 10 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, by 2mmol 3,8- dimethoxy acenaphthene -1,2- diketone, which is added to, fills 80mL second
In the three-necked flask of nitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 2mmol 2,6- diisopropyl benzene
Amine (being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product
Precipitation.Wash precipitating with 5 × 50mL normal heptane, after 70 DEG C, vacuum drying 48 hours.Product C1-10 0.69g is obtained, is produced
Rate is 86%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 1mmol C1-10
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.10 0.458g of product ligand L is obtained,
Yield is 83%.1H-NMR(400MHz,CDCl3,δin ppm):8.32~8.38 (m, 8H, Py-H), 7.79 (s, 4H, Py-H),
7.51(s,2H,Ar-H),7.12(s,4H,Ar-H),6.99(s,4H,Ar-H),3.96(s,2H,CH2),3.83(s,12H,
OCH3),2.87(sept,8H,CH(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2)。
Elem.Anal.Calcd.For C75H82N4O4:C, 81.60%；H, 7.43%；N, 5.08%.Found:C,
81.66%；H, 7.39%；N, 5.12%.
ESI-MS:m/z 1103.0([M+H]+)
Embodiment 11
The synthesis of ligand L 11
The chemical structural formula of ligand L 11 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, 2mmol cyclopenta [f, g] acenaphthylene -1,2- diketone is added to and fills 80mL second
In the three-necked flask of nitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 2mmol 2,6- diisopropyl benzene
Amine (being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stands, natural cooling, product
Precipitation.Wash precipitating with 5 × 50mL normal heptane, after 70 DEG C, vacuum drying 48 hours.Product C1-11 0.609g is obtained,
Yield is 83%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 1mmol C1-11
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.11 0.433g of product ligand L is obtained,
Yield is 84%.1H-NMR(400MHz,CDCl3,δin ppm):8.22(s,4H,Py-H),7.64(s,4H,Py-H),7.51
(s,2H,Ar-H),7.15(s,4H,C-H),7.12(s,4H,Ar-H),6.99(s,4H,Ar-H),3.96(s,2H,CH2),
2.87(sept,8H,CH(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2)。
Elem.Anal.Calcd.For C75H74N4:C, 87.29%；H, 7.18%；N, 5.43%.Found:C,
87.35%；H, 7.15%；N, 5.48%.
ESI-MS:m/z 1031.0([M+H]+)
Embodiment 12
The synthesis of ligand L 12
The chemical structural formula of ligand L 12 is as follows：
Under the conditions of nitrogen atmosphere and 85 DEG C, by 2mmol 5,6- dimethyl acenaphthene -1,2- diketone, which is added to, fills 80mL acetonitrile
Three-necked flask in, after half an hour, be added 15mL acetic acid, stirring, dissolution two hours after, by 2mmol 2,6-DIPA
(being dissolved in 20mL acetonitrile in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after 70 DEG C, vacuum drying 48 hours.Product C1-12 0.649g is obtained, is produced
Rate is 88%.
Under the conditions of nitrogen atmosphere and 85 DEG C, by 0.5mmol 4,4'- methylene bis- (2,6-DIPAs) is added to Sheng
In the three-necked flask for having 80mL acetonitrile, after half an hour, 15mL acetic acid is added, stirs, after dissolution two hours, by 1mmol C1-12
(being dissolved in 20mL ethyl alcohol in advance) is added dropwise in three-necked flask.Stop reaction after 24 hours, stand, natural cooling, product is heavy
Precipitation goes out.Wash precipitating with 5 × 50mL normal heptane, after be dried in vacuo 48 hours at 70 DEG C.12 0.447g of product ligand L is obtained,
Yield is 86%.1H-NMR(400MHz,CDCl3,δin ppm):8.22(s,4H,Py-H),7.51(s,2H,Ar-H),7.23
(s,4H,Py-H),7.12(s,4H,Ar-H),6.99(s,4H,Ar-H),3.96(s,2H,CH2),2.87(sept,8H,CH
(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2)。
Elem.Anal.Calcd.For C75H82N4:C, 86.62%；H, 7.89%；N, 5.39%.Found:C,
86.66%；H, 7.88%；N, 5.42%.
