CN111377827B - Alpha-diimine ligand compound, complex and preparation method of polyolefin lubricating oil base oil - Google Patents
Alpha-diimine ligand compound, complex and preparation method of polyolefin lubricating oil base oil Download PDFInfo
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- CN111377827B CN111377827B CN201811633475.9A CN201811633475A CN111377827B CN 111377827 B CN111377827 B CN 111377827B CN 201811633475 A CN201811633475 A CN 201811633475A CN 111377827 B CN111377827 B CN 111377827B
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- ligand
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- diimine
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- 239000003446 ligand Substances 0.000 title claims abstract description 142
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 77
- 239000002199 base oil Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 19
- 238000010668 complexation reaction Methods 0.000 title description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 62
- 229910052801 chlorine Inorganic materials 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 37
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 33
- -1 diketone compound Chemical class 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 125000006413 ring segment Chemical group 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 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
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 118
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000010516 chain-walking reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 160
- 238000005481 NMR spectroscopy Methods 0.000 description 96
- 230000015572 biosynthetic process Effects 0.000 description 69
- 238000003786 synthesis reaction Methods 0.000 description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 54
- 125000004432 carbon atom Chemical group C* 0.000 description 47
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 34
- 229910052759 nickel Inorganic materials 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 229920013639 polyalphaolefin Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 8
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 8
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000006384 oligomerization reaction Methods 0.000 description 7
- KWZKDAVFBAECCL-UHFFFAOYSA-N 3,10-dichlorotetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaene-15,16-dione Chemical compound ClC1=CC=CC=2C3C4=C(C=CC=C4C(C1=2)C(C3=O)=O)Cl KWZKDAVFBAECCL-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PJNXSALRLZQHHC-UHFFFAOYSA-N ctk2g8685 Chemical compound C12=CC3=CC=CC=C3C=C2C2C(=O)C(=O)C1C1=CC3=CC=CC=C3C=C12 PJNXSALRLZQHHC-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 5
- RQBZXUOVNFIZGW-UHFFFAOYSA-N 2-(furan-2-yl)aniline Chemical compound NC1=CC=CC=C1C1=CC=CO1 RQBZXUOVNFIZGW-UHFFFAOYSA-N 0.000 description 5
- PNENILSCXNGKPX-UHFFFAOYSA-N 3,10-dibromotetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaene-15,16-dione Chemical compound C1=CC2=C(C3C4=C(C2C(=O)C3=O)C(=CC=C4)Br)C(=C1)Br PNENILSCXNGKPX-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000002053 thietanyl group Chemical group 0.000 description 3
- DIMYVOCPPKNNPF-UHFFFAOYSA-N 1,5-dibromoanthracene Chemical compound C1=CC=C2C=C3C(Br)=CC=CC3=CC2=C1Br DIMYVOCPPKNNPF-UHFFFAOYSA-N 0.000 description 2
- SGUDFHYGRVFRTA-UHFFFAOYSA-N 1,5-dichloroanthracene Chemical compound C1=CC=C2C=C3C(Cl)=CC=CC3=CC2=C1Cl SGUDFHYGRVFRTA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-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
- 238000004821 distillation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 2
- UFCVADNIXDUEFZ-UHFFFAOYSA-N pentacene-6,13-dione Chemical compound C1=CC=C2C=C3C(=O)C4=CC5=CC=CC=C5C=C4C(=O)C3=CC2=C1 UFCVADNIXDUEFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 description 1
- SRRLOAAMZYZYQY-UHFFFAOYSA-N 1,5-dibromoanthracene-9,10-dione Chemical compound O=C1C2=C(Br)C=CC=C2C(=O)C2=C1C=CC=C2Br SRRLOAAMZYZYQY-UHFFFAOYSA-N 0.000 description 1
- MQIUMARJCOGCIM-UHFFFAOYSA-N 1,5-dichloroanthracene-9,10-dione Chemical compound O=C1C2=C(Cl)C=CC=C2C(=O)C2=C1C=CC=C2Cl MQIUMARJCOGCIM-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- RDWOKNADTSWGGB-UHFFFAOYSA-N 2-naphthalen-1-ylaniline Chemical compound NC1=CC=CC=C1C1=CC=CC2=CC=CC=C12 RDWOKNADTSWGGB-UHFFFAOYSA-N 0.000 description 1
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- YUTPSMJOCLLMBK-UHFFFAOYSA-N 3-thiophen-2-ylaniline Chemical compound NC1=CC=CC(C=2SC=CC=2)=C1 YUTPSMJOCLLMBK-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- BXYRAPNURYRQSP-UHFFFAOYSA-N 4-pyridin-2-ylaniline Chemical compound C1=CC(N)=CC=C1C1=CC=CC=N1 BXYRAPNURYRQSP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000006859 Swern oxidation reaction Methods 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003725 azepanyl group Chemical group 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 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
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 1
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical compound C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 description 1
- 125000005043 dihydropyranyl group Chemical group O1C(CCC=C1)* 0.000 description 1
- 125000004655 dihydropyridinyl group Chemical group N1(CC=CC=C1)* 0.000 description 1
- 125000005057 dihydrothienyl group Chemical group S1C(CC=C1)* 0.000 description 1
- 125000005072 dihydrothiopyranyl group Chemical group S1C(CCC=C1)* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940054441 o-phthalaldehyde Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000003551 oxepanyl group Chemical group 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000004853 tetrahydropyridinyl group Chemical group N1(CCCC=C1)* 0.000 description 1
- 125000004632 tetrahydrothiopyranyl group Chemical group S1C(CCCC1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Images
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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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- 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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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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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
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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Abstract
The invention provides an alpha-diimine ligand compound which has a structure shown as a formula (I), and also provides an alpha-diimine complex obtained by the ligand compound. In addition, the invention also provides a preparation method of the polyolefin lubricating oil base oil by taking the alpha-diimine complex as a catalyst and the prepared lubricating oil base oil. According to the ligand compound and the obtained complex provided by the invention, a large steric hindrance group is introduced into a ligand skeleton, and the rigidity of the skeleton is increased, so that the chain walking capability of the complex as a catalyst is improved. The polyolefin lubricating oil base oil provided by the invention has higher long-chain branch content and branching degree, can be used as medium-high viscosity lubricating oil base oil, simplifies the production process, reduces the production cost, is very suitable for industrial scale production, and has excellent economic benefit and social benefit.
Description
Technical Field
The invention relates to the technical field of synthetic lubricating oil base oil, in particular to an alpha-diimine ligand compound, an obtained complex, a preparation method of polyolefin lubricating oil base oil using the complex and prepared medium-high viscosity lubricating oil base oil.
Background
The lubricating oil base oil mainly comprises mineral base oil, synthetic base oil and vegetable oil base oil. Compared with mineral base oil, the synthetic base oil has the characteristics of good viscosity-temperature performance (high viscosity index), good low-temperature fluidity (low pour point), good oxidation stability, small high-temperature loss, less coking and no toxicity. It has wide application in gear oil, hydraulic oil, internal combustion engine oil and other base oil. Among them, polyalphaolefins (PAO) are the fastest growing and very large variety in synthetic base oils. Generally, the base oil can be divided into low, medium and high viscosity base oil, and the kinematic viscosity at 100 ℃ is taken as the standard of viscosity classification; below 10mm 2 S is low viscosity base oil, 10-40mm 2 Has a viscosity of greater than 40mm per second of the base oil 2 And/s is high viscosity base oil. The PAO base oils are predominantly long chain alpha-olefins (C) 8 -C 12 ) The oligomer has excellent viscosity-temperature performance and low-temperature service performance, and the key point is that the oligomer has a special branched structure. The high content of long chain branches in PAOs results in a high viscosity index of the lubricating oil, and the highly branched structure is more favorable for improving low temperature fluidity. Researches show that the optimized long-chain branch has 8 carbon atoms and less than 8 carbon atoms, and the viscosity-temperature performance of the product is poor; above 8 carbons, the branches may crystallize, resulting in poor low temperature fluidity.
PAO base oils are currently predominantly prepared from long chain alpha-olefins by coordination polymerization (Ziegler-Natta or metallocene catalysts) or cationic polymerization (AlCl) 3 Or BF 3 ) And (3) oligomerization. When in useThe former alpha-olefin is expensive and is obtained industrially by catalyzing ethylene oligomerization through an SHOP process. The existing synthesis of PAO base oil by taking ethylene as a raw material needs three-step catalytic reaction and one-step high-temperature reduced distillation process, including selective oligomerization of ethylene to prepare alpha-olefin, oligomerization of alpha-olefin, catalytic hydrogenation and reduced distillation grading, the whole process involves 3 catalyst systems, and the synthesis process is complex, high in energy consumption and large in pollution. If the ethylene is used as the raw material to directly synthesize the polyolefin lubricating oil base oil by the one-step method, the production process can be greatly simplified, and the production cost can be greatly reduced. This requires the design of a suitable catalyst system capable of catalyzing the polymerization of ethylene to produce a product with high long chain branch content similar to the PAO structure.
