CN1142142C - Ethylene oligomerizing catalyst and its synthesis process and use - Google Patents
Ethylene oligomerizing catalyst and its synthesis process and use Download PDFInfo
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- CN1142142C CN1142142C CNB011130571A CN01113057A CN1142142C CN 1142142 C CN1142142 C CN 1142142C CN B011130571 A CNB011130571 A CN B011130571A CN 01113057 A CN01113057 A CN 01113057A CN 1142142 C CN1142142 C CN 1142142C
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- ethylene
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- imine
- ethylene oligomerization
- catalyst
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000005977 Ethylene Substances 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000000034 method Methods 0.000 title 1
- 230000003606 oligomerizing effect Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 26
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 6
- 238000010189 synthetic method Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000004076 pyridyl group Chemical group 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- -1 phenyl pyridyl Chemical group 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 230000002140 halogenating effect Effects 0.000 abstract 2
- 229910001848 post-transition metal Inorganic materials 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 87
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical compound CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 0.000 description 36
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000001291 vacuum drying Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 6
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- CMVJYZNBMRJICR-UHFFFAOYSA-N 2-fluoro-6-methylaniline Chemical compound CC1=CC=CC(F)=C1N CMVJYZNBMRJICR-UHFFFAOYSA-N 0.000 description 4
- RCYMPYMITUEHOJ-UHFFFAOYSA-N 3-fluoro-2-methoxyaniline Chemical compound COC1=C(N)C=CC=C1F RCYMPYMITUEHOJ-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 description 3
- 229910015475 FeF 2 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 3
- 229960005081 diclofenamide Drugs 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- KLOQOWQKKZSVJD-UHFFFAOYSA-N n-fluoro-4-methylaniline Chemical class CC1=CC=C(NF)C=C1 KLOQOWQKKZSVJD-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 3
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to an ethylene oligomerization catalyst, a synthetic method thereof and application thereof. The catalyst is a halogenating phenyl pyridyl di-imine post transition metal complex which is synthesized by halogenating phenyl pyridyl di-imine and post transition metal compounds. The catalyst can be used for catalyzing ethylene oligomerization; the catalyst has high selectivity to short chain alkene, and the catalytic activity is high. The catalytic activity can reach 3.8*10<6>g/mol. Fe. h. atm, the quality percentage content (wt%) of C4 to C12 is higher than 91, and the selectivity of alpha-alkene is higher than 99%.
Description
The present invention relates to a kind of ethylene oligomerization catalyst, preparation method and use.This catalyzer is a kind of halophenyl pyridyl di-imine transition metal compound, is to be synthesized by halogenophenyl pyridyl di-imine and rear transition metal compound to form.Can be used for the catalyzed ethylene oligomerisation.
The annual production of whole world alpha-olefin is approximately 4 * 10
9Pound, it is important industrial raw material, is mainly used in ethylene copolymer producing linear new LDPE (film grade) and is used to prepare lubricant, tensio-active agent, softening agent etc.
These alpha-olefins mainly obtain by ethylene oligomerization.The catalyst system that is used for the catalyzed ethylene oligomerisation at present mainly is an alkyl aluminum system, early transition metal compound/alkyl aluminum system and the neutral nickelous compound that contains the bidentate single anion ligand.(Vogt, D.In Applied Homogeneous Catalysis with OrganometallicCompounds:Comils, B., Hermann, W.A..Eds; VCH Publishers:1996; Vol.I:pp245-256.SkupinSka, J.Chem.Rev.1991,91,613.) at present, some anionic nickelous compounds that contain the diimine bitooth ligand also are in the news and are used for the catalyzed ethylene oligomerisation.(Killian，C.M.；Johnson，L.K.；Brookhart，M.Organometallics 1997，16，2005)
Recently, Brookhart group and Gibson group almost find Fe (II) and Co (II) simultaneously but the oligomerisation of trident pyridinimine title complex catalyzed ethylene, structural formula is as follows:
The catalytic activity of catalyzer is very high, and the selectivity of alpha-olefin very high (Brookhart, M etc., J.Am.Chem.Soc.1998,120,7143; WO 99/02472,1999.Gibson, V.C. etc., J.Chem.Commun.1998,849; Chem.Eur.J.2000,2221).
