CN105482000B - A kind of olefin polymerization catalysis and its methods for making and using same - Google Patents
A kind of olefin polymerization catalysis and its methods for making and using same Download PDFInfo
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- CN105482000B CN105482000B CN201410479028.8A CN201410479028A CN105482000B CN 105482000 B CN105482000 B CN 105482000B CN 201410479028 A CN201410479028 A CN 201410479028A CN 105482000 B CN105482000 B CN 105482000B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title description 5
- 150000001336 alkenes Chemical class 0.000 title description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- -1 C1‐C20Alkyl Chemical group 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 150000002391 heterocyclic compounds Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 36
- 239000005977 Ethylene Substances 0.000 claims description 34
- 239000000460 chlorine Substances 0.000 claims description 25
- 239000003446 ligand Substances 0.000 claims description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910000071 diazene Inorganic materials 0.000 claims description 12
- 239000003426 co-catalyst Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 229910052732 germanium Inorganic materials 0.000 abstract description 2
- VGRFVJMYCCLWPQ-UHFFFAOYSA-N germanium Chemical compound [Ge].[Ge] VGRFVJMYCCLWPQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 125000000962 organic group Chemical group 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 13
- 230000037048 polymerization activity Effects 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 230000020477 pH reduction Effects 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- JMBLSGAXSMOKPN-UHFFFAOYSA-N 2-methylnaphthalen-1-amine Chemical class C1=CC=CC2=C(N)C(C)=CC=C21 JMBLSGAXSMOKPN-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- ZTRJVDUHNRWPAI-UHFFFAOYSA-N 2,4-dimethylnaphthalen-1-amine Chemical class C1=CC=CC2=C(N)C(C)=CC(C)=C21 ZTRJVDUHNRWPAI-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 3
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000005002 naphthylamines Chemical class 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- NCXCFZUKRMOFHW-UHFFFAOYSA-N 2,6-dibenzhydryl-4-methylaniline Chemical compound NC=1C(C(C=2C=CC=CC=2)C=2C=CC=CC=2)=CC(C)=CC=1C(C=1C=CC=CC=1)C1=CC=CC=C1 NCXCFZUKRMOFHW-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical class CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a kind of catalyst for vinyl polymerization, the catalyst includes complex of the chemical structural formula as shown in (I) as major catalyst：In formula (1), X is halogen；R1‑R8It may be the same or different, be each independently selected from hydrogen atom, halogen, C1‑C20Alkyl, heterocyclic compound group or oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom organic group；And R1And R2、R5And R6It is optionally mutually cyclic.The present invention also provides a kind of preparation methods of the catalyst.The present invention also provides a kind of method of olefinic polymerization, including in the presence of the catalyst of the invention, carrying out olefinic polyreaction.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of catalyst for olefines polymerizing and preparation method thereof.More specifically
, it is related to a kind of alpha-diimine nickel olefine polymerization catalyst and its technology of preparing and gained catalyst in terms of olefinic polymerization
Using.
Background technology
China is that synthetic resin consumes fastest-rising country, is also the largest synthetic resin importer, at present polyolefin
Yield proportion nearly 60%, olefin resin has excellent environment compatibility compared with other resin materials, in flourishing state
It is used for the material of emphasis popularization in family's automobile industry, world's output in 2003 has just reached 83,300,000 tons；It is wherein poly-
Ethylene is synthetic resin with fastest developing speed, that yield is maximum, purposes is extremely wide, reaches 51,100,000 tons for the year.Industrialized polyethylene is urged
Agent has Ziegler-Natta types catalyst (DE Pat889229 (1953)；IT Pat 545332 (1956) and IT Pat
536899(1955)；Chem.Rev., 2000,100,1169 and the special issue pertinent literature), Phillips type catalyst
(Belg.Pat.530617(1955)；Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky,
Metalorganic Catalysts for Synthesis and Polymerization,Berlin:Springer,
1999) the efficient ethylene oligomerization and polymerization catalyst of the late transition metal metal compounding material type and in recent years developed.Such as
Nineteen ninety-five, Brookhart etc. report the complex of a kind of alpha-diimine Ni (II), can be with the polymerising ethylene of high activity
(J.Am.Chem.Soc.,1995,117,6414-6415)。
Since alpha-diimine Raney nickel has high activity and polymer molecular weight and the degree of branching can be in very wide range
It is interior regulation and control and receive much attention.The companies such as Du Pont have applied for multiple patents (WO 96/23010, WO 98/03521, WO 98/
40374,WO 99/05189,WO 99/62968,WO 00/06620,US 6,103,658,US 6,660,677).This kind of α-two
Imines Raney nickel is under methylaluminoxane or alkyl aluminum effect, the catalysis ethylene oligomerization of energy high activity under room temperature or low temperature
Or polymerization.But when increasing reaction temperature higher than 50 DEG C, this kind of alpha-diimine nickel catalyst activity reduces rapidly, and prepared is poly-
The molecular weight with polymerisation temperature of ethylene is improved and is declined rapidly.Existing ethene gas-phase polymerization technological requirement polymerization temperature for 85 DEG C with
On, vinyl solution polymerization technique requirement polymerization temperature is 150-250 DEG C, and original late transition metal catalyst can not meet existing gas
The requirement of phase, solwution method ethylene polymerization plants.Catalyst prepared by this patent can still keep higher ethylene at relatively high temperatures
Polymerization activity, and resulting polymers molecular weight is higher, molecular weight distribution is relatively narrow.