Professor Brookhart in the united states developed an alpha-diimine nickel palladium catalyst system (j.am. Chem. Soc.,1995,117, 6414-6415) and found that alpha-diimine nickel palladium catalysts have a unique chain walking capability. The catalyst system catalyzes ethylene to polymerize and obtain a highly branched polymerization product, and the molecular weight of the product can be adjusted by the size of the aromatic ring ortho-substituent. Since the chain walking process is a random process, the branched structure of the obtained product is complex, and generally contains methyl, ethyl, propyl, butyl, pentyl and long-chain branches (C > 6), and the content of methyl is generally higher than 50%, and the content of long-chain branches is relatively low. The alpha-diimine palladium catalyst has stronger chain walking capability, and can obtain a highly branched liquid polyethylene product by catalyzing ethylene polymerization, and the branching degree is as high as 300/1000C. However, since the product mainly contains methyl groups and has very little long chain branch content, the viscosity-temperature performance of the product is poor and cannot meet the basic requirements for lubricating oil use (ind. Eng.chem.res.,2007,46,1174-1178, mm. Eng.sci.,2010,50, 911-918.
Thangyong, CN 105503763A, CN 103360517A and CN 102786435B disclose a catalytic system for preparing highly branched alkane from olefin, wherein the catalyst is mainly an alpha-nickel diimine catalyst system, and high molecular weight branched polymer and low molecular weight branched oily product are prepared by adjusting different size substituents at ortho-position of aromatic ring. CN 104803899A patent disclosesThe heteroatom-assisted alpha-nickel diimine catalyst is used for catalyzing ethylene polymerization to directly prepare polyolefin base oil. Since the framework structures of these nickel alpha-diimine catalyst systems are similar to those reported in the earlier professor Brookhart, the chain-walking mechanism is essentially the same. The liquid products prepared using these catalyst systems have a relatively low kinematic viscosity at 100 ℃ owing to the high content of short chain branches (<11mm 2 S) can only be used as a low viscosity base oil. CN 104277165A patent proposes that ionic liquid is used for catalyzing ethylene oligomerization and reducing evaporation for grading to prepare polyolefin base oil, the obtained base oil is still low-viscosity base oil, CN 106519087A patent discloses that alpha-nickel diimine is used for catalyzing ethylene polymerization to obtain liquid polyethylene product, the content of long chain branches of the liquid polyethylene product is less than 25mol%, and the product serving as liquid rubber can be used as adhesive, coating, paint, reactive operation oil, resin modified material and sealing caulking material. Based on the existing research results, it is not difficult to find that the current catalyst system can obtain products with high short chain branch content and low long chain branch content according to a chain walking mechanism, so that the lubricating oil base oil with medium and high viscosity can not be prepared in one step by ethylene oligomerization.
Disclosure of Invention
In order to overcome the defects of the existing alpha-diimine catalyst system in the preparation of polyolefin lubricant base oil, the invention aims to provide an alpha-diimine ligand compound.
Another object of the present invention is to provide an α -diimine complex.
It is a further object of the present invention to provide a process for preparing a polyolefin lubricant base oil and the lubricant base oil so prepared.
The alpha-diimine ligand compound has a structure shown as a formula (I),
in the formula (I), R 1 、R 1 ' independently of one another represent a substituted or unsubstituted heteroaryl radical having from 4 to 14 ring atomsOr an aryl group;
y, Z, Y 'and Z' each independently represent hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, substituted or unsubstituted heterocyclyl or cycloalkyl having 3 to 10 ring atoms, substituted or unsubstituted heteroaryl or aryl having 4 to 14 ring atoms; or Y, Z and the adjacent carbon atoms together form a substituted or unsubstituted heteroaryl or aryl group having 4 to 14 ring atoms; or Y ', Z' together with the adjacent carbon atoms form a substituted or unsubstituted heteroaryl or aryl group having from 4 to 14 ring atoms;
wherein, R is 1 、R 1 ', Y, Z, Y ', Z ' represent a substituted group, the substituent is one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl.
In the current research, the alpha-diimine catalyst is mainly used for adjusting substituents on an aniline aromatic ring in an alpha-diimine ligand to improve the catalytic performance, and substituents on a ligand framework are all substituents with small steric hindrance, such as methyl or acenaphthylene with a planar structure. In the ligand compound, the substituent group on the ligand skeleton is bicyclooctane with higher rigidity, the rigid skeleton has large steric hindrance effect, and the chain walking capability and speed of the catalyst can be enhanced. In addition, in the ligand compound, only one substituent is arranged at the ortho position of the aniline aromatic ring, so that the axial steric hindrance of the complex can be reduced, and the preparation of a low-molecular-weight base oil product is facilitated.
In the ligand compound provided by the invention, the expression meanings of each substituent group are as follows:
halogen may include fluorine, chlorine, bromine, iodine.
The C1-C6 alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-l-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-l-butyl, 2-methyl-3-butyl, 2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-l-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-dimethyl-l-butyl, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, and the like.
C1-C6 alkoxy may be represented by-OC 1-C6 alkyl, wherein C1-C6 alkyl includes groups as previously defined; for example, C1-C6 alkoxy can include, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and the like.
The C1-C6 halogenated alkyl can be a group formed by replacing any number of hydrogen atoms in the C1-C6 alkyl by halogen, wherein the groups included by the C1-C6 alkyl and the halogen are defined as before; for example, C1-C6 haloalkyl can include, but is not limited to, -CF 3 And the like.
Cycloalkyl groups may be represented by non-aromatic saturated carbocyclic rings, including mono-carbocyclic rings (having one ring) and bi-carbocyclic rings (having two rings), for example, cycloalkyl groups may include, but are not limited to
And the like.
The heterocyclic group may be a cycloalkyl group in which any number of ring atoms are substituted with a hetero atom such as O, S, N, P, si or the like, wherein the cycloalkyl group includes the groups as defined above. For example, heterocyclyl groups can include, but are not limited to, oxiranyl, thietanyl, cycloazanyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuryl, pyrrolidinyl, oxazolidinyl, tetrahydropyrazolyl, pyrrolinyl, dihydrofuranyl, dihydrothienyl, piperidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, piperazinyl, dihydropyridinyl, tetrahydropyridinyl, dihydropyranyl, dihydrothiopyranyl, azepanyl, oxepanyl, thietanyl, oxaazabicyclo [2.2.1] heptyl, azaspiro [3.3] heptyl, and the like.
Aryl groups may include monocyclic aryl, bicyclic aryl, or higher cyclic aryl groups, and may include, for example, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, azulenyl, and the like.
The heteroaryl group may represent an unsaturated group containing any number of heteroatoms such as O, S, N, P, and Si as ring atoms. For example, heteroaryl groups can include, but are not limited to, pyrrolyl, furanyl, thienyl, imidazolyl, oxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, tetrazolyl, triazolyl, triazinyl, benzofuranyl, benzothienyl, indolyl, isoindolyl, and the like.
In the above definitions, when the number of carbon atoms is changed, the above definitions are changed only according to the change of the number of carbon atoms, and the definition of the group species is not affected; for example, "C1-C4 alkyl" may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and all of the groups having 1 to 4 carbon atoms in the definition of "C1-C6 alkyl" described above.
In one embodiment of the ligand compound provided herein, R is 1 、R 1 ' may each independently represent a substituted or unsubstituted heteroaryl group having 4 to 8 (e.g., may be 4, 5, 6, 7, 8) ring atoms including at least one heteroatom of N, S or O; wherein, the substituent can be one or more of chlorine, bromine, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 halogenated alkyl.
In one embodiment of the ligand compound provided herein, R is 1 、R 1 ' may also each independently represent a substituted or unsubstituted aryl group having 6 to 14 (e.g., may be 6, 7, 8, 9,10, 11,12, 13, 14) ring atoms; wherein, the substituent can be one or more of chlorine, bromine, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 halogenated alkyl.
One embodiment of the ligand compound provided by the present inventionIn the above-mentioned manner, R 1 、R 1 ' may represent the same group at the same time.
In one embodiment of the ligand compound provided herein, R is 1 、R 1 ' may each independently represent furyl, thienyl, pyridyl, phenyl or naphthyl.
In one embodiment of the ligand compound provided herein, R is 1 、R 1 ' may each independently be located at the ortho, meta or para position of the aniline aromatic ring; preferably in the ortho position.