In the three tooth imine compositions that they reported, an ortho-substituent of aniline must be hydrogen, and the substituting group of rest part is a hydrogen, electron-donating groups such as methyl or sec.-propyl.People are still constantly inquiring into and are seeking three new tooth imine compositions, to improve catalytic activity.Synthesized the title complex of two halo imines Fe (II), structural formula is as follows:
X=Br=Cl
It is several thousand～several ten thousand that these two complex-catalyzed vinyl polymerizations obtain number-average molecular weight, and weight-average molecular weight is the High molecular weight polyethylene of several ten thousand～hundreds of thousands of.
Obtain ultra high molecular weight polyethylene for a complex-catalyzed vinyl polymerization, still obtain low-molecular-weight ethylene oligomer (molecular weight is less than 500), depend on its structure.If it is difficult that its structure makes that β-H eliminates, just obtain ultra high molecular weight polyethylene, otherwise just obtain low-molecular-weight ethylene oligomer.So for a title complex, if it is the poly-catalyzer of a kind of good ethene height, it just can not be good ethylene oligomerization catalyst.For example two above-mentioned complex-catalyzed vinyl polymerizations just can only obtain ultra high molecular weight polyethylene, rather than obtain low-molecular-weight ethylene oligomer.People still expect to have the catalyzer that new being used to prepares low-molecular-weight ethylene oligomer.
The purpose of this invention is to provide a kind of ethylene oligomerization catalyst.It is a kind of halophenyl pyridyl di-imine transition metal compound.
Purpose of the present invention also provides a kind of synthetic method of above-mentioned ethylene oligomerization catalyst.System forms by halogenophenyl pyridyl di-imine and rear transition metal compound are synthetic.
Another object of the present invention provides a kind of purposes of above-mentioned ethylene oligomerization catalyst, can be used for the catalyzed ethylene oligomerisation.
The invention provides ethylene oligomerization catalyst, is the following halophenyl pyridyl di-imine transition metal compound of a kind of structural formula:
In the said structure formula, X
1Or/and X
6Be H, halogen, C
1-4Alkyl, C
1-6Ester group, C
1-6Amido or C
1-6Ether, R
4Or/and R
8Be halogen, M is Fe (II), Fe (III), Co (II) and Ru (II), Z is-H ,-C
1-4Alkyl, aryl or trihalomethyl group, Y
1, Y
2=chlorine, bromine, iodine, C
1-4Alkyl, methyl ethyl diketone or fluoroarylboron, M=Fe (II), Fe (III), Co (II) and Ru (II), R
1, R
2, R
3, R
5, R
6Or R
7For halogen ,-H, nitro, cyano group ,-C
1-4Alkyl, aryl, C
1-6Ester group, C
1-6Amido or C
1-6Ether.
Above-mentioned catalyzer can represent in a variety of forms, as: R in the molecular formula
4, R
8For-H, C
1-4Alkyl, aryl or inertia group, X
1, X
6Be halogen, X
1, X
6Can be identical, also can be different, R
1-R
3, R
5-R
7For halogen ,-H, nitro, cyano group ,-C
1-4Alkyl, aryl, C
1-6Ester group, C
1-6Amido or C
1-6Ether, M, Y
1, Y
2With Z as mentioned above;
X in the molecular formula
1, R
4, X
6, R
8Be fluorine, R
1-R
3, R
5-R
7Be halogen ,-H ,-C
1-4Alkyl, aryl, C
1-6Ester group, C
1-6Amido or C
1-6Ether, M, Y
1, Y
2With Z as mentioned above;
X in the molecular formula
1, X
6Be fluorine, R
1-R
4, R
5-R
8Be halogen ,-H ,-C
1-4Alkyl, aryl, nitro, cyano group, C
1-6Ester group, C
1-6Amido or C
1-6Ether, M, Y
1, Y
2With Z as mentioned above.