Invention content
One of the object of the invention is to overcome the shortcomings of the prior art, provides a kind of α-two with good thermal stability
Imine nickel complex catalyst under methylaluminoxane or alkyl aluminum activation, can realize catalyzed ethylene polymerization under higher temperature,
Prepare the branched polyethylene of high molecular weight.
First embodiment of the present invention provides a kind of catalyst for vinyl polymerization, and the catalyst includes making
Complex of the chemical structural formula as shown in (I) for major catalyst：
In formula (1), X is halogen；R1-R8It may be the same or different, be each independently selected from hydrogen atom, halogen, C1-C20Hydrocarbon
Base, heterocyclic compound group or oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom organic group；And R1And R2、R5With
R6It is optionally mutually cyclic.
In one preferred embodiment, the X is selected from chlorine or bromine.
In one preferred embodiment, the complex is selected from the complex of Formula II or formula III structure；
Wherein, X is chlorine or bromine；R3、R4、R7-R11It may be the same or different, be respectively selected from hydrogen atom, halogen, C1- C20's
Alkyl, heterocyclic compound group.
In further preferred embodiment, the complex is selected from least one of following compound：
1) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=Me, X=Br；
2) complex, wherein R shown in formula (II)3=R7=R4=R8=Me, R9=H, X=Br；
3) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=iPr, X=Br；
4) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=CHPh2, X=Br；
5) complex, wherein R shown in formula (II)3=R7=H, R4=R8=R9=CHPh2, X=Br；
6) complex, wherein R shown in formula (II)3=R7=R4=R8=R9=CHPh2, X=Br；
7) complex, wherein R shown in formula (III)11=Ph, R10=H, X=Br；
8) complex, wherein R shown in formula (III)11=Ph, R10=Cl, X=Br；
9) complex, wherein R shown in formula (III)11=Ph, R10=CH3, X=Br；
10) complex, wherein R shown in formula (III)11=Ph, R10=iPr, X=Br；
11) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=Me, X=Cl；
12) complex, wherein R shown in formula (II)3=R7=R4=R8=Me, R9=H, X=Cl；
13) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=iPr, X=Cl；
14) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=CHPh2, X=Cl；
15) complex, wherein R shown in formula (II)3=R7=H, R4=R8=R9=CHPh2, X=Cl；
16) complex, wherein R shown in formula (II)3=R7=R4=R8=R9=CHPh2, X=Cl；
17) complex, wherein R shown in formula (III)11=Ph, R10=H, X=Cl；
18) complex, wherein R shown in formula (III)11=Ph, R10=Cl, X=Cl；
19) complex, wherein R shown in formula (III)11=Ph, R10=CH3, X=Cl；And
20) complex, wherein R shown in formula (III)11=Ph, R10=iPr, X=Cl.
Wherein Me represents that methyl, Ph represent that phenyl, iPr represent isopropyl.
In a preferred embodiment of the present invention, the catalyst further includes co-catalyst, the co-catalyst choosing
From at least one of alkylaluminoxane, alkyl aluminum and chloralkane, preferably trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three
In n-butylaluminum, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride at least
It is a kind of.
In further preferred embodiment, the gold in metallic aluminium and the major catalyst in the co-catalyst
The molar ratio of category is 200-5000.