In one embodiment of the ligand compound provided by the present invention, Y and Z may represent a substituted or unsubstituted aryl group having 6 to 14 (for example, 6, 7, 8, 9,10, 11,12, 13, 14) ring atoms, which is formed by Y and Z together with adjacent carbon atoms; and/or said Y ', Z' may represent a substituted or unsubstituted aryl group having 6 to 14 (e.g. may be 6, 7, 8, 9,10, 11,12, 13, 14) ring atoms which Y ', Z' together with the adjacent carbon atoms form; wherein, the substituent can be one or more of chlorine, bromine, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 halogenated alkyl.
In a preferred embodiment of the ligand compound provided by the present invention, the ligand compound has a structure represented by formula (1), formula (2) or formula (3),
wherein R is 1 Represents the same group as defined above;
R 2 represents chlorine, bromine, C1-C4 alkyl or C1-C4 haloalkyl.
The invention also provides a preparation method of the ligand compound, namely, the diketone compound shown as the formula (I-1) and R 1 And/or R 1 ' substituted aniline derivatives are prepared by a ketoamine condensation reaction.
In one embodiment of the process for producing a ligand compound provided by the present invention, the diketone compound represented by the formula (I-1) can be produced by the following process: the method comprises the steps of carrying out Diles-Alder addition reaction on conjugated diene containing a cyclic structure and vinylene carbonate to generate a carbonate compound, hydrolyzing under an alkaline condition to obtain an o-diol compound, and carrying out Swern oxidation to generate a diketone compound.
The invention also provides an alpha-diimine complex which has a structure as shown in a formula (II),
wherein R is 1 、R 1 ', Y, Z, Y ', Z ' represent the same groups as previously defined;
m represents Ni or Pd;
x represents halogen, C1-C6 alkyl or C1-C6 haloalkyl.
The alpha-diimine complex provided by the invention can be prepared by reacting the ligand compound provided by the invention with a salt of metal M. For example, the alpha-diimine ligand compound can be prepared by coordination reaction of a salt of nickel or palladium (e.g., 1, 2-dimethoxyethane nickel halide) in a solvent (e.g., dichloromethane) at room temperature under anhydrous and oxygen-free conditions.
In a preferred embodiment of the complex provided by the invention, the complex has a structure shown as a formula (A), a formula (B) or a formula (C),
wherein R is 1 、R 2 Denotes a group as defined above;
x represents chlorine or bromine.
The invention also provides a preparation method of the polyolefin lubricating oil base oil, which takes ethylene as a polymerization monomer and is prepared through a polymerization process under the catalysis of the alpha-diimine complex, wherein the alpha-diimine complex is the alpha-diimine complex in the technical scheme.
In the preparation method provided by the invention, the polymerization process can be carried out in conventional solvents, including but not limited to toluene, n-hexane and the like.
In the preparation method provided by the invention, the polymerization pressure in the polymerization process can be 0.5-10 atm.
In the preparation method provided by the invention, the polymerization temperature in the polymerization process can be 25-75 ℃.
In the preparation method provided by the invention, the polymerization time in the polymerization process can be 0.25-24 h.
In the preparation method provided by the invention, the polymerization process can be carried out under the anhydrous and anaerobic conditions.
In the preparation method provided by the invention, alkyl aluminum can be also contained as a cocatalyst in the polymerization process. The alkylaluminum cocatalyst can be of all kinds used for the preparation of polyethylene base oils, including but not limited to methylaluminoxane, modified methylaluminoxane, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum monochloride, etc., and the aluminum/M ratio can be 100 to 800.
In the preparation method provided by the invention, the method can further comprise the following steps after the polymerization reaction is finished: and pouring the obtained reaction material into acidified ethanol with the mass fraction of 1-10%, washing to remove the cocatalyst, separating liquid, and removing the solvent to obtain the polyolefin base oil.
The invention also provides the polyolefin lubricating oil base oil prepared by the preparation method, wherein the content of branched chains with the length of more than C6 (the carbon number of the branched chains is more than or equal to 6) is 30-80 mol%, and the branching degree is 130-190 branched chains/1000 carbon atoms.
The molecular weight of the base oil of the polyolefin lubricating oil provided by the invention can be conveniently adjusted and can be 500-10,0000g/mol, preferably 500-2,0000g/mol. The polyolefin base oil provided by the invention can also be low molecular weight base oil, and the molecular weight can be 1000-10000 g/mol.
The invention provides polyolefinsThe lubricating oil base oil has higher long-chain branch content and branching degree, the ideal molecular structure of the base oil product and the PAO base oil is closer due to the high content of long-chain branches, and the high branching degree is beneficial to reducing the pour point of the base oil. Therefore, the base oil provided by the invention has excellent viscosity-temperature performance (viscosity index is 160-240) and low-temperature fluidity (pour point is-36-60 ℃) at the same time, and is very suitable for being used as medium and high viscosity (kinematic viscosity is 10-80 mm at 100 ℃) 2 S) lubricant base oil.
The invention has the following beneficial effects:
(1) The alpha-diimine ligand compound and the obtained complex provided by the invention introduce a large steric hindrance group into a ligand framework, and the rigidity of the framework is increased, so that the chain walking capability of the complex as a catalyst is improved, and the performance of a product obtained by catalysis can be improved. Moreover, the ligand compound and the obtained complex have simple preparation process and mild reaction condition.
(2) The polyolefin lubricating oil base oil provided by the invention is prepared by the catalytic action of the alpha-diimine complex, has higher long-chain branch content and branching degree, has good low-temperature fluidity and excellent viscosity-temperature performance compared with the traditional PAO base oil, has higher viscosity index, and can be used as medium-high viscosity lubricating oil base oil.
(3) The polyolefin lubricating oil base oil provided by the invention is prepared by taking cheap ethylene as a raw material and the alpha-diimine complex as a catalyst through one-step polymerization, greatly simplifies the production process and reduces the production cost compared with the traditional three-step catalytic reaction and reduced evaporation process of PAO, is very suitable for industrial scale production, and has excellent economic benefit and social benefit.
Drawings
FIG. 1 is a photograph of a polyethylene base oil obtained by the preparation method of the present invention.
FIG. 2 is a nuclear magnetic carbon spectrum of a polyethylene base oil obtained in example 68 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, technical solutions of exemplary embodiments of the present invention will be further described below.
The ligands and catalysts of the present invention can be prepared by the following examples. The following examples are for illustrative purposes only and these schemes and examples should not be construed as limiting the invention in any way. The ligands and catalysts described herein can also be synthesized using standard synthetic techniques known to those skilled in the art, or using methods known in the art in combination with the methods described herein.
The synthetic methods and polymerization methods used in the following examples are conventional methods or literature-referenced methods unless otherwise specified. The materials, reagents and the like used in the following examples are commercially available or can be prepared by literature unless otherwise specified.
For the sake of conciseness and clarity of the ligands and complexes in the examples, the following are illustrated:
ligands
The ligand L1 is (1) type alpha-diimine ligand, wherein R 1 Is 2- (2-furyl);
the ligand L2 is an alpha-diimine ligand of type (1), wherein R 1 Is 3- (2-thienyl);
the ligand L3 is an alpha-diimine ligand of type (1), wherein R 1 Is 4- (2-pyridyl);
ligand L4 is an alpha-diimine ligand of type (1), wherein R 1 Is 2-phenyl;
ligand L5 is an alpha-diimine ligand of type (1), wherein R 1 Is 2- (1-naphthyl);
ligand L6 is an alpha-diimine ligand of type (2) wherein R 1 Is 2- (2-furyl), R 2 Is a chlorine atom;
ligand L7 is an alpha-diimine ligand of type (2), wherein R 1 Is 3- (2-thienyl), R 2 Is a chlorine atom;
ligand L8 is an alpha-diimine ligand of type (2), wherein R 1 Is 4- (2-pyridyl), R 2 Is a chlorine atom;
ligand L9 is an alpha-diimine ligand of type (2), wherein R 1 Is 2-phenyl, R 2 Is a chlorine atom;
ligand L10 is an alpha-diimine ligand of type (2), wherein R 1 Is 2- (1-naphthyl), R 2 Is a chlorine atom;
ligand L11 is an alpha-diimine ligand of type (2), wherein R 1 Is 2- (2-furyl), R 2 Is a bromine atom;
ligand L12 is an alpha-diimine ligand of type (2), wherein R 1 Is 3- (2-thienyl), R 2 Is a bromine atom;
ligand L13 is an alpha-diimine ligand of type (2), wherein R 1 Is 4- (2-pyridyl), R 2 Is a bromine atom;
ligand L14 is an alpha-diimine ligand of type (2) wherein R 1 Is 2-phenyl, R 2 Is a bromine atom;
ligand L15 is an alpha-diimine ligand of type (2), wherein R 1 Is 2- (1-naphthyl), R 2 Is a bromine atom;
the ligand L16 is an alpha-diimine ligand of type (3), wherein R 1 Is 2- (2-furyl);
ligand L17 is an alpha-diimine ligand of type (3) wherein R 1 Is 3- (2-thienyl);
ligand L18 is an alpha-diimine ligand of type (3) wherein R 1 Is 4- (2-pyridyl);
ligand L19 is an alpha-diimine ligand of type (3) wherein R 1 Is 2-phenyl;
ligand L20 is an alpha-diimine ligand of type (3), wherein R 1 Is 2- (1-naphthyl).