In above-mentioned ethylene oligomerization catalyst of the present invention, when an ortho position of aniline is a halogen, another ortho position is a hydrogen, for example following structural formula:
, X
1And X
6=H; R
4And R
8When=Br, Cl or F, so complex-catalyzed vinyl polymerization obtains oligomerization product.When two ortho positions of aniline are that atomic radius is very little, during the very big fluorine of electronegativity, structural formula is as follows:
Such compound for catalysis vinyl polymerization mainly obtains C
4-C
12The short chain alpha-olefin.
Catalyzer of the present invention, promptly above-mentioned structural formula
Halophenyl pyridyl di-imine transition metal compound is by halogenophenyl pyridyl di-imine and rear transition metal compound MQ
nMH
2O is in organic solvent or water, and reaction 0.01～10h obtains halogenophenyl pyridyl di-imine part and MQ
nMH
2The mol ratio of O is 1: 0.2-5, Q are chlorine, bromine, iodine or methyl ethyl diketone, and n=2-3, M are Fe (II), Fe (III), Co (II) and Ru (II), m=0,1,2,3,4,5 or 6.Described organic solvent can be a tetrahydrofuran (THF), methyl alcohol, ethanol, butanols or methylene dichloride etc.That this reaction is adopted is more, greater than 5 moles MQ
nMH
2O is to not influence of reaction.Usually yield is 50～100%.
The purposes of halophenyl pyridyl di-imine transition metal compound of the present invention is to be used for the catalyzed ethylene oligomerisation.
Oligomerisation reaction carries out in round-bottomed flask or autoclave, and ethylene pressure is 0.1～1000 * 10
5Pa, polymerization temperature are 500～-50 ℃, with C
4-8Alkane or aromatic hydrocarbons are solvent, with MAO (methylaluminoxane), and MMAO (methylaluminoxane of modification), EAO (ethyl aikyiaiurnirsoxan beta), BAO (butyl aikyiaiurnirsoxan beta), LiR (R=C
1-4Alkyl), AlR
mCl
n(R=C
1-3Alkyl, m=1-3, n=0-2), Lewis acid (Lewis acid), LiR/Lewis acid (R=C
1-4Alkyl), AlR
mCl
n/ Lewis acid (R=C
1-3Alkyl, m=1-3 n=0-2) makes promotor.Behind the reaction certain hour, with 5% hydrochloric acid termination reaction.
Catalyzer of the present invention is than trident pyridinimine title complex (Brookhart, M etc., J.Am.Chem.Soc.1998,120,7143 of the Fe (II) of Brookhart group and Gibson group; WO 99/02472,1999.Gibson, V.C. etc., J.Chem.Commun.1998,849; Chem.Eur.J.2000,2221), being used for the catalyzed ethylene polymerization oligomerisation, the selectivity of short chain olefin is higher, and catalytic activity is very high.At ethylene pressure is 10atm, and when polymerization temperature was 60 ℃, the catalytic activity of title complex can reach 3.8 * 10
6G/molFehatm, C
4-C
12Quality percentage composition (wt%)＞91, the selectivity of alpha-olefin＞99%.
The present invention will be helped further to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1
The preparation of (2,6-diacetyl pyridine two (2, the 6-difluoroaniline)) iron protochloride (A)
Preparation feedback carries out under argon gas atmosphere.Get 27mg FeCl
24H
2O adds THF 4ml, stirs.Add 72mg 2,6-diacetyl pyridine two (2, the 6-fluoroaniline) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 15ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2, the 6-fluoroaniline)) iron protochloride (A).Productive rate 89%.Ultimate analysis: C
21H
15N
3FeF
4Cl
2: calculated value C, 49.25; H, 2.95; N, 8.20.Measured value C, 48.42; H, 3.36, N, 7.66.