Second embodiment of the present invention is related to a kind of preparation method of the catalyst, wherein, the complex
Preparation method：
1) in the presence of a catalyst, by 9,10- dihydros -9,10- ethylene anthracene -11,12- diketone and the aniline of substitution molten
It flows back in agent, reacts and alpha-diimine ligand is made；
2) under conditions of anhydrous and oxygen-free, the alpha-diimine ligand and (DME) NiX that step 1) is obtained2Matched
Position reaction, obtains complex of the chemical constitution as shown in formula (I).
In a preferred embodiment of the present invention, the catalyst in the step 1) is acetic acid and/or the step
1) solvent in is ethyl alcohol.
In a preferred embodiment of the present invention, the reaction temperature of the reaction be 70-80 DEG C, preferably 78 DEG C, institute
The time for stating reflux is 1-7 days.
In a preferred embodiment of the present invention, it 9,10- dihydros -9,10- ethylene anthracene -11,12- diketone and takes
The molar ratio of the aniline in generation is 1:1~1:10, preferably 1:1~1:3.
The complex of the present invention and the specific preparation process of catalyst are as follows：
1st, the conventional method of ligand synthesis
A) 9,10- dihydros -9,10- ethylenes anthracene -11,12- diketone and the aniline of substitution are catalyst in solvent second using acetic acid
It flows back 1-7 days in alcohol, parlkaline aluminium oxide pillar after solvent is removed after filtering, with petrol ether/ethyl acetate (20:1) it elutes, point
From obtaining product；
B) 9,10- dihydros -9,10- ethylenes anthracene -11,12- diketone and substitution aniline in toluene with p-methyl benzenesulfonic acid
It flows back 1-7 days for catalyst, reaction solution is evaporated rear parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) it elutes, point
From obtaining product.
9,10- dihydro -9,10- ethylene anthracene -11,12- the diimide ligands of above-mentioned all synthesis all by nuclear-magnetism, it is infrared and
Elemental analysis is confirmed.
2nd, the conventional method of nickel (II) complex synthesis
Under inert gas shielding, by (DME) NiCl2Or (DME) NiBr2Dichloromethane solution in molar ratio (1:1~
1:1.2) it is added drop-wise in the solution of 9,10- dihydro -9,10- ethylene anthracene -11,12- diimide ligands, is stirred at room temperature, precipitation is precipitated,
Filtering is dried in vacuo after being washed with ether just obtains 9,10- dihydro -9,10- ethylene anthracene -11,12- diimine nickel complexes.
The third embodiment of the present invention is related to a kind of method of olefinic polymerization, and the method includes of the present invention
Catalyst in the presence of, carry out olefinic polyreaction.
In a preferred embodiment of the present invention, it is -78 DEG C that the reaction temperature of the polymerisation, which is polymerization temperature,
~200 DEG C, preferably -20 DEG C~150 DEG C；Polymerization pressure is 0.01~10.0MPa, preferably 0.01~2.0MPa.
Catalyst prepared by the present invention can be used for homopolymerization or the copolymerization of alkene, equal especially suitable for ethylene
Polymerization or the copolymerization of ethylene and other alpha-olefins, wherein alpha-olefin is using propylene, butylene, amylene, hexene, octene, 4-
At least one of -1 grade of methylpentene.
In some preferred embodiments of the present invention, wherein solvent is selected from alkane, aromatic hydrocarbon or halogen used in polymerization
For hydrocarbon.It is preferred that one kind or their mixture in hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes,
One kind or their mixture most preferably in hexane, toluene, heptane.
The present invention has the following advantages compared with prior art:
9,10- dihydros -9,10- ethylenes anthracene -11,12- diketone and the benzene of substitution can be used in complex ligand of the present invention
Amine flows back obtained in ethanol using acetic acid as catalyst, and ligand synthetic method is more simple and practicable.
Under methylaluminoxane or alkyl aluminum effect, the catalysis ethylene of energy high activity gathers catalyst of the present invention
It closes.Especially (80 degree can be higher than) under higher polymerization temperature and still keep higher polymerization activity.(previous literature or patent report
Diimine nickel catalyst is significantly decayed, and molecular weight is greatly lowered in 50 degree or more activity).
Catalyst of the present invention has the ability of the copolymerization of good catalysis ethylene and high alpha-olefin,
Copolymerization activity is high.