ESI-MS:m/z 1039.0([M+H]+)
Various types of diketone (or aldehyde) compound and different types of aniline are subjected to condensation reaction, condensation product divides again
Not with 4,4 '-diamino -3,3 ', 5,5 '-four substituent group biphenyl, which carry out reaction, can be obtained by matching for various different molecular structures
Body.Since reaction process and reaction condition are similar, the specific preparation method of various ligands will not enumerate.
Two, the preparation of double-core (alpha-diimine) palladium complex
Embodiment 13
The synthesis of catalyst Pd1
0.2mmol ligand L 1 and 0.4mmol 1,5- cyclo-octadiene methyl chloride palladium are added to the Schlenk bottle of 50mL
(the inside is nitrogen atmosphere) injects 20mL methylene chloride, stirs 24 hours at 23 DEG C.After reaction, it stands, by solution mistake
Filter, filtrate decompression drain removing methylene chloride.Solid powder then is washed with 4 × 10mL ether, it is small to be dried in vacuo 10 at room temperature
When, obtain solid powder 0.249g, yield 90%.
1H-NMR(400MHz,CDCl3,δin ppm):8.32~8.38 (m, 8H, Py-H), 7.79 (s, 4H, Py-H),
7.38(s,2H,Ar-H),6.99(s,4H,Ar-H),6.57(s,,2H,Ar-H),3.96(s,2H,CH2), 3.06 (s, 6H, N
(CH3)2),2.87(sept,8H,CH(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2), 0.50~0.80 (s, 6H, Pd-
CH3)。
Elem.Anal.Calcd.For C75H84N6O2Pd2Cl2:C, 65.03%；H, 6.07%；N, 6.07%.Found:
C, 64.91%；H, 6.05%；N, 6.08%.
ESI-MS:m/z 1384.0([M+H]+)
Embodiment 14
The synthesis of catalyst Pd7
0.2mmol ligand L 7 and 0.4mmol 1,5- cyclo-octadiene methyl chloride palladium are added to the Schlenk bottle of 50mL
(the inside is nitrogen atmosphere) injects 20mL methylene chloride, stirs 24 hours at 23 DEG C.After reaction, it stands, by solution mistake
Filter, filtrate decompression drain removing methylene chloride.Solid powder then is washed with 4 × 10mL ether, it is small to be dried in vacuo 10 at room temperature
When, obtain solid powder 0.218g, yield 93%.1H-NMR(400MHz,CDCl3,δinppm):8.32~8.38 (m, 4H, Py-
H), 7.79 (s, 2H, Py-H), 7.51 (s, 2H, Ar-H), 7.50 (d, 2H, CH), 7.12 (s, 4H, Ar-H), 6.99 (s, 4H,
Ar-H),3.96(s,2H,CH2),2.87(sept,8H,CH(CH3)2), 0.86~1.26 (dd, 48H, CH (CH3)2), 0.50~
0.80(s,6H,Pd-CH3)。
Elem.Anal.Calcd.For C63H74N4Pd2Cl2:C, 64.62%；H, 6.32%；N, 4.79%.Found:C,
64.57%；H, 6.35%；N, 4.81%.
ESI-MS:m/z 1170.0([M+H]+)
Various types of ligands and 1,5- cyclo-octadiene methyl chloride palladium, which are carried out complexing, can be obtained various double-core (α-two
Imines) palladium complex.Since reaction process and reaction condition are similar, various double-cores (alpha-diimine) palladium will not enumerate
The specific preparation method of complex compound.
Three, the preparation of double-core (alpha-diimine) nickel complex
Embodiment 15
The synthesis of catalyst n i1
By 0.4mmol (DME) NiBr2It is added to single neck round-bottom flask (the inside is nitrogen atmosphere) of 50mL, injects 10mL
Methylene chloride, stirring are light yellow suspension.0.2mmol ligand L 1 is added in Schlenk bottles of 50mL (nitrogen atmosphere),
Inject 10mL methylene chloride.(DME) NiBr is injected into syringe2Suspended matter in, about 5min has been infused.With 5mL dichloro
Methane rinses remaining ligand.It is stirred 24 hours at 23 DEG C, stops reaction, stood, there is a small amount of precipitating in lower layer.Solution is filtered,
Filtrate decompression drains removing methylene chloride.Solid powder is washed with 4 × 15mL ether, is dried in vacuo 10 hours, must consolidate at room temperature
Body powder 0.284g, yield 94%.Elem.Anal.Calcd.For C73H78N6O2Ni2Br4:C, 58.09%；H, 5.17%；N,
5.57%.Found:C, 57.95%；H, 5.12%；N, 5.58%.It is by the content that ICP measures metallic nickel in complex compound
7.85%, theoretical value 7.82%.