Embodiment 2
The preparation of (2,6-diacetyl pyridine two (2, the 6-difluoroaniline)) cobalt chloride (B)
Preparation feedback carries out under argon gas atmosphere.Get 21mg CoCl
2, add THF 3ml, stir.Add 53mg2,6-diacetyl pyridine two (2, the 6-fluoroaniline) generates pale brown look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 15ml ether.Vacuum-drying 10 hours.Obtain pale brown look solid (2,6-diacetyl pyridine two (2, the 6-fluoroaniline)) cobalt chloride (B).Productive rate 81%.Ultimate analysis: C
21H
15N
3CoF
4Cl
2: calculated value C, 48.95; H, 2.93; N, 8.15.Measured value C, 48.18; H, 3.17; N, 7.78.
Embodiment 3
The preparation of (2,6-diacetyl pyridine two (2-fluoroaniline)) iron protochloride (C)
Preparation feedback carries out under argon gas atmosphere.Get 80mg FeCl
24H
2O adds THF 6ml, stirs.Add 157mg 2,6-diacetyl pyridine two (2-fluoroaniline) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 20ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2-fluoroaniline)) iron protochloride (C).Productive rate 93%.Ultimate analysis: C
21H
17N
3FeF
2Cl
2: calculated value C, 52.97; H, 3.60; N, 8.82.Measured value C, 53.12; H, 3.93, N, 8.43.
Embodiment 4
The preparation of (2,6-diacetyl pyridine two (2-dichlorphenamide bulk powder)) iron protochloride (D)
Preparation feedback carries out under argon gas atmosphere.Get 80mg FeCl
24H
2O adds THF 6ml, stirs.Add 172mg 2,6-diacetyl pyridine two (2-chloroaniline) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 20ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2-chloroaniline)) iron protochloride (D).Productive rate 82%.Ultimate analysis: C
21H
17N
3FeCl
4: calculated value C, 49.55; H, 3.37; N, 8.25.Measured value C, 51.12; H, 3.63, N, 8.03.
Embodiment 5
The preparation of (2,6-diacetyl pyridine two (2-bromaniline)) iron protochloride (E)
Preparation feedback carries out under argon gas atmosphere.Get 160mg FeCl
24H
2O adds THF 6ml, stirs.Add 424mg 2,6-diacetyl pyridine two (2-bromaniline) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 20ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2-bromaniline)) iron protochloride (E).Productive rate 87%.Ultimate analysis: C
21H
17N
3FeBr
2Cl
2: calculated value C, 42.18; H, 2.86; N, 7.03.Measured value C, 42.62; H, 3.07, N, 6.83.
Embodiment 6
The preparation of (2,6-diacetyl pyridine two (2-fluoro-6-monomethylaniline)) iron protochloride (F)
Preparation feedback carries out under argon gas atmosphere.Get 160mg FeCl
24H
2O adds THF 6ml, stirs.Add 400mg 2,6-diacetyl pyridine two (2-fluoro-6-monomethylaniline) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 20ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2-fluoro-6-monomethylaniline)) iron protochloride (F).Productive rate 81%.Ultimate analysis: C
23H
21N
3FeF
2Cl
2: calculated value C, 54.26; H, 4.19; N, 8.33.Measured value C, 54.32; H, 3.98, N, 8.13.
Embodiment 7
The preparation of (2,6-diacetyl pyridine two (2-fluoro-6-anisidine)) iron protochloride (G)
Preparation feedback carries out under argon gas atmosphere.Get 160mg FeCl
24H
2O adds THF 6ml, stirs.Add 412mg 2,6-diacetyl pyridine two (2-fluoro-6-anisidine) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 20ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2-fluoro-6-anisidine)) iron protochloride (G).Productive rate 82%.Ultimate analysis: C
23H
21N
3FeF
2Cl
2O
2: calculated value C, 51.49; H, 3.95; N, 7.84.Measured value C, 51.87; H, 3.97, N, 7.53.
