CN100400552C - Metallocene chromium catalyst with lateral group containing heteroatom, its preparation method and use - Google Patents
Metallocene chromium catalyst with lateral group containing heteroatom, its preparation method and use Download PDFInfo
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- CN100400552C CN100400552C CNB2003101150366A CN200310115036A CN100400552C CN 100400552 C CN100400552 C CN 100400552C CN B2003101150366 A CNB2003101150366 A CN B2003101150366A CN 200310115036 A CN200310115036 A CN 200310115036A CN 100400552 C CN100400552 C CN 100400552C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 34
- 239000011651 chromium Substances 0.000 title claims description 32
- 229910052804 chromium Inorganic materials 0.000 title claims description 16
- 125000005842 heteroatom Chemical group 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 69
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 239000004711 α-olefin Substances 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl compound Chemical class 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 5
- 229960000359 chromic chloride Drugs 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000001845 chromium compounds Chemical group 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 30
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 230000001186 cumulative effect Effects 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 230000000740 bleeding effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000005773 Enders reaction Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OKICHZSTRJQITD-UHFFFAOYSA-N 5-methylcyclopenta-1,3-diene zirconium(2+) Chemical compound [Zr++].C[c-]1cccc1.C[c-]1cccc1 OKICHZSTRJQITD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019590 Cr-N Inorganic materials 0.000 description 1
- 229910019588 Cr—N Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
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Abstract
The present invention discloses a preparation method of novel metallocene chromium compounds substituted by nitrogen-containing heteroatoms and an application of the compounds in olefinic polymerization. In the present invention, a nitrogen heteroatom substituted cyclopentadiene ligand is introduced into the same central metal, and a series of the compounds are synthesized. The polymerization of different alpha-olefins and the copolymerization of olefins are controlled by different substitutents (R1) on a cyclopentadiene ring and different substitutents (R2, R3) on a bridged ring. The catalyst has a novel structure; when used for the polymerization of olefines, the catalyst has high activity; the catalyst has the advantages of easy synthesis, good stability and good low temperature resistance.
Description
Technical field
The invention belongs to the synthetic and high molecular polymer synthetic complex art field of orgnometallic catalyst, relate to a kind of cyclopentadienyl metallic compound preparation method, and the application of this compound in alpha-olefin homopolymerization or copolymerization.
Background technology
The beginning of the fifties, the CrO that the Hogan of Ziegler-Natta catalyst (J.Am.Chem.Soc.1957,79,2975.) and PhillipsPetroleum Co. and Banks (L.US 2 825 721 for Hogan, J.P.R.Banks, 1958) find
3The agent of/SiOization is applied to the success of vinyl polymerization, makes organometallics obtain swift and violent development.Since nineteen sixty, being synthesized of numerous novel metal organic compound successes, and provide the new catalyst of a series of high reactivities, highly selective, be widely used in the polymerization of alpha-olefin and numerous organic synthesis, and also demonstrate huge vitality at the synthetic and life science of type material.
The beginning of the eighties, people such as Kaminsky (Makromol.Chem.Rapid Commun.1983,4,417.) find the homogeneous catalysis system that is dissolved in toluene that methylaluminoxane (MAO) and dimethyl zirconocene are formed, vinyl polymerization is had high catalytic activity, and the discovery of this achievement is once to shock greatly for whole academia and industry member.Contemporary world, polyolefinic annual production is up to tens million of ton, and economic benefit is very considerable, becomes people's inseparable part of living.Therefore, each big chemical company also throws the organic research and development with this field of homogeneous catalysis in metal of huge fund one after another.
In recent years, Jolly people such as (Organometallics.2000,19,388.Organometallics.2001,20,2234.) has reported a series of N of containing, the luxuriant ring chromium complex that P replaces, and synthesized and contain S, O, imines replace the chromium complex of luxuriant ring.At Cr: MAO=1: 100, Pethylene is under the condition of 2atm, along with the H on the luxuriant ring is replaced by alkyl and Cl is replaced by alkyl, activity enlarges markedly.Studied ethene-1-hervene copolymer and closed, obtained low-molecular-weight elastomerics, activity is 40000kg mol
-1h
-1Ender people such as (Organometallics.2001,20,5005) has reported the chromium complex of following structure, finds that they are used for ethylene rolymerization catalyst has higher activity.