Catalyst and process for preparing same
Catalyst 1 is an alpha-diimine nickel complex of type (A), wherein R 1 Is 2- (2-furyl) and X is a chlorine atom;
catalyst 2 is (A) type alpha-diimine nickel complex, wherein R 1 Is 2- (2-furyl) and X is a bromine atom;
catalyst 3 is (A) type alpha-diimine nickel complex, wherein R 1 Is 3- (2-thienyl), and X is a chlorine atom;
catalyst 5 is (A) type alpha-diimine nickel compoundCompound (I) wherein R 1 Is 2-phenyl, X is chlorine atom;
catalyst 6 is an alpha-diimine nickel complex of type (A), wherein R 1 Is 2- (1-naphthyl), X is chlorine atom;
catalyst 7 is an alpha-diimine nickel complex of type (B), wherein R 1 Is 2- (2-furyl), R 2 Is a chlorine atom, X is a chlorine atom;
catalyst 8 is (B) type alpha-nickel diimine complex, wherein R 1 Is 2- (2-furyl), R 2 Is a chlorine atom and X is a bromine atom;
catalyst 9 is (B) type alpha-diimine nickel complex, wherein R 1 Is 3- (2-thienyl), R 2 Is a chlorine atom, and X is a chlorine atom;
catalyst 11 is an alpha-nickel diimine complex of type (B) wherein R 1 Is 2-phenyl, R 2 Is a chlorine atom, X is a chlorine atom;
catalyst 12 is an alpha-diimine nickel complex of type (B) wherein R 1 Is 2- (1-naphthyl), R 2 Is a chlorine atom, and X is a chlorine atom;
catalyst 13 is an alpha-diimine nickel complex of type (B), wherein R 1 Is 2- (2-furyl), R 2 Is bromine atom, X is chlorine atom;
catalyst 14 is an alpha-diimine nickel complex of type (B) wherein R 1 Is 2- (2-furyl), R 2 Is a bromine atom, and X is a bromine atom;
catalyst 16 is an alpha-diimine nickel complex of type (B) wherein R 1 Is 4- (2-pyridyl), R 2 Is bromine atom, X is chlorine atom;
catalyst 17 is an alpha-diimine nickel complex of type (B), wherein R 1 Is 2-phenyl, R 2 Is bromine atom, X is chlorine atom;
catalyst 18 is an alpha-diimine nickel complex of type (B) wherein R 1 Is 2- (1-naphthyl), R 2 Is bromine atom, X is chlorine atom;
catalyst 19 is an alpha-nickel diimine complex of the type (C) in which R 1 Is 2- (2-furyl) and X is a chlorine atom;
catalyst 21 is an alpha-diimine nickel complex of the type (C) wherein R 1 Is 3- (2-thienyl), and X is a chlorine atom;
catalyst 22 is an alpha-nickel diimine complex of the type (C) wherein R 1 Is 4- (2-pyridyl), and X is a chlorine atom;
catalyst 23 is an alpha-diimine nickel complex of the type (C) wherein R 1 Is 2-phenyl, X is a chlorine atom;
catalyst 24 is an alpha-nickel diimine complex of the type (C) wherein R 1 Is 2- (1-naphthyl) and X is a chlorine atom.
Synthesis of ligands
Example 1 Synthesis of ligand L1
Synthesis of bicyclo [2, 2] octane-2, 3-dione:
8.0g of 1, 3-cyclohexadiene (0.1 mol) and 43g of vinylene carbonate (0.5 mol) were charged into a pressure-resistant bottle and reacted at 180 ℃ for 24 hours. Cooling to room temperature and precipitating with methanol to obtain the addition product. Dissolving the product in tetrahydrofuran, adding 50mg Pd/C, reacting for 12h at 60 ℃ in hydrogen atmosphere, filtering, and removing the solvent by rotary evaporation. And dissolving the product in 5g of ethanol solution of potassium hydroxide, performing reflux reaction for 8 hours, washing with water, and drying to obtain the diol. Dissolving the product in a mixture of 200mL of dichloromethane and 8mL of dimethyl sulfoxide, dropwise adding 12mL of trifluoroacetic anhydride at-78 ℃, reacting for 2h, dropwise adding 25mL of triethylamine, continuously stirring for reacting for 2h, washing with liquid, drying with anhydrous sodium sulfate, and recrystallizing to obtain 10.86g of product with the yield of 56%. 1 H NMR(400MHz,CDCl 3 ,ppm)：2.08(m,4H,CH 2 )，2.04(m,2H,CH),1.83(m,4H,CH 2 ).
3.18g of 2- (2-furyl) aniline (20 mmol) was charged into a 100mL reaction flask, vacuum-pumped and nitrogen-filled three times, 50mL of toluene and 10mL of a 2mol/L solution of trimethylaluminum in toluene were injected, and the mixture was refluxed at 110 ℃ for 2 hours, and 1.38g of bicyclo [2, 2] dissolved in toluene was added]A solution of octane-2, 3-dione (10 mmol) in 10mL of toluene was refluxed for 6h. And cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 5% to terminate the reaction, separating the liquid, drying the organic phase by using anhydrous sodium sulfate, removing the solvent by rotary evaporation, and recrystallizing to obtain 2.86g of the ligand with the yield of 68.2%. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.79,7.51,7.41,7.39(m,8H,Ph-H)，7.86,7.07,6.68(m,6H,furyl)，2.42(m,2H,CH)，1.64(m,4H,CH 2 )，1.35(m,4H,CH 2 ).
Example 2 Synthesis of ligand L2
The synthesis of ligand L1 in example 1 was carried out using 3- (2-thienyl) aniline instead of 2- (2-furyl) aniline, under otherwise identical operating conditions, in 80.3% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.79,7.72,7.51,6.94(m,8H,Ph-H)，7.69,7.40,7.17(m,6H,thienyl)，2.56(m,2H,CH)，1.71(m,4H,CH 2 )，1.45(m,4H,CH 2 ).
Example 3 Synthesis of ligand L3
The synthesis of ligand L1 in example 1 was carried out using 4- (2-pyridyl) aniline instead of 2- (2-furyl) aniline under otherwise identical operating conditions, in 72.9% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.35,8.21,7.76,7.65(m,8H,Ph-H)，8.50,7.51,7.26,7.00(m,8H,pyridyl)，2.48(m,2H,CH)，1.84(m,4H,CH 2 )，1.53(m,4H,CH 2 ).
Example 4 Synthesis of ligand L4
The synthesis of ligand L1 in example 1 was carried out using 2-aminobiphenyl instead of 2- (2-furyl) aniline, under otherwise identical operating conditions, in 66.7% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.79,7.52-7.39(m,18H,Ph-H)，2.12(m,2H,CH)，1.45(m,4H,CH 2 )，1.12(m,4H,CH 2 ).
Example 5 Synthesis of ligand L5
The synthesis of ligand L1 in example 1 was carried out using 2- (1-naphthyl) aniline instead of 2- (2-furyl) aniline, under otherwise identical operating conditions, in 54.1% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.55-8.42,8.08-7.79,7.61-7.35(m,22H,Ar-H)，2.05(m,2H,CH)，1.38(m,4H,CH 2 )，1.06(m,4H,CH 2 ).
EXAMPLE 6 Synthesis of ligand L6
Synthesis of 1, 5-dichloro-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione:
adding 1, 5-dichloroanthraquinone (20g, 72.2mmol, 1equiv.), ammonia water (25%, 240 mL) and ultrapure water (180 mL) into a three-necked bottle, mechanically stirring under ice bath, slowly adding zinc powder (99.1g, 1.52mol, 21equiv.), naturally heating to room temperature and continuously stirring for 10min, then heating the solution to 75 ℃ and stirring for 4h, cooling to the ambient temperature after the reaction is finished, filtering suspended matters, extracting a filter cake with hot dichloromethane, collecting an organic layer, and distilling under reduced pressure to obtain 1, 5-dichloroanthracene grayish yellow solid. Adding 1, 5-dichloroanthracene and vinylene carbonate into a pressure-resistant bottle, reacting for 24 hours at 180 ℃, cooling to room temperature, and precipitating with methanol to obtain an addition product. And dissolving the product in an ethanol solution of potassium hydroxide, performing reflux reaction for 8 hours, washing with water, and drying to obtain the diol. Dissolving the product in a mixture of 200mL of dichloromethane and 8mL of dimethyl sulfoxide, dropwise adding 12mL of trifluoroacetic anhydride at-78 ℃, reacting for 2h, dropwise adding 25mL of triethylamine, continuously stirring for reacting for 2h, separating, washing with water, drying with anhydrous sodium sulfate, and recrystallizing to obtain the diketone compound. 1 HNMR(CDCl 3 ,400MHz),δ(ppm):7.49-7.31(m,6H,Ph),5.50(s,2H,CH).