Embodiment 8
The preparation of (2,6-diacetyl pyridine two (2,6-two fluoro-4-monomethylanilines)) iron protochloride (H)
Preparation feedback carries out under argon gas atmosphere.Get 160mg FeCl
24H
2O adds THF 6ml, stirs.Add 430mg 2,6-diacetyl pyridine two (2,6-two fluoro-4-monomethylanilines) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 20ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2,6-two fluoro-4-monomethylanilines)) iron protochloride (H).Productive rate 82%. ultimate analyses: C
23H
17N
3FeF
4Cl
2: calculated value C, 51.10; H, 3.52; N, 7.72.Measured value C, 51.44; H, 3.66, N, 7.56.
Embodiment 9
The preparation of (2,6-diacetyl pyridine two (2,4, the 6-trifluoromethyl aniline)) iron protochloride (I)
Preparation feedback carries out under argon gas atmosphere.Get 160mg FeCl
24H
2O adds THF 6ml, stirs.Add 430mg 2,6-diacetyl pyridine two (2,4, the 6-trifluoromethyl aniline) generates blue look precipitation immediately.Stirred overnight at room temperature.Centrifugal, remove THF.And then divide 3 cleanings with the 20ml ether.Vacuum-drying 10 hours.Obtain blue look solid (2,6-diacetyl pyridine two (2,4, the 6-trifluoromethyl aniline)) iron protochloride (I).Productive rate 88%. ultimate analyses: C
21H
13N
3FeF
6Cl
2: calculated value C, 45.98; H, 2.37; N, 7.66.Measured value C, 46.12; H, 2.46, N, 7.46.
Embodiment 9
In the autoclave of 0.5L, add 100ml toluene, add MMAO (commercial goods, Al/Fe mol ratio=2000), constant temperature to 25 ℃.Add 20ml again and contain the toluene solution and the 30ml toluene of 1 μ mol (2,6-diacetyl pyridine two (2, the 6-difluoroaniline)) iron protochloride.Under vigorous stirring, feed ethylene gas, ethylene pressure is constant to be 10 normal atmosphere.React after 1 hour, with 5% hydrochloric acid termination reaction.Oligomerization product is determined its composition by GC-MS, and determines each component concentration by GC.The result is as shown in table 1.
Embodiment 10
In the autoclave of 0.5L, add 100ml toluene, add MMAO (Al/Fe mol ratio=2000), constant temperature to 40 ℃.Add 20ml again and contain the toluene solution and the 30ml toluene of 1 μ mol (2,6-diacetyl pyridine two (2, the 6-difluoroaniline)) iron protochloride.Under vigorous stirring, feed ethylene gas, ethylene pressure is constant to be 10 normal atmosphere.React after 1 hour, with 5% hydrochloric acid termination reaction.Oligomerization product is determined its composition by GC-MS, and determines each component concentration by GC.The result is as shown in table 1.
Embodiment 11
In the autoclave of 0.5L, add 100ml toluene, add MMAO (Al/Fe mol ratio=2000), constant temperature to 60 ℃.Add 20ml again and contain the toluene solution and the 30ml toluene of 1 μ mol (2,6-diacetyl pyridine two (2, the 6-difluoroaniline)) iron protochloride (E).Under vigorous stirring, feed ethylene gas, ethylene pressure is constant to be 10 normal atmosphere.React after 1 hour, with 5% hydrochloric acid termination reaction.Oligomerization product is determined its composition by GC-MS, and determines each component concentration by GC.The result is as shown in table 1.
Embodiment 12
In the autoclave of 0.5L, add 100ml toluene, add MMAO (Al/Fe mol ratio=2000), constant temperature to 40 ℃.Add 20ml again and contain the toluene solution and the 30ml toluene of 1 μ mol (2,6-diacetyl pyridine two (2-fluoroaniline)) iron protochloride (C).Under vigorous stirring, feed ethylene gas, ethylene pressure is constant to be 10 normal atmosphere.React after 1 hour, with 5% hydrochloric acid termination reaction.Oligomerization product is determined its composition by GC-MS, and determines each component concentration by GC.The result is as shown in table 1.