Specific embodiment
The present invention will be described in detail with reference to embodiments, but it is to be appreciated that the embodiment is only used for pair
The present invention is illustratively described, and can not form any restrictions to protection scope of the present invention.It is all to be included in this hair
Reasonable changes and combinations in bright invention teachings each fall within protection scope of the present invention.
Analysis and characterization instrument used in the present invention is as follows:
Nuclear Magnetic Resonance：Bruker DMX 300 (300MHz), tetramethylsilane (TMS) are internal standard.
Embodiment 1
Shown in the present embodiment complex such as structural formula (II), wherein R4、R8For methyl, R3、R7、R9For hydrogen, X Br.
1) preparation of ligand：
11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2- methyl naphthylamines)：
9,10- dihydro -9,10- ethylene anthracene -11,12- diketone (1.14g, 4.8mmol) and 2- methyl naphthylamines (1.63g,
10.4mmol), 0.5g p-methyl benzenesulfonic acid is catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtering, residue is used
Dichloromethane dissolves, parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) it elutes, isolated product, removes
Solvent obtains yellow solid, yield 46%.1H NMR(CDCl3,δ,ppm):2.46(s,6H),4.86(s,2H),7.05-
7.36 (m, 14H), 7.62-7.72 (m, 6H).
2) preparation of complex 1：Bromination [11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2- methyl naphthylamines)] is closed
Nickel (II)：By 10ml (DME) NiBr2The dichloromethane solution of (277mg, 0.9mmol) is added drop-wise to 10ml 11,12- (9,10- bis-
Hydrogen -9,10- ethylene anthracene) two (contracting 2- methyl naphthylamines) ligands (461mg, 0.9mmol) dichloromethane solution in, be stirred at room temperature 6
Hour, precipitation is precipitated, filtering is dried to obtain dark red powder solid, yield 90% after being washed with ether.Elemental analysis
(C38H28Br2N2Ni)：C,62.42；H,3.86；N,3.83；Experiment value (%)：C,62.56；H,4.03；N,4.16.
3) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.It adds in 7.3mg (10 μm of ol) complexs 1 and then vacuumizes and replaced 3 times with ethylene again.
The hexane of 500ml is injected, 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l) is added, makes Al/Ni=
1000.At 50 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.In ethanol solution with the acidification of 5% hydrochloric acid
With obtain polyethylene, polymerization activity is 8.62 × 106g·mol-1(Ni)·h-1。
Embodiment 2
10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, while hot
It vacuumizes and uses N2Gas is replaced 3 times.It adds in 6.6mg (10 μm of ol) complexs 1 and then vacuumizes and replaced 3 times with ethylene again.Note
Enter the hexane of 500ml, add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000.
At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.It is neutralized, obtained with the ethanol solution that 5% hydrochloric acid is acidified
To polyethylene, polymerization activity is 6.28 × 106g·mol-1(Ni)·h-1。
Embodiment 3
Shown in the present embodiment complex such as structural formula (II), wherein R3、R4、R7、R8For methyl, R9For hydrogen, X Br.
1) preparation of ligand：11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2,4- dimethyl-naphthylamines)：9,10-
Dihydro -9,10- ethylene anthracene -11,12- diketone (1.82g, 7.8mmol) and 2,4- dimethyl-naphthylamine (2.98g, 17.4mmol),
0.5g p-methyl benzenesulfonic acid is catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtering, residue dichloromethane is molten
Solution, parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) it elutes, isolated product, removes solvent and obtain Huang
Color solid, yield 42%.1H NMR(CDCl3,δ,ppm):2.45(s,6H),2.67(s,6H),4.86(s,2H),7.05-
7.34 (m, 14H), 7.60-7.71 (m, 4H).
2) preparation of complex 2：Bromination [11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2,4- dimethylnaphthalenes
Amine)] close nickel (II)：By 10ml (DME) NiBr2The dichloromethane solution of (155mg, 0.5mmol) is added drop-wise to 10ml 11,12-
The dichloromethane solution of (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2,4- dimethyl-naphthylamines) ligand (270mg, 0.5mmol)
In, it is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dried to obtain dark red powder solid, yield 87% after being washed with ether.
Elemental analysis (C40H32Br2N2Ni)：C,63.28；H,4.25；N,3.69；Experiment value (%)：C,63.42；H,4.56；N,3.92.