In infrared spectroscopy, ligand the stretching vibration of C=N double bond characteristic absorption peak mainly in 1630~1665cm-1。
The characteristic absorption peak of the stretching vibration of C=N double bond in complex compound obviously deviates (1615~1650cm to lower wave number-1), thus
It can be seen that effective coordination has occurred between nitrogen-atoms and metal nickle atom.
Embodiment 16
The synthesis of catalyst n i7
By 0.4mmol (DME) NiBr2It is added to single neck round-bottom flask (the inside is nitrogen atmosphere) of 50mL, injects 10mL
Methylene chloride, stirring are light yellow suspension.0.2mmol ligand L 7 is added in Schlenk bottles of 50mL (nitrogen atmosphere),
Inject 10mL methylene chloride.(DME) NiBr is injected into syringe2Suspended matter in, about 5min has been infused.With 5mL dichloro
Methane rinses remaining ligand.It is stirred 24 hours at 23 DEG C, stops reaction, stood, there is a small amount of precipitating in lower layer.Solution is filtered,
Filtrate decompression drains removing methylene chloride.Solid powder is washed with 4 × 15mL ether, is dried in vacuo 10 hours, must consolidate at room temperature
Body powder 0.238g, yield 92%.Elem.Anal.Calcd.For C61H68N4Ni2Br4:C, 56.57%；H, 5.26%；N,
4.33%.Found:C, 56.61%；H, 5.19%；N, 4.32%.It is by the content that ICP measures metallic nickel in complex compound
9.21%, theoretical value 9.12%.
In infrared spectroscopy, ligand the stretching vibration of C=N double bond characteristic absorption peak mainly in 1630~1665cm-1。
The characteristic absorption peak of the stretching vibration of C=N double bond in complex compound obviously deviates (1615~1650cm to lower wave number-1), thus
It can be seen that effective coordination has occurred between nitrogen-atoms and metal nickle atom.
Embodiment 17
The synthesis of catalyst n i7 '
By 0.4mmol NiCl2·6H2O is added to single neck round-bottom flask (the inside is nitrogen atmosphere) of 50mL, injects 10mL
Methylene chloride, stirring.0.2mmol) L7 is added in Schlenk bottles of 50mL (nitrogen atmosphere), 10mL methylene chloride is injected.
NiCl is injected into syringe2·6H2In the suspended matter of O, about 5min has been infused.Remaining ligand is rinsed with 5mL methylene chloride.
It is stirred 24 hours at 23 DEG C, stops reaction, stood, there is a small amount of precipitating in lower layer.Solution is filtered, filtrate decompression drains removing two
Chloromethanes.Solid powder is washed with 4 × 15mL ether, is dried in vacuo 10 hours at room temperature, obtains solid powder 0.210g, yield
94%.Elem.Anal.Calcd.For C61H68N4Ni2Cl4:C, 65.59%；H, 6.09%；N, 5.02%.Found:C,
65.51%；H, 5.92%；N, 5.01%%.The content that metallic nickel in complex compound is measured by ICP is 10.61%, and theoretical value is
10.57%.
In infrared spectroscopy, ligand the stretching vibration of C=N double bond characteristic absorption peak mainly in 1630~1665cm-1。
The characteristic absorption peak of the stretching vibration of C=N double bond in complex compound obviously deviates (1615~1650cm to lower wave number-1), thus
It can be seen that effective coordination has occurred between nitrogen-atoms and metal nickle atom.
By various types of ligands and (DME) NiBr2Or NiCl2·6H2O, which carries out complexing, can be obtained various double-core (α-two
Imines) nickel complex.Since reaction process and reaction condition are similar, various double-cores (alpha-diimine) nickel will not enumerate
The specific preparation method of complex compound.