Embodiment 13
In the autoclave of 0.5L, add 100ml toluene, add MMAO (Al/Fe mol ratio=2000), constant temperature to 40 ℃.Add 20ml again and contain the toluene solution and the 30ml toluene of 1 μ mol (2,6-diacetyl pyridine two (2-bromaniline)) iron protochloride (E).Under vigorous stirring, feed ethylene gas, ethylene pressure is constant to be 10 normal atmosphere.React after 1 hour, with 5% hydrochloric acid termination reaction.Oligomerization product is determined its composition by GC-MS, and determines each component concentration by GC.The result is as shown in table 1.
Embodiment 14
In the autoclave of 0.5L, add 100ml toluene, add MMAO (Al/Fe mol ratio=2000), constant temperature to 40 ℃.Add 20ml again and contain the toluene solution and the 30ml toluene of 1 μ mol (2,6-diacetyl pyridine two (2-fluoro-6-monomethylaniline)) iron protochloride (F).Under vigorous stirring, feed ethylene gas, ethylene pressure is constant to be 10 normal atmosphere.React after 1 hour, with 5% hydrochloric acid termination reaction.Oligomerization product is determined its composition by GC-MS, and determines each component concentration by GC.The result is as shown in table 1.
Embodiment 15
In the autoclave of 0.5L, add 100ml toluene, add MMAO (Al/Fe mol ratio=2000), constant temperature to 40 ℃.Add 20ml again and contain the toluene solution and the 30ml toluene of 1 μ mol (2,6-diacetyl pyridine two (2-fluoro-6-anisidine)) iron protochloride (G).Under vigorous stirring, feed ethylene gas, ethylene pressure is constant to be 10 normal atmosphere.React after 1 hour, with 5% hydrochloric acid termination reaction.Oligomerization product is determined its composition by GC-MS, and determines each component concentration by GC.The result is as shown in table 1.
Table 1 ethylene oligomerization
| Catalyzer | T (℃) | Active (kg/molhatm) | Selectivity a C 4-C 12 (Wt％) | C 4(Wt％) | C 6 (Wt％) | C 8 (Wt％) | C 10 (Wt％) | C 12 (Wt％) | C 14 (Wt％) | C 16 (Wt％) |
| A | 25 | 3400 | 80.7 | 26 | 21 | 15 | 11 | 7.7 | 5.3 | 3.5 |
| A | 40 | 4300 | 85.3 | 34 | 24 | 14 | 8.3 | 5 | 3 | 1.8 |
| A | 60 | 3800 | 91.3 | 40 | 27 | 14 | 6.8 | 3.5 | 1.8 | 0.95 |
| C | 25 | 50 | 97 | 45 | 27 | 15 | 7 | 3 | 1.5 | 0.7 |
| C | 40 | 12 | 97 | 46 | 27 | 14 | 7 | 3 | 1.3 | 0.6 |
| E | 40 | 18 | 51 | 10 | 11 | 11 | 10 | 8 | 7 | 6 |
| F | 40 | 1300 | 78 | 22 | 19 | 16 | 12 | 9 | 6.5 | 4.5 |
| G | 40 | 970 | 74 | 20 | 18 | 15 | 12 | 9 | 7 | 5 |
Alpha-olefin content is greater than 99%.