3.10atm vinyl polymerization：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.It adds in 7.6mg (10 μm of ol) complexs 2 and then vacuumizes and replaced 3 times with ethylene again.
The hexane of 500ml is injected, 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l) is added, makes Al/Ni=
1000.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.In ethanol solution with the acidification of 5% hydrochloric acid
With obtain polyethylene, polymerization activity is 4.72 × 106g·mol-1(Ni)·h-1。
Embodiment 4
Shown in the present embodiment complex such as structural formula (II), wherein R4、R8For benzhydryl, R3、R7、R9For hydrogen, X Br.
1) preparation of ligand：11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2- benzhydryls naphthylamines)：9,10-
Dihydro -9,10- ethylene anthracene -11,12- diketone (1.82g, 7.8mmol) and 2- benzhydryls naphthylamines (5.38g, 17.4mmol),
0.5g p-methyl benzenesulfonic acid is catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtering, residue dichloromethane is molten
Solution, parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) it elutes, isolated product, removes solvent and obtain yellow
Solid, yield 30%.1H NMR(CDCl3,δ,ppm):4.88 (s, 2H), 5.32 (s, 2H), 7.05-7.35 (m, 34H),
7.60-7.70 (m, 6H).
2) preparation of complex 4：Bromination [11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2- benzhydryl naphthalenes
Amine)] close nickel (II)：By 10ml (DME) NiBr2The dichloromethane solution of (155mg, 0.5mmol) is added drop-wise to 10ml 11,12-
The dichloromethane solution of (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2- benzhydryls naphthylamines) ligand (408mg, 0.5mmol)
In, it is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dried to obtain dark red powder solid, yield 87% after being washed with ether.
Elemental analysis (C62H44Br2N2Ni)：C,71.91；H,4.28；N,2.71；Experiment value (%)：C,71.46；H,4.63；N,2.52.
3) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.It adds in 10.4mg (10 μm of ol) complexs 4 and then vacuumizes and replaced 3 times with ethylene again.
The hexane of 500ml is injected, 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l) is added, makes Al/Ni=
1000.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.In ethanol solution with the acidification of 5% hydrochloric acid
With obtain polyethylene, polymerization activity is 3.27 × 106g·mol-1(Ni)·h-1。
Embodiment 5
Shown in the present embodiment complex such as structural formula (III), wherein R11For phenyl, R10For methyl, X Br.
1) preparation of ligand：11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2,6- bis- (benzhydryl) -4- first
Base aniline)：9,10- dihydro -9,10- ethylene anthracene -11,12- diketone (2.10g, 9.0mmol) and 2,6- bis- (benzhydryl) -4-
Methylaniline (8.66g, 19.7mmol), 0.5g p-methyl benzenesulfonic acid are catalyst, in 100mL reflux in toluene 1 day, are removed after filtering
Solvent is removed, residue is dissolved with dichloromethane, parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) it elutes, separation
Product is obtained, solvent is removed and obtains yellow solid, yield 36%.1H NMR(CDCl3,δ,ppm):2.15(s,6H),4.95
(s, 2H), 5.34 (s, 4H), 6.70 (s, 4H), 6.97 (d, J=6.9Hz, 8H), 7.06 (d, J=7.4Hz, 8H), 7.12-
7.35(m,32H)。
2) preparation of complex 9：Bromination [11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2,6- diisopropyl benzenes
Amine)] close nickel (II)：By 10ml (DME) NiBr2The dichloromethane solution of (506mg, 1.6mmol) is added drop-wise to 10ml 11,12-
(9,10- dihydro -9,10- ethylenes anthracene) two ((the benzhydryl) -4- of contracting 2,6- bis- methylanilines) ligand (1723mg, 1.6mmol)
Dichloromethane solution in, be stirred at room temperature 6 hours, precipitation be precipitated, filtering is dried to obtain dark red powder after being washed with ether and consolidates
Body, yield 88%.Elemental analysis (C82H64Br2N2Ni)：C,76.00；H,4.98；N,2.16；Experiment value (%)：C,76.27；
H,5.24；N,2.52.
3) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.It adds in 12.96mg (10 μm of ol) complexs 9 and then vacuumizes again and replace 3 with ethylene
It is secondary.The hexane of 500ml is injected, 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l) is added, makes Al/Ni=
1000.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.In ethanol solution with the acidification of 5% hydrochloric acid
With obtain polyethylene, polymerization activity is 5.21 × 106g·mol-1(Ni)·h-1。
Embodiment 6
Shown in the present embodiment complex such as structural formula (II), wherein R4、R8For methyl, R3、R7、R9For hydrogen, X Cl.
1) preparation of complex 11：Chlorination [11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2- methyl naphthylamines)]
Close nickel (II)：By 10ml (DME) NiCl2The dichloromethane solution of (352mg, 1.6mmol) is added drop-wise to 10ml 11,12- (9,10-
Dihydro -9,10- ethylene anthracene) two (contracting 2- methyl naphthylamines) ligands (820mg, 1.6mmol) dichloromethane solution in, be stirred at room temperature
6 hours, precipitation is precipitated, filtering is dried to obtain orange red powder solid, yield 87% after being washed with ether.Elemental analysis
(C38H28Cl2N2Ni)：C,71.06；H,4.39；N,4.36；Experiment value (%)：C,71.32；H,4.88；N,4.24.
2) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.It adds in 6.4mg (10 μm of ol) complexs 11 and then vacuumizes and replaced 3 times with ethylene again.
The hexane of 500ml is injected, 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l) is added, makes Al/Ni=
1000.At 80 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.In ethanol solution with the acidification of 5% hydrochloric acid
With obtain polyethylene, polymerization activity is 5.20 × 106g·mol-1(Ni)·h-1。
Embodiment 7
The present embodiment complex is as shown in structure formula (II), wherein R3、R4、R7、R8For methyl, R9For hydrogen, X Cl.
1) preparation of complex 12：Chlorination [11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2,4- dimethylnaphthalenes
Amine)] close nickel (II) (1)：By 10ml (DME) NiCl2The dichloromethane solution of (352mg, 1.6mmol) is added drop-wise to 10ml 11,
The dichloromethane of two (contracting 2,4- dimethyl-naphthylamines) ligands (864mg, 1.6mmol) of 12- (9,10- dihydro -9,10- ethylenes anthracene) is molten
It in liquid, is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dried to obtain orange red powder solid after being washed with ether, yield is
90%.Elemental analysis (C40H32Cl2N2Ni)：C,71.67；H,4.81；N,4.18；Experiment value (%)：C,71.87；H,5.02；N,
3.88。
2) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.It adds in 6.7mg (10 μm of ol) complexs 12 and then vacuumizes and replaced 3 times with ethylene again.
The hexane of 500ml is injected, 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l) is added, makes Al/Ni=
1000.At 80 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.In ethanol solution with the acidification of 5% hydrochloric acid
With obtain polyethylene, polymerization activity is 3.22 × 106g·mol-1(Ni)·h-1。
Embodiment 8
10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, while hot
It vacuumizes and uses N2Gas is replaced 3 times.It adds in 7.3mg (10 μm of ol) complexs 1 and then vacuumizes and replaced 3 times with ethylene again.Note
Enter the hexane of 500ml, add 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), make Al/Ni=1000,
10ml hexenes.At 80 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.The ethyl alcohol being acidified with 5% hydrochloric acid is molten
Liquid neutralizes, and obtains polyethylene, and polymerization activity is 5.27 × 106g·mol-1(Ni)·h-1。
Comparative example 1
10atm ethylene：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken out while hot true
Sky simultaneously uses N2Gas is replaced 3 times.It adds in 7.2mg (10 μm of ol) comparative catalyst A (its structure such as formula (IV)) and then vacuumizes again simultaneously
It is replaced 3 times with ethylene.The hexane of 500ml is injected, adding 6.5ml methylaluminoxane (MMAO), (toluene of 1.53mol/l is molten
Liquid), make Al/Ni=1000,10ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With
The ethanol solution of 5% hydrochloric acid acidification neutralizes, and obtains polyethylene, and polymerization activity is 0.08 × 106g·mol-1(Ni)·h-1。
Comparative example 2
10atm ethylene：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken out while hot true
Sky simultaneously uses N2Gas is replaced 3 times.It adds in 6.2mg (10 μm of ol) comparative catalyst B (its structure such as formula (V)) and then vacuumizes again and be used in combination
Ethylene is replaced 3 times.The hexane of 500ml is injected, adds 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l),
Make Al/Ni=1000,10ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With 5% salt
The ethanol solution of acid acidification neutralizes, and obtains polyethylene, and polymerization activity is 0.02 × 106g·mol-1(Ni)·h-1。
Table 1
As can be seen from Table 1, relative to the complex of comparative example 1 and 2, using the metal complex of the present invention as main reminder
For agent in use, polymerization activity is much higher under the conditions of high temperature polymerization, the molecular weight of resulting polymers is apparently higher than comparative example
Resulting polymers.