Four, double-core (alpha-diimine) palladium catalyst catalyzed ethylene polymerization reacts
Embodiment 18
Ethylene pressure polymerization is carried out in 100mL stainless steel polymeric kettle.10 μm of ol catalyst Pd1 and 20 μm of ol are helped
Catalyst (Li (Et2O)2.8B(C6F5)4) be dissolved in 10mL methylene chloride.It, will be above-mentioned under room temperature, ethylene pressure 0.2MPa
Dichloromethane solution injection.After polymerization 20 hours, polymer solution is instilled in methanol or acetone soln rapidly with rubber head dropper
It is precipitated, filtered polymeric, then for several times with methanol or acetone washing, is weighed after constant weight is dried under vacuum at 50 DEG C
8.22g polymer.Catalyst activity is 2.06 × 104g[mol(Pd)h]-1, the weight average molecular weight at the peak polymerizate GPC 1 is
336.7kg/mol, polydispersity coefficient 2.0, the weight average molecular weight at peak 2 are 5.3kg/mol, polydispersity coefficient 1.9.1H-NMR
Measuring polymer branching degree is 119/1000 carbon atom.
Embodiment 19
Ethylene pressure polymerization is carried out in 100mL stainless steel polymeric kettle.10 μm of ol catalyst Pd7 and 20 μm of ol are helped
Catalyst (Li (Et2O)2.8B(C6F5)4) be dissolved in 10mL methylene chloride.It, will be above-mentioned under room temperature, ethylene pressure 0.2MPa
Dichloromethane solution injection.After polymerization 20 hours, polymer solution is instilled in methanol or acetone soln rapidly with rubber head dropper
It is precipitated, filtered polymeric, then for several times with methanol or acetone washing, is weighed after constant weight is dried under vacuum at 50 DEG C
7.56g polymer.Catalyst activity is 1.89 × 104g[mol(Pd)h]-1, the weight average molecular weight at the peak polymerizate GPC 1 is
267.3kg/mol, polydispersity coefficient 2.1, the weight average molecular weight at peak 2 are 4.5kg/mol, polydispersity coefficient 1.9.1H-NMR
Measuring polymer branching degree is 109/1000 carbon atom.
Five, double-core (alpha-diimine) Raney nickel catalyzed ethylene polymerization reacts
Embodiment 20
Ethylene polymerization under atmospheric pressure is carried out under the conditions of anhydrous and oxygen-free.Room temperature and ethylene pressure are under 0.1MPa, by 40mL
Methylene chloride injects in the Schlenk bottle of 100mL, then injects 2mmol co-catalyst methylaluminoxane thereto.With 10mL bis-
Chloromethanes dissolves 5 μm of ol major catalyst Ni1, is injected into Schlenk bottles.After polymerizeing half an hour, rapidly will with rubber head dropper
Polymer solution is instilled in methanol or acetone soln and is precipitated, filtered polymeric, then for several times with methanol or acetone washing,
2.87g polymer is weighed to obtain after being dried under vacuum to constant weight at 50 DEG C.Catalyst activity is 5.74 × 105g[mol(Ni)h]-1, gather
The weight average molecular weight for closing the peak product GPC 1 is 251.5kg/mol, and the weight average molecular weight of polydispersity coefficient 2.2, peak 2 is
61.4kg/mol, polydispersity coefficient 1.9.1The polymer branching degree of H-NMR measurement is 79/1000 carbon atom.
Embodiment 21
Ethylene polymerization under atmospheric pressure is carried out under the conditions of anhydrous and oxygen-free.Room temperature and ethylene pressure are under 0.1MPa, by 40mL
Methylene chloride injects in the Schlenk bottle of 100mL, then injects 2mmol co-catalyst methylaluminoxane thereto.With 10mL bis-
Chloromethanes dissolves 5 μm of ol major catalyst Ni7, is injected into Schlenk bottles.After polymerizeing half an hour, rapidly will with rubber head dropper
Polymer solution is instilled in methanol or acetone soln and is precipitated, filtered polymeric, then for several times with methanol or acetone washing,
2.53g polymer is weighed to obtain after being dried under vacuum to constant weight at 50 DEG C.Catalyst activity is 5.06 × 105g[mol(Ni)h]-1, gather
The weight average molecular weight for closing the peak product GPC 1 is 217.8kg/mol, and the weight average molecular weight of polydispersity coefficient 2.4, peak 2 is
52.6kg/mol, polydispersity coefficient 2.2.1The polymer branching degree of H-NMR measurement is 72/1000 carbon atom.