The synthesis of ligand L1 in example 1 was followed, using 1, 5-dichloro-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2-dione]Octane-2, 3-dione, in the same operating conditions, in 69.4% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.81-7.42,7.20-7.13(m,14H,Ph-H)，7.95,7.12,6.75(m,6H,furyl)，3.95(s,2H,CH).
Example 7 Synthesis of ligand L7
The synthesis of ligand L2 as in example 2 was followed, using 1, 5-dichloro-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2-dione]Octane-2, 3-dione, in 62.1% yield, the other operating conditions being the same. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.93-7.51,7.35-7.26,7.22-7.10(m,20H,Ar-H)，4.12(s,2H,CH).
Example 8 Synthesis of ligand L8
The synthesis of ligand L3 in example 3 was followed, using 1, 5-dichloro-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2] -dione]Octane-2, 3-dione, in 63.7% yield, under otherwise identical operating conditions. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.50-8.32,7.93-7.51,7.22-7.13(m,22H,Ar-H)，4.36(s,2H,CH).
Example 9 Synthesis of ligand L9
The synthesis of ligand L4 in example 4 was followed, using 1, 5-dichloro-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2] -dione]Octane-2, 3-dione, in 54.6% yield, the other operating conditions being the same. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.83-7.35,7.21-7.05(m,24H,Ph-H)，3.74(s,2H,CH).
EXAMPLE 10 Synthesis of ligand L10
The synthesis of ligand L5 in example 5 was followed, using 1, 5-dichloro-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2] -dione]Octane-2, 3-dione, in 58.4% yield, the other operating conditions being the same. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.55-6.87(m,30H,Ar-H)，3.65(s,2H,CH).
EXAMPLE 11 Synthesis of ligand L11
Synthesis of 1, 5-dibromo-9, 10-dihydro-9, 10-ethano [ anth ] ene-11, 12-dione:
1, 5-diaminoanthraquinone (10.0g, 42.0mmol), copper bromide (21.2g, 94.6mmol) were added to acetonitrile (200 mL), and the suspension was added with rapid stirringTert-butyl nitrite (12.5mL, 90%), was warmed to 65 ℃ and stirred for 2h, cooled to room temperature after the reaction was complete, diluted hydrochloric acid (3M, 100mL) and water (100 mL) were added, stirring was continued for 20min, a large amount of precipitate was formed, filtered and washed with water and ethanol, respectively, and the remaining solid was dried in vacuo. Stirring the solid and silica gel uniformly, performing Soxhlet extraction by using chloroform as a solvent, and performing vacuum distillation and drying on the organic phase to obtain a yellow crude product 1, 5-dibromoanthraquinone. The resulting solid (13.7 g) was dissolved in isopropanol (250 mL), sodium borohydride (3.59g, 95mmol) was added under ice-bath conditions, and the reaction was stirred at 0 ℃ for 1.5h and at room temperature for 2h. The mixture was poured into a large volume of water (500 mL) and the resulting suspension was stirred for a further 3h until the green colour disappeared. The remaining precipitate was then filtered, washed with water and dried under vacuum to give an off-white solid powder. Adding 200mL of acetic acid and 19.0g of stannous chloride into the reaction bottle, 100mol, and heating and refluxing the system for 2h. After the reaction was completed, it was cooled to room temperature, and the mixture was poured into a large amount of water while stirring to precipitate a solid, the precipitate was filtered and washed with water, and the product after vacuum drying was separated by column chromatography using chloroform as a solvent to obtain 1, 5-dibromoanthracene in a pale yellow color with a yield of 71%. Adding 1, 5-dibromoanthracene and vinylene carbonate into a pressure-resistant bottle, reacting for 24 hours at 180 ℃, cooling to room temperature, and precipitating with methanol to obtain an addition product. And dissolving the product in an ethanol solution of potassium hydroxide, performing reflux reaction for 8 hours, and washing and drying to obtain the diol. Dissolving the product in a mixture of 200mL of dichloromethane and 8mL of dimethyl sulfoxide, dropwise adding 12mL of trifluoroacetic anhydride at-78 ℃, reacting for 2h, dropwise adding 25mL of triethylamine, continuously stirring for reacting for 2h, separating, washing with water, drying with anhydrous sodium sulfate, and recrystallizing to obtain the diketone compound. 1 H NMR(CDCl 3 ,400MHz),δ(ppm):7.62(d,1H,Ph),7.60(d,1H,Ph),7.49(s,1H,Ph),7.47(s,1H,Ph),7.31-7.25(m,2H,Ph),5.51(s,2H,CH).
The synthesis of ligand L1 in example 1 was followed, using 1, 5-dibromo-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2-dione]Octane-2, 3-dione, in the same operating conditions, in 75.3% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.75-7.36,7.25-7.08(m,14H,Ph-H)，7.86,7.12,6.68(m,6H,furyl)，3.84(s,2H,CH).
EXAMPLE 12 Synthesis of ligand L12
The synthesis of ligand L2 as in example 2 was followed, using 1, 5-dibromo-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [ 2.2.2 ] dione]Octane-2, 3-dione, in the same operating conditions, in 80.5% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.86-7.55,7.40-7.25,7.17-6.94(m,20H,Ar-H)，3.97(s,2H,CH).
Example 13 Synthesis of ligand L13
The synthesis of ligand L3 in example 3 was followed, using 1, 5-dibromo-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2-dione]Octane-2, 3-dione, in the same operating conditions, in 76.3% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.62-8.27,7.68-7.36,7.26-7.00(m,22H,Ar-H)，4.14(s,2H,CH).
EXAMPLE 14 Synthesis of ligand L14
The synthesis of ligand L4 in example 4 was followed, using 1, 5-dibromo-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2-dione]Octane-2, 3-dione, in 54.6% yield, the other operating conditions being the same. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.78-7.36,7.25-7.08(m,24H,Ph-H)，3.88(s,2H,CH).
Example 15 Synthesis of ligand L15
The synthesis of ligand L5 in example 5 was followed, using 1, 5-dibromo-9, 10-dihydro-9, 10-ethano-anthracene-11, 12-dione instead of bicyclo [2, 2-dione]Octane-2, 3-dione, in 85.6% yield, under otherwise identical operating conditions. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.56-7.08(m,30H,Ar-H)，3.74(s,2H,CH).
EXAMPLE 16 Synthesis of ligand L16
Synthesis of 6, 13-dihydro-6, 13-ethanopentacene-15, 16-dione:
o-phthalaldehyde (4.02g, 30mmol) and 1, 4-cyclohexanedione (1.68g, 15.0mmol) were dissolved in anhydrous ethanol, stirred uniformly, and added with NaOH aqueous solution (15mL, 15%), reactantThe lines immediately turned tan. The reaction was stirred at 60 ℃ for 4h, cooled to room temperature after completion of the reaction, the solid was filtered and washed with acetone until the filtrate was colorless to give 3.95g of 6, 13-pentacenequinone as a yellow solid product in 85% yield, and the product was ground to a powder for use. Under the protection of nitrogen, 6, 13-pentacenequinone (2.0 g,6.5 mmol) and 100mL of dry tetrahydrofuran were added to the dried bottle, and LiAlH was rapidly added under ice bath conditions 4 (0.98g, 25mmol) of a solid powder, gradually returned to room temperature naturally under stirring, and then the suspension was refluxed for 30min. And then cooling the system to room temperature, slowly adding a hydrochloric acid solution under the condition of an ice salt bath, and continuously heating and refluxing for 3 hours after dropwise adding is finished and no gas is generated in the system. After the reaction was complete, the precipitate was filtered, the filter cake was washed sequentially with deionized water (2X 30 mL), dichloromethane (2X 30 mL), methanol (2X 30 mL) and ether (2X 30 mL), respectively, and the above procedure was repeated again for the dried remaining solid to give pentacene as a dark blue solid in 54% yield. 27.8g of pentacene (0.1 mol) and 43g of vinylene carbonate (0.5 mol) were placed in a pressure bottle and reacted at 220 ℃ for 24 hours. Cooling to room temperature and precipitating with methanol to obtain the addition product. And dissolving the product in 5g of ethanol solution of potassium hydroxide, performing reflux reaction for 8 hours, washing with water and drying to obtain the diol. Dissolving the product in a mixture of 200mL of dichloromethane and 8mL of dimethyl sulfoxide, dropwise adding 12mL of trifluoroacetic anhydride at-78 ℃, reacting for 2h, dropwise adding 25mL of triethylamine, continuously stirring for reacting for 2h, washing with liquid, drying with anhydrous sodium sulfate, and recrystallizing to obtain 22.0g of product with the yield of 66%. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.05-7.95(m,4H,Ph),7.65-7.55(m,4H,Ar),7.42-7.34(m,4H,Ar),4.80(s,2H,CH).