Claims (10)
1. a kind of catalyst for vinyl polymerization, the catalyst includes the chemical structural formula such as (II) institute as major catalyst
The complex shown：
Wherein, X is chlorine or bromine；R3、R4、R7-R9It may be the same or different, be each independently selected from hydrogen atom, halogen, C1- C20's
Alkyl, heterocyclic compound group.
2. catalyst according to claim 1, which is characterized in that the complex in following compound at least one
Kind：
1) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=Me, X=Br；
2) complex, wherein R shown in formula (II)3=R7=R4=R8=Me, R9=H, X=Br；
3) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=iPr, X=Br；
4) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=CHPh2, X=Br；
5) complex, wherein R shown in formula (II)3=R7=H, R4=R8=R9=CHPh2, X=Br；
6) complex, wherein R shown in formula (II)3=R7=R4=R8=R9=CHPh2, X=Br；
11) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=Me, X=Cl；
12) complex, wherein R shown in formula (II)3=R7=R4=R8=Me, R9=H, X=Cl；
13) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=iPr, X=Cl；
14) complex, wherein R shown in formula (II)3=R7=R9=H, R4=R8=CHPh2, X=Cl；
15) complex, wherein R shown in formula (II)3=R7=H, R4=R8=R9=CHPh2, X=Cl；
16) complex, wherein R shown in formula (II)3=R7=R4=R8=R9=CHPh2, X=Cl.
3. catalyst according to claim 1 or 2, which is characterized in that the catalyst further includes co-catalyst, described to help
Catalyst is selected from least one of alkylaluminoxane, alkyl aluminum and chloralkane.
4. catalyst according to claim 3, which is characterized in that the co-catalyst be selected from trimethyl aluminium, triethyl aluminum,
Triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride and dichloride second
At least one of base aluminium.
5. catalyst according to claim 3, which is characterized in that metallic aluminium and the main catalytic in the co-catalyst
The molar ratio of metal in agent is 200-5000.
A kind of 6. preparation method of catalyst according to any one of claims 1 to 5, which is characterized in that the cooperation
The preparation method of object includes：
1) in the presence of a catalyst, by 9,10- dihydros -9,10- ethylene anthracene -11,12- diketone and the aniline of substitution in a solvent
Reflux reacts and alpha-diimine ligand is made；
2) under conditions of anhydrous and oxygen-free, the alpha-diimine ligand and (DME) NiX that step 1) is obtained2Be coordinated anti-
Should, obtain complex.
7. according to the method described in claim 6, it is characterized in that, catalyst in the step 1) is acetic acid and/or described
Solvent in step 1) is ethyl alcohol.
8. the method described in any one of according to claim 6 or 7, which is characterized in that 9,10- dihydros -9,10- ethylene
The molar ratio of anthracene -11,12- diketone and the aniline of substitution is 1:1~1:10.
9. according to the method described in claim 8, it is characterized in that, 9,10- dihydros -9,10- ethylene anthracene -11,12- diketone
Molar ratio with substituted aniline is 1:1~1:3.
A kind of 10. method of olefinic polymerization, which is characterized in that the method includes according to any one of claims 1 to 5
In the presence of catalyst, olefinic polyreaction is carried out.
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| CN111116783A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Olefin polymer and preparation method thereof |
| CN111116786B (en) * | 2018-10-31 | 2022-03-15 | 中国石油化工股份有限公司 | Diamine ligand, diamine complex, and catalyst comprising the diamine complex |
| CN111377827B (en) * | 2018-12-29 | 2022-11-25 | 辽宁奥克化学股份有限公司 | Alpha-diimine ligand compound, complex and preparation method of polyolefin lubricating oil base oil |
| JP7586908B2 (en) * | 2019-10-31 | 2024-11-19 | 中国石油化工股▲ふん▼有限公司 | Aminoimine metal complexes and their preparation method and application |
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| CN114426605B (en) * | 2020-10-09 | 2023-03-24 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
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