Embodiment 26
Ethylene polymerization under atmospheric pressure is carried out under the conditions of anhydrous and oxygen-free.Room temperature and ethylene pressure are under 0.1MPa, by 40mL
Methylene chloride injects in the Schlenk bottle of 100mL, then injects 2mmol co-catalyst methylaluminoxane thereto.With 10mL bis-
Chloromethanes dissolves 5 μm of ol major catalyst Ni7', is injected into Schlenk bottles.After polymerizeing half an hour, rapidly will with rubber head dropper
Polymer solution is instilled in methanol or acetone soln and is precipitated, filtered polymeric, then for several times with methanol or acetone washing,
2.62g polymer is weighed to obtain after being dried under vacuum to constant weight at 50 DEG C.Catalyst activity is 5.24 × 105g[mol(Ni)h]-1, gather
The weight average molecular weight for closing the peak product GPC 1 is 199.8kg/mol, and the weight average molecular weight of polydispersity coefficient 2.2, peak 2 is
53.5kg/mol, polydispersity coefficient 2.4.1The polymer branching degree of H-NMR measurement is 71/1000 carbon atom.
Embodiment 27
Co-catalyst is changed to aluminium diethyl monochloride, other conditions are identical as embodiment 20 as polymer processing methods.?
5.56g polymer.Catalyst activity is 1.11 × 106g[mol(Ni)h]-1, the weight average molecular weight at the peak polymerizate GPC 1 is
174.8kg/mol, polydispersity coefficient 2.2, the weight average molecular weight at peak 2 are 73.1kg/mol, polydispersity coefficient 1.9.1H-
The polymer branching degree of NMR measurement is 79/1000 carbon atom.
Embodiment 28
Co-catalyst is changed to ethyl aluminum dichloride, other conditions are identical as embodiment 20 as polymer processing methods.?
7.68g polymer.Catalyst activity is 1.54 × 106g[mol(Ni)h]-1, the weight average molecular weight at the peak polymerizate GPC 1 is
155.8kg/mol, polydispersity coefficient 2.3, the weight average molecular weight at peak 2 are 54.5kg/mol, polydispersity coefficient 2.1.1H-
The polymer branching degree of NMR measurement is 82/1000 carbon atom.
Embodiment 29
Co-catalyst is changed to sesquialter aluminium ethide, other conditions are identical as embodiment 20 as polymer processing methods.?
7.26g polymer.Catalyst activity is 1.45 × 106g[mol(Ni)h]-1, the weight average molecular weight at the peak polymerizate GPC 1 is
171.5kg/mol, polydispersity coefficient 2.1, the weight average molecular weight at peak 2 are 68.1kg/mol, polydispersity coefficient 2.2.1H-
The polymer branching degree of NMR measurement is 81/1000 carbon atom.
Embodiment 30
Ethylene polymerization under atmospheric pressure is carried out under the conditions of anhydrous and oxygen-free.Room temperature and ethylene pressure are under 0.1MPa, by 40mL
Methylene chloride injects in the Schlenk bottle of 100mL, then injects 2mmol co-catalyst methylaluminoxane thereto, then thereto
Inject 0.1mmol chain shuttling agent trimethyl aluminium.5 μm of ol major catalyst Ni1 are dissolved with 10mL methylene chloride, are injected into
In Schlenk bottles.After polymerizeing half an hour, polymer solution is instilled in methanol or acetone soln rapidly with rubber head dropper and is sunk
Form sediment, filtered polymeric, then for several times with methanol or acetone washing, be dried under vacuum at 50 DEG C after constant weight weigh 2.68g is poly-
Close object.Catalyst activity is 5.36 × 105g[mol(Ni)h]-1, the weight average molecular weight of polymerizate is 225.3kg/mol, more points
Dissipating coefficient is 2.5.1The polymer branching degree of H-NMR measurement is 71/1000 carbon atom.
Embodiment 31
Chain shuttling agent is changed to triethyl aluminum, other conditions are identical as embodiment 30 as polymer processing methods.Obtain 2.35g
Polymer.Catalyst activity is 4.70 × 105g[mol(Ni)h]-1, the weight average molecular weight of polymerizate is 213.7kg/mol, more
The coefficient of dispersion is 2.6.1The polymer branching degree of H-NMR measurement is 73/1000 carbon atom.
Embodiment 32
Chain shuttling agent is changed to triisobutyl aluminium, other conditions are identical as embodiment 30 as polymer processing methods.?