Embodiment 16
For the ease of making comparisons with the high poly-catalyzer of ethene, we provide embodiment 16-18, the catalyzer that utilization structure is following:
X=Br=Cl
In the autoclave of 1L, add 500ml toluene, add 0.15ml Al (iBu)
3, at room temperature stirring reaction is 1 hour.Add MMAO (Al/Fe mol ratio=1500) again, be cooled to 15 ℃ then.Add 10ml contain 0.8 μ mol (2,6-diacetyl pyridine two (2, the 6-dibromo aniline) iron protochloride H
2The toluene solution of O under vigorous stirring, feeds ethylene gas, and ethylene pressure is constant to be 6 normal atmosphere.React after 0.5 hour, the emptying ethylene gas is with the ethanol termination reaction that contains 5% hydrochloric acid.Behind the polymer filtration, under 60 ℃, vacuum-drying is to constant weight.Obtain product 29.2g.Catalytic activity is 7.3 * 10
7G PE/molFeh.The poly molecular weight M of gained
w=25.5 ten thousand (GPC, orthodichlorobenzene is made eluent), molecular weight distribution is 20.6, peak
Melting point is 133 ℃, and degree of crystallinity is 70%.
Embodiment 17
In the autoclave of 1L, add 500ml toluene, add 0.15ml Al (iBu)
3, at room temperature stirring reaction is 1 hour.Add MMAO (Al/Fe mol ratio=1500) again, be cooled to 15 ℃ then.Adding 10ml contains the toluene solution of 0.8 μ mol (2,6-diacetyl pyridine two (2, the 6-dichlorphenamide bulk powder)) iron protochloride, under vigorous stirring, feeds ethylene gas, and ethylene pressure is constant to be 6 normal atmosphere.React after 0.5 hour, the emptying ethylene gas is with the ethanol termination reaction that contains 5% hydrochloric acid.Behind the polymer filtration, under 60 ℃, vacuum-drying is to constant weight.Obtain product 28.8g.Catalytic activity is 7.2 * 10
7G PE/molFeh.The poly molecular weight M of gained
w=4.14 ten thousand (GPC, orthodichlorobenzene is made eluent), molecular weight distribution is 5.3, and peakmelting point is 132 ℃, and degree of crystallinity is 54%.
Embodiment 18
In the round-bottomed flask of 100ml, add 40ml toluene, add MMAO (Al/Fe mol ratio=2500) again, be cooled to 0 ℃ then.Feed ethylene gas, ethylene pressure is constant to be a normal atmosphere.Under vigorous stirring, add 10ml and contain 0.8 μ mol (2,6-diacetyl pyridine two (2, the 6-bromaniline)) iron protochloride H
2The toluene solution of O.React after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Behind the polymer filtration, under 60 ℃, vacuum-drying is to constant weight.Obtain polyethylene 4.87g.Catalytic activity is 1.22 * 10
7G PE/molFeh.The poly molecular weight M of gained
w=6.9 ten thousand (GPC, orthodichlorobenzene is made eluent), molecular weight distribution is 45.8, peak melting point is 127 ℃.
Embodiment 19
In the round-bottomed flask of 100ml, add 40ml toluene, add MMAO (Al/Fe mol ratio=1250) again, be cooled to 0 ℃ then.Feed ethylene gas, ethylene pressure is constant to be a normal atmosphere.Under vigorous stirring, add 10ml contain 0.8 μ mol (2, the toluene solution of 6-diacetyl pyridine two (2, the 6-dichlorphenamide bulk powder) iron protochloride.React after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Behind the polymer filtration, under 60 ℃, vacuum-drying is to constant weight.Obtain polyethylene 5.13g.Catalytic activity is 1.28 * 10
7GPE/molFeh.The poly molecular weight M of gained
w=1.26 ten thousand (GPC, orthodichlorobenzene is made eluent), molecular weight distribution is 5.0, peak melting point is 128 ℃.
Claims (5)
1, a kind of ethylene oligomerization catalyst is characterized in that the halophenyl pyridyl di-imine transition metal compound that a kind of structural formula is following:
In the said structure formula, X
1Or X
6Be H, halogen, C
1～6Ester group, C
1～6Amido or C
1～6Ether, R
4Or R
8Be halogen, M is Fe (II), Fe (III) or Co (II), Z is-H ,-C
1～4Alkyl, aryl, trihalomethyl group, Y
1, Y
2=chlorine, bromine, iodine, C
1～4Alkyl, methyl ethyl diketone or fluoroarylboron, R
1, R
2, R
3, R
5, R
6Or R
7For halogen ,-H, nitro, cyano group ,-C
1～4Alkyl, aryl, C
1～6Ester group, C
1～6Amido or C
1～6Ether; And work as X
1Or X
6During for chlorine, bromine, iodine, R
4Or R
8Be fluorine, R
1, R
2, R
3, R
5, R
6Or R
7For fluorine ,-H, nitro, cyano group ,-C
1～4Alkyl, aryl, C
1～6Ester group, C
1～6Amido or C
1～6Ether.