X＝Cl，Me，CH
2Ph
Jolly?et?al Ender?et?al.
Along with science and technology development, it is higher that people try hard to the development research activity, and cost is lower, and the luxuriant more widely chromium metallic compound of purposes is to satisfy the needs that olefinic polymerization is produced.
Summary of the invention
One of purpose of the present invention provides the novel side group of a class and contains heteroatomic metallocene chrome catalysts and this Preparation of catalysts method.
Another object of the present invention provides the method that above-mentioned catalyzer is used for olefinic polymerization.
The novel side group of a class provided by the present invention contains heteroatomic metallocene chrome catalysts novel structure, and it is higher to be used for olefin polymerizating activity, and catalyzer is easily synthetic, good stability, and cold resistance is good.
To describe the present invention below.
A kind of side group that is used for olefinic polymerization or copolymerization contains heteroatomic metallocene chrome catalysts, and its structure has following general formula:
R in the formula (I)
1Cp is a cyclopentadienyl, substituted cyclopentadienyl, R
1Be selected from hydrogen, C
1-C
12Alkyl, C
1-C
12Alkoxyl group or C
6-C
12Aryl, R
2, R
3Be C
1-C
12Straight chained alkyl, branched-chain alkyl, cycloalkyl, alkoxyl group or C
6-C
12Aryl; Y is a nitrogen, and X is a halogen atom.
R
1Preferred hydrogen or C
1-C
4Alkyl, hydrogen most preferably, R
2, R
3Preferred hydrogen or C
1-C
4Alkyl, cyclohexyl, most preferably hydrogen, methyl, ethyl, the preferred chlorine of X; Two groups that link to each other with Y in addition in the structural formula are generally alkyl, preferable methyl.
The side group that is used for olefinic polymerization or copolymerization of the present invention contains the preparation method of heteroatomic metallocene chrome catalysts, comprises the steps:
(1) ligand compound α, α-dialkyl group replaces adjacent N, and N-dialkyl amino benzyl replaces luxuriant synthesizing;
Under the protection of inert gas, alkali alkyl compound solution and adjacent N, N-dialkyl amino bromobenzene removes by filter solvent-78～25 ℃ of following stirring reactions 4～8 hours, with organic solvent washing gained precipitation, add organic solvent and obtain the alkali alkyl salts solution after with this resolution of precipitate; 6,6 '-dialkyl group fulvene solution and abovementioned alkyl alkali metal salt soln were-78～25 ℃ of following stirring reactions 4～24 hours; Reaction mixture is told organic layer after the hydrolysis in frozen water; Organic phase frozen water and salt acid elution; And use the organic solvent extraction water, at 0～5 ℃, under pH 12～14 conditions, add organic solvent aqueous phase extracted once more; Merge organic phase, add anhydrous Na
2SO
4Dry 12～24 hours, to filter, underpressure distillation obtains part;
(2) ligand compound and the alkali alkyl compound shown in the formula (II) reacted in organic medium, temperature of reaction is-78～25 ℃, mol ratio such as presses and under agitation reacts 12～24 hours, generates an alkali metal salt of ligand compound; R in the formula (II)
1Cp is a cyclopentadienyl, substituted cyclopentadienyl, R
1Be selected from hydrogen, C
1-C
12Alkyl, C
1-C
12Alkoxyl group or C
6-C
12Aryl, R
2, R
3Be C
1-C
12Straight chained alkyl, branched-chain alkyl, cycloalkyl, alkoxyl group or C
6-C
12Aryl, Y is a nitrogen; R
1Preferred hydrogen or C
1-C
4Alkyl, hydrogen most preferably, R
2, R
3Preferred hydrogen or C
1-C
4Alkyl, cyclohexyl, most preferably hydrogen, methyl, ethyl; Two groups that link to each other with Y in addition in the structural formula are generally alkyl, preferable methyl.
(3) an alkali metal salt with part reacts with chromium trichloride or four chromium chlorides in organic medium, by chromium/part molar ratio computing is 1～3, preferred 1～1.2, reaction times is 12～20 hours, temperature of reaction is-78～25 ℃, remove and desolvate, after resistates organic solvent washing, the filtration, will obtain catalyst prod behind the filtrate recrystallization.