2.58g polymer.Catalyst activity is 5.16 × 105g[mol(Ni)h]-1, the weight average molecular weight of polymerizate is 225.7kg/
Mol, polydispersity coefficient 2.5.1The polymer branching degree of H-NMR measurement is 72/1000 carbon atom.
Embodiment 33
Chain shuttling agent is changed to dibutylmagnesium, other conditions are identical as embodiment 30 as polymer processing methods.Obtain 2.48g
Polymer.Catalyst activity is 4.96 × 105g[mol(Ni)h]-1, the weight average molecular weight of polymerizate is 232.1kg/mol, more
The coefficient of dispersion is 2.4.1The polymer branching degree of H-NMR measurement is 70/1000 carbon atom.
Embodiment 34
Chain shuttling agent is changed to dimethyl magnesium, other conditions are identical as embodiment 30 as polymer processing methods.Obtain 2.68g
Polymer.Catalyst activity is 5.36 × 105g[mol(Ni)h]-1, the weight average molecular weight of polymerizate is 228.2kg/mol, more
The coefficient of dispersion is 2.6.1The polymer branching degree of H-NMR measurement is 73/1000 carbon atom.
Embodiment 35
Chain shuttling agent is changed to diethyl zinc, other conditions are identical as embodiment 30 as polymer processing methods.Obtain 2.59g
Polymer.Catalyst activity is 5.18 × 105g[mol(Ni)h]-1, the weight average molecular weight of polymerizate is 225.3kg/mol, more
The coefficient of dispersion is 2.5.1The polymer branching degree of H-NMR measurement is 73/1000 carbon atom.
Six, double-core (alpha-diimine) Raney nickel is catalyzed alpha-olefin homopolymerization and reacts with ethylene copolymer
Embodiment 36
Ethylene and the combined polymerization of 1- laurylene are carried out under the conditions of anhydrous and oxygen-free.Room temperature and ethylene pressure are 0.1MPa
Under, by the Schlenk bottle of 40mL toluene injection 100mL, 3.3mL 1- laurylene is reinjected, then injects 2mmol thereto
Co-catalyst methylaluminoxane.5 μm of ol major catalyst Ni1 are dissolved with 10mL toluene, are injected into Schlenk bottles.Polymerization half
After hour, polymer solution is instilled in methanol or acetone soln rapidly with rubber head dropper and is precipitated, filtered polymeric, then
For several times with methanol or acetone washing, 2.22g polymer is weighed to obtain after constant weight is dried under vacuum at 50 DEG C.Catalyst activity is
4.44×105g[mol(Ni)h]-1, the weight average molecular weight of polymerizate is 226.3kg/mol, polydispersity coefficient 2.1.Through DSC
Measurement, melting enthalpy 24.3J/g, fusing point are -43.1 DEG C.
Embodiment 37
Polymerization is carried out in the case where 4.5mL 1- octadecylene is added, other conditions and polymer processing methods and reality
It is identical to apply example 36.Obtain 2.17g polymer.Catalyst activity is 4.34 × 105g[mol(Ni)h]-1, the Weight-average molecular of polymerizate
Amount is 227.1kg/mol, polydispersity coefficient 2.2.It is measured through DSC, melting enthalpy 40.7J/g, fusing point is -18.5 DEG C.
Embodiment 38
Polymerization is carried out in the case where 9.6mL 1- octadecylene is added, other conditions and polymer processing methods and reality
It is identical to apply example 36.Obtain 2.35g polymer.Catalyst activity is 4.70 × 105g[mol(Ni)h]-1, the Weight-average molecular of polymerizate
Amount is 235.3kg/mol, polydispersity coefficient 2.0.It is measured through DSC, melting enthalpy 65.6J/g, fusing point is 2.8 DEG C.
Embodiment 39
Polymerization is carried out in the case where 14.4mL 1- octadecylene is added, other conditions and polymer processing methods with
Embodiment 36 is identical.Obtain 2.85g polymer.Catalyst activity is 5.70 × 105g[mol(Ni)h]-1, polymerizate divides equally again
Son amount is 244.1kg/mol, polydispersity coefficient 2.2.It is measured through DSC, melting enthalpy 60.1J/g, fusing point is 6.5 DEG C.