The synthesis of ligand L1 in example 1 was followed, using 6, 13-dihydro-6, 13-ethanopentacene-15, 16-dione instead of bicyclo [2, 2] -dione]Octane-2, 3-dione, in the same operating conditions, in 59.6% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：7.98-6.68(m,26H,Ar-H)，4.06(s,2H,CH).
EXAMPLE 17 Synthesis of ligand L17
The procedure for the synthesis of ligand L2 in example 2 was followed, using 6, 13-dihydro-6, 13-ethanopentacene-15, 16-dione instead of bisRing [2, 2]]Octane-2, 3-dione, in the same operating conditions, in 68.5% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.03-6.94(m,26H,Ar-H)，4.33(s,2H,CH).
EXAMPLE 18 Synthesis of ligand L18
The synthesis of ligand L3 in example 3 was followed, using 6, 13-dihydro-6, 13-ethanopentacene-15, 16-dione instead of bicyclo [2, 2] -dione]Octane-2, 3-dione, in 78.6% yield, under otherwise identical operating conditions. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.58-7.05(m,28H,Ar-H)，4.56(s,2H,CH).
EXAMPLE 19 Synthesis of ligand L19
The synthesis of ligand L4 in example 4 was followed, using 6, 13-dihydro-6, 13-ethanopentacene-15, 16-dione instead of bicyclo [2, 2] -dione]Octane-2, 3-dione, in 87.2% yield, under otherwise identical operating conditions. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.14-7.41(m,30H,Ph-H)，3.72(s,2H,CH).
Example 20 Synthesis of ligand L20
The synthesis of ligand L5 in example 5 was followed, using 6, 13-dihydro-6, 13-ethanopentacene-15, 16-dione instead of bicyclo [2, 2] -dione]Octane-2, 3-dione, in the same operating conditions, in 68.5% yield. 1 H NMR(400MHz,CDCl 3 ,ppm)：8.68-7.39(m,34H,Ar-H)，3.58(s,2H,CH).
Synthesis of the catalyst
EXAMPLE 21 preparation of catalyst 1
0.840g of ligand L1 (2 mmol) from example 1, 0.395g of (DME) NiCl 2 (1.8 mmol) was charged into a 100mL Schlenk flask, evacuated with nitrogen three times, charged with 30mL of dichloromethane, and the reaction was stirred at room temperature for 24h. The solvent was drained and n-hexane was added for washing, and filtration was carried out to obtain 0.910g of the catalyst, the yield being 92.3%. Anal.calcd.c 28 H 24 O 2 N 2 NiCl 2 ：C 61.13；H 4.37；N 5.09；Found：C 61.06；H 4.53；N 5.16。
EXAMPLE 22 preparation of catalyst 2
The synthesis of catalyst 1 in example 21 was carried out with 0.555g of (DME) NiBr 2 (1.8 mmol) instead of (DME) NiCl 2 The yield was 95.6% under the same operating conditions. Anal.calcd.c 28 H 24 O 2 N 2 NiBr 2 ：C 52.62；H 3.76；N 4.38；Found：C 52.54；H 3.81；N 4.45。
Example 23 preparation of catalyst 3
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L2 for L1, under otherwise identical operating conditions, giving a yield of 94.5%. Anal.calcd.c 28 H 24 S 2 N 2 NiCl 2 ：C 57.77；H 4.13；N 4.81；Found：C 57.66；H 4.06；N 4.65。
Example 24 preparation of catalyst 4
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L3 for L1, under otherwise identical operating conditions, giving a yield of 97.6%. Anal.calcd.c 30 H 26 N 4 NiCl 2 ：C 62.98；H 4.55；N 9.80；Found：C 62.86；H 4.46；N 9.75。
Example 25 preparation of catalyst 5
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L4 for L1, under otherwise identical operating conditions, giving a yield of 98.2%. Anal.calcd.c 32 H 28 N 2 NiCl 2 ：C 67.42；H 4.92；N 4.92；Found：C 67.56；H 4.85；N 4.88。
Example 26 preparation of catalyst 6
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L5 for L1, under otherwise identical operating conditions, giving a yield of 96.3%. Anal.calcd.c 40 H 32 N 2 NiCl 2 ：C 71.68；H 4.78；N 4.18；Found：C 71.56；H 4.75；N 4.10。
Example 27 preparation of catalyst 7
The procedure for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L6 for L1, in a yield of 91.5%. Anal.calcd.c 36 H 22 O 2 N 2 NiCl 4 ：C 60.45；H 3.08；N 3.92；Found：C 60.56；H 3.15；N 3.88。
EXAMPLE 28 preparation of catalyst 8
As described in example 21Synthesis of reagent 1, substituting ligand L6 for L1, and 0.555g (DME) NiBr 2 In place of (DME) NiCl 2 The other operating conditions were the same, giving a yield of 94.8%. Anal.calcd.c 36 H 22 O 2 N 2 NiBr 2 Cl 2 ：C 53.76；H 2.74；N 3.48；Found：C 53.66；H 2.81；N3.45。
Example 29 preparation of catalyst 9
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L7 for L1, under otherwise identical operating conditions, giving a yield of 95.5%. Anal.calcd.c 36 H 22 S 2 N 2 NiCl 4 ：C 57.86；H 2.95；N 3.75；Found：C 57.76；H 2.86；N 3.64。
EXAMPLE 30 preparation of catalyst 10
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L8 for L1, under otherwise identical operating conditions, giving a yield of 96.1%. Anal.calcd.c 38 H 24 N 4 NiCl 4 ：C 61.90；H 3.26；N 7.60；Found：C 61.86；H 3.46；N 7.75。
EXAMPLE 31 preparation of catalyst 11
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L9 for L1, under otherwise identical operating conditions, giving a yield of 95.6%. Anal.calcd.c 40 H 26 N 2 NiCl 4 ：C 65.34；H 3.54；N 3.81；Found：C 65.24；H 3.65；N 3.88。
Example 32 preparation of catalyst 12
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L10 for L1, under otherwise identical operating conditions, giving a yield of 93.4%. Anal.calcd.c 48 H 30 N 2 NiCl 4 ：C 69.02；H 3.59；N 3.35；Found：C 68.95；H 3.75；N 3.30。
EXAMPLE 33 preparation of catalyst 13
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L11 for L1, in 92.5% yield. Anal, calcd, c36h 22 O 2 N 2 NiBr 2 Cl 2 ：C 52.45；H 2.67；N 3.39；Found：C 52.36；H 2.76；N 3.28。
Example 34 preparation of catalyst 14
The synthesis of catalyst 1 in example 21 was carried out, replacing L1 with ligand L11 and replacing 0.555g of (DME) NiBr 2 In place of (DME) NiCl 2 The other operating conditions were the same, with a yield of 95.8%. Anal.calcd.c 36 H 22 O 2 N 2 NiBr 4 ：C 47.34；H 2.41；N 3.07；Found：C 47.26；H 2.52；N 3.05。
EXAMPLE 35 preparation of catalyst 15
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L12 for L1, under otherwise identical operating conditions, giving a yield of 96.5%. Anal.calcd.c 36 H 22 S 2 N 2 NiBr 2 Cl 2 ：C 50.49；H 2.57；N3.27；Found：C 50.36；H 2.66；N 3.14。
Example 36 preparation of catalyst 16
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L13 for L1, under otherwise identical operating conditions, giving a yield of 96.8%. Anal.calcd.c 38 H 24 N 4 NiBr 2 Cl 2 ：C 53.93；H 2.84；N 6.62；Found：C 53.84；H 2.76；N 6.75。
Example 37 preparation of catalyst 17
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L14 for L1, under otherwise identical operating conditions, giving a yield of 95.1%. Anal.calcd.c 40 H 26 N 2 NiBr 2 Cl 2 ：C 56.90；H 3.08；N 3.32；Found：C 56.76；H 3.15；N 3.28。
EXAMPLE 38 preparation of catalyst 18
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L15 for L1, under otherwise identical operating conditions, giving a yield of 93.4%. Anal.calcd.c 48 H 30 N 2 NiBr 2 Cl 2 ：C 61.04；H 3.18；N 2.97；Found：C 60.96；H 3.25；N 3.00。
Example 39 preparation of catalyst 19
The synthesis of catalyst 1 in example 21 was followed, with ligandL16 replaced L1, yield 93.4%. Anal.calcd.c 44 H 28 O 2 N 2 NiCl 2 ：C 68.97；H 3.66；N 3.66；Found：C 68.85；H 3.76；N 3.58。
EXAMPLE 40 preparation of catalyst 20
The procedure for the synthesis of catalyst 1 in example 21 was followed, replacing L1 with ligand L16 and adding 0.555g (DME) NiBr 2 In place of (DME) NiCl 2 The other operating conditions were the same, with a yield of 95.3%. Anal.calcd.c 44 H 28 O 2 N 2 NiBr 2 ：C 61.79；H 3.28；N 3.28；Found：C 61.67；H 3.36；N 3.35。
EXAMPLE 41 preparation of catalyst 21
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L17 for L1, under otherwise identical operating conditions, giving a yield of 91.7%. Anal.calcd.c 44 H 28 S 2 N 2 NiCl 2 ：C 66.20；H 3.51；N 3.51；Found：C 66.36；H 3.66；N 3.64。
EXAMPLE 42 preparation of catalyst 22
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L18 for L1, under otherwise identical operating conditions, giving a yield of 96.3%. Anal.calcd.c 46 H 30 N 4 NiCl 2 ：C 69.12；3.81；N 7.11；Found：C 69.03；H 3.76；N 6.99。
EXAMPLE 43 preparation of catalyst 23
The procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L19 for L1, under otherwise identical operating conditions, giving a yield of 93.4%. Anal.calcd.c 48 H 32 N 2 NiCl 2 ：C 73.32；H 4.07；N 3.56；Found：C 73.25；H 4.15；N 3.68。