2, a kind of ethylene oligomerization catalyst as claimed in claim 1 is characterized in that a kind of structural formula is as follows:
X
1And X
6=H, R
8And R
4=Br, Cl or F.
3, a kind of ethylene oligomerization catalyst as claimed in claim 1 is characterized in that a kind of structural formula is as follows:
4, a kind of synthetic method of ethylene oligomerization catalyst as claimed in claim 1 is characterized in that by halogenophenyl pyridyl di-imine and rear transition metal compound MQ
nMH
2O is in organic solvent or water, and reaction 0.01～10h obtains halogenophenyl pyridyl di-imine part and MQ
nMH
2The mol ratio of O is 1: 0.2-5, Q are chlorine, bromine, iodine or methyl ethyl diketone, and n=2-3, M are Fe (II), Fe (III) or Co (II), m=0-6,
Halogenophenyl pyridyl di-imine structural formula is
5, a kind of purposes of ethylene oligomerization catalyst as claimed in claim 1 is characterized in that being used for the catalyzer of ethylene oligomerization.
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| CNB011130571A CN1142142C (en) | 2001-06-01 | 2001-06-01 | Ethylene oligomerizing catalyst and its synthesis process and use |
| PCT/CN2002/000337 WO2002096919A1 (en) | 2001-06-01 | 2002-05-20 | Catalysts for the oligomerization of ethylene, method for preparing them and their usage |
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| CNB011130571A CN1142142C (en) | 2001-06-01 | 2001-06-01 | Ethylene oligomerizing catalyst and its synthesis process and use |
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| US20050187418A1 (en) | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| US20070043181A1 (en) | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | Methods of preparation of an olefin oligomerization catalyst |
| US7384886B2 (en) | 2004-02-20 | 2008-06-10 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US20050187098A1 (en) | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
| US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| CN1706552B (en) * | 2005-04-21 | 2012-02-08 | 中国科学院上海有机化学研究所 | Ethylene oligomerizing catalyst and its use |
| US7727926B2 (en) | 2005-07-21 | 2010-06-01 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and method of using in oligomerization and polymerization |
| US7129304B1 (en) | 2005-07-21 | 2006-10-31 | Chevron Phillips Chemical Company Lp | Dimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
| US7268096B2 (en) | 2005-07-21 | 2007-09-11 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
| US7271121B2 (en) | 2005-07-21 | 2007-09-18 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
| US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
| CN101475602B (en) * | 2009-01-22 | 2012-01-04 | 华中师范大学 | Dinuclear cobalt complex, and its preparation and use |
| US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
| CN105854947B (en) * | 2016-05-01 | 2018-08-17 | 上海大学 | Double imidazole ligands transition metal complex catalysts of chiral pyridyl and preparation method thereof |
| US9944661B2 (en) | 2016-08-09 | 2018-04-17 | Chevron Phillips Chemical Company Lp | Olefin hydroboration |
| CN114702529B (en) * | 2022-05-09 | 2023-08-11 | 东北石油大学 | Nickel phthalocyanine complex, preparation method thereof and application thereof in ethylene oligomerization |
| CN115400788B (en) * | 2022-08-30 | 2024-02-02 | 华东理工大学 | MCM-22 molecular sieve catalyst and modification method and application thereof |
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| CN1139574C (en) * | 2001-01-21 | 2004-02-25 | 中国科学院上海有机化学研究所 | Halophenyl pyridyl di-imine transition metal compound and its synthesis process and use |
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