Embodiment 40
Propylene pressure polymerization is carried out in 100mL stainless steel polymeric kettle.Room temperature and propylene pressure are to incite somebody to action under 0.4MPa
40mL toluene injects in stainless steel polymeric kettle, then injects 2mmol co-catalyst methylaluminoxane thereto.It is molten with 10mL toluene
5 μm of ol major catalyst Ni1 are solved, are injected into stainless steel polymeric kettle.After polymerizeing half an hour, kettle is opened in pressure release, fast with rubber head dropper
Polymer solution is instilled in methanol or acetone soln and is precipitated by speed, filtered polymeric, then uses methanol or acetone washing number
It is secondary, 0.72g polymer is weighed to obtain after constant weight is dried under vacuum at 50 DEG C.Catalyst activity is 1.44 × 105g[mol(Ni)h
]-1, the weight average molecular weight of polymerizate is 153.4kg/mol, polydispersity coefficient 2.6.1H-NMR measures polymer branching degree
275/1000 carbon atom.
Claims (5)
1. a kind of double-core (alpha-diimine) nickel/palladium alkene catalyst, which is characterized in that its chemical structural formula such as Formulas I or Formula II institute
Show：
In above formula, R1For methyl or isopropyl, R2For methyl or isopropyl, R3For H, methyl or by 2 R3Form camphyl or naphthalene
And its derivative, R4For H, methyl or by 2 R4Form camphyl or naphthalene and its derivative, R5For methyl, tert-butyl, diphenyl
Methyl or isopropyl, R6For methyl, tert-butyl, diphenyl methyl or isopropyl, R7For H, methyl, tert-butyl, methoxyl group, N, N-
Dimethyl-amino, Cl, Br, CF3Or NO2, R8For H, methyl, tert-butyl, methoxyl group, N, N- dimethyl-amino, Cl, Br, CF3
Or NO2；R7And R8When being simultaneously H, 2 R3With 2 R4It is not simultaneously naphthalene；X is Cl or Br.
2. a kind of method for preparing double-core described in claim 1 (alpha-diimine) nickel/palladium alkene catalyst, which is characterized in that
Include the following steps：
(1) aniline is added drop-wise to progress ketoamine condensation reaction in equimolar diketone, obtains compound C1；Wherein, it is wrapped in aniline
It include substituent R 3 in diketone containing substituent R 5 and R7；
(2) aniline is added drop-wise to progress ketoamine condensation reaction in equimolar diketone, obtains compound C2；Wherein, it is wrapped in aniline
It include substituent R 4 in diketone containing substituent R 6 and R8；
(3) compound C1 is added drop-wise in equimolar 4,4'- methylene bis- (the disubstituted aniline of 2,6-) and carries out ketoamine condensation instead
It answers, obtains compound C3：
(4) compound C3 and equimolar compound C2 is subjected to ketoamine condensation reaction, obtains ligand L：
(5) under conditions of anhydrous and oxygen-free, by ligand L respectively with (DME) NiBr2、NiCl2·6H2O or (COD) PdCH3Cl network
It closes, obtains double-core described in Formulas I or Formula II (alpha-diimine) nickel/palladium alkene catalyst.
3. a kind of double-core (alpha-diimine) nickel/palladium alkene catalyst composition, which is characterized in that the composition is in addition to including right
It is required that also including the second component co-catalyst except double-core described in 1 (alpha-diimine) nickel/palladium alkene catalyst；This, which is helped, urges
Agent is Li (Et2O)2.8B(C6F5)4, methylaluminoxane, aluminium diethyl monochloride, appointing in ethyl aluminum dichloride or sesquialter aluminium ethide
It anticipates one kind.
4. double-core (alpha-diimine) nickel/palladium alkene catalyst composition according to claim 3, which is characterized in that the group
Closing in object further includes chain shuttling agent, is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, dibutylmagnesium, dimethyl magnesium or diethyl
Any one in zinc.
5. the double-core of claim 3 or 4 (alpha-diimine) nickel/palladium alkene catalyst composition is preparing polyethylene, polypropylene
Or the application in ethylene and alpha olefin copolymer.
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| CN101125866A (en) * | 2007-07-26 | 2008-02-20 | 浙江大学 | Double-core nickel series compounds, preparation method and application thereof |
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| WO2020124557A1 (en) * | 2017-12-25 | 2020-06-25 | 杭州星庐科技有限公司 | VINYLIDENE ACENAPHTHENE α-DIIMINE NICKEL OLEFIN CATALYST AND PREPARATION METHOD AND APPLICATION THEREOF |
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