Example 44 preparation of catalyst 24:
the procedure used for the synthesis of catalyst 1 in example 21 was followed, substituting ligand L20 for L1, under otherwise identical operating conditions, giving a yield of 96.6%. Anal.calcd.c 56 H 36 N 2 NiCl 2 ：C 75.88；H 4.07；N 2.82；Found：C 75.96；H 3.95；N 2.93。
Preparation of lubricant base oil by catalyzing ethylene oligomerization
Example 45
Under an ethylene atmosphere, 50mL of toluene, 4mL of a toluene solution containing 2mmol of methylaluminoxane (Al/Ni = 400), and 5mL of a toluene solution containing 11.0mg (20. Mu. Mol) of catalyst 1 were added to a 100mL reaction vessel, and the reaction was carried out at 50 ℃ and 3atm for 6 hours. After the reaction, the solution containing the polymer was poured into 100mL of a 5% by mass solution of a hydrochloric acid-acidified ethanol, and the cocatalyst was removed by washing, and after the liquid separation, the solvent was removed by rotary evaporation to obtain 46.8g of an oily product.
1 The product was found by H NMR to have a degree of branching of 160 branches/1000 carbon atoms, 13 the product has a long chain branch content of 56mol% by C NMR and a molecular weight of 4000g/mol by GPC.
Example 46
The polymerization was carried out in an n-hexane solvent under the same other operating conditions as in example 45. 42.0g of an oily product was obtained.
1 The product was found to have a degree of branching of 150 branches/1000 carbon atoms by H NMR, 13 the long chain branch content of the product was 60mol% by C NMR and the molecular weight was 3500g/mol by GPC.
Example 47
The polymerization was carried out at 25 ℃ under the same operating conditions as in example 45. 56.8g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 130 branches/1000 carbon atoms, 13 the long chain branch content of the product was 80mol% by C NMR and the molecular weight was 2600g/mol by GPC.
Example 48
The polymerization was carried out at 75 ℃ under the same operating conditions as in example 45. 42.0g of an oily product was obtained.
1 H NMR determines the product to have a degree of branching of 190 branches/1000 carbon atoms, 13 the product has a long chain branch content of 40mol% by C NMR and a molecular weight of 1050g/mol by GPC.
Example 49
The polymerization time was shortened to 0.25h, and other operating conditions were the same as in example 45. 12.8g of oily product was obtained.
1 The product has a degree of branching of 165 branches/1000 carbon atoms as determined by H NMR, 13 the product has a long chain branch content of 50mol% by C NMR and a molecular weight of 4200g/mol by GPC.
Example 50
The polymerization time was extended to 24 hours and the other operating conditions were the same as in example 45. 80.6g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 146 branches/1000 carbon atoms, 13 the long-chain branch content of the product is 40mol% by C NMR, and the molecular weight of the product is 6000g/mol by GPC.
Example 51
The polymerization pressure was reduced to 0.5atm, and other operating conditions were the same as in example 45. 24.3g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 186 branches/1000 carbon atoms, 13 the product has a long chain branch content of 45mol% by C NMR and a molecular weight of 1350g/mol by GPC.
Example 52
The polymerization pressure was raised to 10atm, and other operating conditions were the same as in example 45. 98.4g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 130 branches/1000 carbon atoms, 13 the product has a long chain branch content of 30mol% by C NMR and a molecular weight of 6800g/mol by GPC.
Example 53
The polymerization cocatalyst was replaced by modified methylaluminoxane (MMAO, commercially available from Akzo Nobel) and the other operating conditions were the same as in example 45. 56.4g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 155 branches/1000 carbon atoms, 13 the product has a long chain branch content of 72mol% by C NMR and a molecular weight of 3800g/mol by GPC.
Example 54
The polymerization cocatalyst was replaced by aluminum sesquiethylate chloride and the other operating conditions were the same as in example 45. 36.8g of oily product was obtained.
1 H NMR determined the product to have a degree of branching of 164 branches/1000 carbon atoms, 13 the product has a long chain branch content of 45mol% by C NMR and a molecular weight of 5000g/mol by GPC.
Example 55
The polymerization cocatalyst was replaced by ethylaluminum dichloride, and the other operating conditions were the same as in example 45. 32.6g of oily product was obtained.
1 The product was determined by H NMR to have a degree of branching of 172 branches/1000 carbon atoms, 13 the long chain branch content of the product was 54mol% by C NMR and the molecular weight was 5500g/mol by GPC.
Example 56
The polymerization cocatalyst was replaced by diethylaluminum monochloride and the other operating conditions were the same as in example 45. 52.6g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 154 branches/1000 carbon atoms, 13 the long chain branch content of the product was 65mol% by C NMR and the molecular weight of the product was 6300g/mol by GPC.
Example 57
The polymerization Al/Ni was changed to 100, and the other operating conditions were the same as in example 45. 22.7g of oily product was obtained.
1 H NMR determined the product to have a degree of branching of 144 branches/1000 carbon atoms, 13 the product has a long chain branch content of 70mol% as determined by C NMR and a molecular weight of 5300g/mol as determined by GPC.
Example 58
The Al/Ni polymerization was changed to 800, and the other operating conditions were the same as in example 45. 22.7g of oily product was obtained.
1 H NMR determined the product to have a degree of branching of 185 branches/1000 carbon atoms, 13 the product has a long chain branch content of 33mol% by C NMR and a molecular weight of 2800g/mol by GPC.
Example 59
Catalyst 2 was used in the polymerization and the other operating conditions were the same as in example 45. 44.2g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 175 branches/1000 carbon atoms, 13 the long chain branch content of the product was 41mol% by C NMR and the molecular weight of the product was 3100g/mol by GPC.
Example 60
Catalyst 3 was used in the polymerization and the other operating conditions were the same as in example 45. 47.5g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 164 branches/1000 carbon atoms, 13 the product has a long chain branch content of 48mol% by C NMR and a molecular weight of 4250g/mol by GPC.
Example 61
1 H NMR determines the product to have a degree of branching of 174 branches/1000 carbon atoms, 13 the product has a long chain branch content of 35mol% by C NMR and a molecular weight of 4300g/mol by GPC.
Example 62
Catalyst 5 was used in the polymerization and the other operating conditions were the same as in example 45. 34.8g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 154 branches/1000 carbon atoms, 13 the product has a long chain branch content of 63mol% by C NMR and a molecular weight of 4500g/mol by GPC.
Example 63
Catalyst 6 was used in the polymerization and the other operating conditions were the same as in example 45. 40.5g of oily product was obtained.
1 The product was determined by H NMR to have a degree of branching of 181 branches/1000 carbon atoms, 13 the product has a long chain branch content of 33mol% by C NMR and a molecular weight of 1700g/mol by GPC.
Example 64
Catalyst 7 was used in the polymerization, and the other operating conditions were the same as in example 45. 39.8g of oily product was obtained.
1 The product was found to have a degree of branching of 136 branches/1000 carbon atoms by H NMR, 13 the product has a long chain branch content of 73mol% as determined by C NMR and a molecular weight of 2900g/mol as determined by GPC.
Example 65
Catalyst 8 was used in the polymerization and the other operating conditions were the same as in example 45. 50.7g of oily product was obtained.
1 The product has a degree of branching of 143 branches/1000 carbon atoms as determined by H NMR, 13 the product has a long chain branch content of 63mol% by C NMR and a molecular weight of 3000g/mol by GPC.
Example 66
Catalyst 9 was used in the polymerization and the other operating conditions were the same as in example 45. 48.8g of oily product was obtained.
1 The product was found to have a degree of branching of 165 branches/1000 carbon atoms by H NMR, 13 the product has a long chain branch content of 52mol% by C NMR and a molecular weight of 3250g/mol by GPC.
Example 67
1 The product was found by H NMR to have a degree of branching of 177 branches/1000 carbon atoms, 13 the product has a long chain branch content of 46mol% by C NMR and a molecular weight of 3750g/mol by GPC.
Example 68
Catalyst 11 was used in the polymerization, and the other operating conditions were the same as in example 45. 43.4g of oily product was obtained.
1 The product has a degree of branching, determined by H NMR, of 135 branches/1000 carbon atoms, 13 the product has a long chain branch content of 76mol% by C NMR and a molecular weight of 5400g/mol by GPC.
Example 69
Catalyst 12 was used in the polymerization and the other operating conditions were the same as in example 45. 40.9g of oily product was obtained.
1 The product has a branching degree of 144 determined by H NMRBranched-chain/1000 carbon atoms, and a linear chain, 13 the product has a long chain branch content of 66mol% by C NMR and a molecular weight of 5800g/mol by GPC.
Example 70
Catalyst 13 was used in the polymerization, and the other operating conditions were the same as in example 45. 44.7g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 154 branches/1000 carbon atoms, 13 the long chain branch content of the product was 36mol% by C NMR and the molecular weight of the product was 4000g/mol by GPC.
Example 71
Catalyst 14 was selected for the polymerization and the other operating conditions were the same as in example 45. 42.3g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 152 branches/1000 carbon atoms, 13 the long chain branch content of the product was 41mol% by C NMR and the molecular weight of the product was 1600g/mol by GPC.
Example 72
1 The product has a degree of branching of 165 branches/1000 carbon atoms as determined by H NMR, 13 the product has a long chain branch content of 45mol% by C NMR and a molecular weight of 4200g/mol by GPC.
Example 73
Catalyst 16 was used in the polymerization and the other operating conditions were the same as in example 45. 48.5g of oily product was obtained.
1 The product was found to have a degree of branching of 145 branches/1000 carbon atoms by H NMR, 13 the long chain branch content of the product was 59mol% by C NMR and the molecular weight of the product was 3600g/mol by GPC.
Example 74
Catalyst 17 was used in the polymerization reaction, and the other operating conditions were the same as in example 45. 41.9g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 168 branches/1000 carbon atoms, 13 c NMR measurement of Long chain branches of the productThe content was 44mol%, and the molecular weight of the product was 5100g/mol as determined by GPC.
Example 75
Catalyst 18 was used for the polymerization and the other operating conditions were the same as in example 45. 39.5g of oily product was obtained.
1 The product was determined by H NMR to have a degree of branching of 181 branches/1000 carbon atoms, 13 the long chain branching content of the product was 34mol% by C NMR and the molecular weight of the product was 4800g/mol by GPC.
Example 76
Catalyst 19 was used for the polymerization and the other operating conditions were the same as in example 45. 49.4g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 172 branches/1000 carbon atoms, 13 the long chain branch content of the product was 37mol% by C NMR and the molecular weight of the product was 3000g/mol by GPC.
Example 77
1 The product has a degree of branching of 147 branches/1000 carbon atoms as determined by H NMR, 13 the product has a long chain branch content of 56mol% by C NMR and a molecular weight of 3300g/mol by GPC.
Example 78
Catalyst 21 was used in the polymerization reaction, and the other operating conditions were the same as in example 45. 36.5g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 166 branches/1000 carbon atoms, 13 the product has a long chain branch content of 55mol% by C NMR and a molecular weight of 4900g/mol by GPC.
Example 79
Catalyst 22 was selected for the polymerization and the other operating conditions were the same as in example 45. 45.2g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 155 branches/1000 carbon atoms, 13 the long chain branch content of the product was 63mol% by C NMR and the molecular weight of the product was 3500g/mol by GPC.
Example 80
Catalyst 23 was used in the polymerization reaction, and the other operating conditions were the same as in example 45. 38.8g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 163 branches/1000 carbon atoms, 13 the long chain branch content of the product was 47mol% by C NMR and the molecular weight was 4500g/mol by GPC.
Example 81
Catalyst 24 was used in the polymerization reaction, and the other operating conditions were the same as in example 45. 46.6g of oily product was obtained.
1 The product was found by H NMR to have a degree of branching of 153 branches/1000 carbon atoms, 13 the product has a long chain branch content of 61mol% by C NMR and a molecular weight of 2700g/mol by GPC.
Base oil Performance test
The lubricating properties were evaluated by measuring the kinematic viscosity of the product at different temperatures according to the national standards GB/T265-88 and GB/T1995-88 and calculating the viscosity index.
The pour point of the product is determined according to GB/T3535-2006 so as to evaluate the low-temperature service performance of the product.
The evaporation loss and the flash point of the product are determined according to the petrochemical industry standard SH/T0731-2004 and the national standard GB/T3536-2008, and then the stability and the safety of the product are evaluated.
The performance test results of the polyethylene base oil obtained in the inventive example are shown in table 1.
TABLE 1 Performance test results of the polyethylene base oils obtained in the examples
As can be seen from the results in Table 1, the polyolefin lubricant base oil prepared by the embodiment of the invention has both higher viscosity and better low-temperature fluidity, has excellent performance, and is very suitable for being used as lubricant base oil with medium and high viscosity.
As shown in FIG. 2, from the nuclear magnetic carbon spectrum of the base oil product obtained in example 68, it can be seen that the methyl short chain branch (characteristic peak 1B) is present in the product 1 ) Very low content of C or more 6 Long chain branch (characteristic peak 1B) 4+ 、2B 5+ 、3B 5+ ) The content is very high. Thus, the base oils prepared in the examples of the present invention have desirable long chain branch content and branching.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (8)
1. An alpha-diimine ligand compound, wherein the ligand compound has a structure shown as a formula (1), a formula (2) or a formula (3),
in the formulae (1) to (3), R 1 Represents a substituted or unsubstituted heteroaryl or aryl group having 4 to 14 ring atoms; said R is 1 When the substituted group is represented, the substituent is one or more of halogen, C1-C6 alkyl, C1-C6 alkoxy and C1-C6 halogenated alkyl; r 2 Represents chlorine, bromine, C1-C4 alkyl or C1-C4 haloalkyl.
2. The ligand compound according to claim 1, wherein R is 1 Represents a substituted or unsubstituted heteroaryl group having 4 to 8 ring atoms, including at least one heteroatom of N, S or O; or said R 1 Represents a substituted or unsubstituted aryl group having 6 to 14 ring atoms;
wherein, R is 1 Represents substitutedWhen the group is selected, the substituent is one or more of chlorine, bromine, C1-C4 alkyl, C1-C4 alkoxy and C1-C4 halogenated alkyl.
3. The ligand compound according to claim 2, wherein R is 1 Represents furyl, thienyl, pyridyl, phenyl or naphthyl.
4. A process for producing a ligand compound as claimed in any one of claims 1 to 3, which comprises reacting a diketone compound represented by the formula (I-1) with R 1 Substituted aniline derivatives are prepared by a ketoamine condensation reaction,
（Ⅰ-1）。
5. an alpha-diimine complex, wherein the complex has a structure shown as a formula (A), a formula (B) or a formula (C),
wherein R is 1 、R 2 Represents the same as defined in claim 1;
x represents chlorine or bromine.
6. A preparation method of polyolefin lubricating oil base oil, which takes ethylene as a polymerization monomer and is prepared through a polymerization process under the catalysis of an alpha-diimine complex, wherein the alpha-diimine complex is the alpha-diimine complex of claim 5.
7. The preparation method according to claim 6, wherein the polymerization process is carried out in toluene or n-hexane, the polymerization pressure is 0.5 to 10atm, the polymerization temperature is 25 to 75 ℃, and the polymerization time is 0.25 to 24 hours.
8. The preparation method of claim 6 or 7, wherein the polymerization process further comprises an alkylaluminum as a cocatalyst, wherein the alkylaluminum is one or more of methylaluminoxane, modified methylaluminoxane, sesquiethylaluminum chloride, ethylaluminum dichloride or diethylaluminum monochloride, and the ratio of aluminum/M is 100-800.
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