The side group that is used for olefinic polymerization or copolymerization of the present invention contains the preparation method of heteroatomic metallocene chrome catalysts, wherein (1), in the reaction of (2) step, described alkali alkyl compound is a n-Butyl Lithium, in the reaction in (3) step, the preferred chromium trichloride of chromium cpd.
The side group that is used for olefinic polymerization or copolymerization of the present invention contains the preparation method of heteroatomic metallocene chrome catalysts, and described organic medium or organic solvent are selected from tetrahydrofuran (THF), ether, toluene, benzene, normal hexane, sherwood oil or their mixture.
In the reaction in (1) step, dissolving alkyl an alkali metal salt and 6, the organic solvent of 6 '-dialkyl group fulvene is preferably ether, and the organic solvent that is used to wash preferably is selected from normal hexane;
(2), organic medium or the organic solvent described in the reaction of (3) step preferably is selected from tetrahydrofuran (THF), ether, toluene;
The organic solvent that is used to wash in the reaction of (3) step preferably is selected from ether, toluene, normal hexane, sherwood oil or their mixture.
The preparation method that the side group that is used for olefinic polymerization or copolymerization provided by the invention contains heteroatomic metallocene chrome catalysts is with ligand compound α, α-dialkyl group replaces adjacent N, N-dialkyl amino benzyl replaces an alkali metal salt luxuriant and alkali alkyl compound reaction generation ligand compound, obtains with the halide reaction of chromium again; The halogenide of chromium is general to generate CrCl with tetrahydrofuran (THF) earlier
3(THF)
3Adducts is participated in reaction.Reaction raw materials comprises: adjacent N, and N-dialkyl amino bromobenzene, cyclopentadiene, letones is as acetone, methylethylketone, pimelinketone etc.; Normal hexane, tetrahydrofuran (THF), ether, benzene, toluene, chloroform, methylene dichloride, sherwood oil, n-Butyl Lithium, chromium trichloride, four chromium chlorides, sodium hydroxide, anhydrous Na
2SO
4, frozen water etc.;
The side group that is used for olefinic polymerization or copolymerization of the present invention contains heteroatomic metallocene chrome catalysts and prepares step and see Fig. 1.
A kind of alpha-olefin closes poly-method, and containing heteroatomic metallocene chrome catalysts with the side group that is used for olefinic polymerization or copolymerization of the present invention is Primary Catalysts, is promotor with the alkylaluminoxane, the preferable methyl aikyiaiurnirsoxan beta; Polymerizing condition is: 10～110 ℃ of polymerization temperatures, and polymerization pressure 0.1～1.0MPa, aluminium during polymerization in the promotor and the chromium mol ratio in the Primary Catalysts are 50～4000: 1, preferred 100～2000: 1.
Alpha-olefin of the present invention is an ethene, propylene, 1-hexene etc.Polymerization methods can be mass polymerization, slurry polymerization or vapour phase polymerization.
Side group of the present invention contains that heteroatomic metallocene chrome catalysts is used for olefinic polymerization or copolymerization compared with prior art has following tangible advantage:
The catalyst structure novelty, it is higher to be used for olefin polymerizating activity, and catalyzer is easily synthetic, good stability, cold resistance is good.
Embodiment 1
Preparation α, alpha-alpha-dimethyl replaces adjacent N, and N dimethylamine base benzyl replaces luxuriant chromium cpd 1.
(1) 6, the preparation of 6 '-dimethyl fulvene:
Under argon shield, in the there-necked flask of 150mL, add the new cyclopentadiene that steams of 33g (0.50mol), and 37mL (0.50mol) acetone; reaction solution splashes into 20g methylethylolamine solution under 0 ℃, solution by colourless become orange; stir 4h; add 30～50mL water, use the n-hexane extraction organic layer, the gained organic phase is behind anhydrous magnesium sulfate drying; carry out underpressure distillation after extracting solvent; collect 43 ℃/9mmHg cut, get glassy yellow liquid 35.0g, productive rate 66.3%.
(2) preparation ligand compound
Under the protection of inert gas, the adjacent N of what, N dimethylamine base bromobenzene (39.30mmol, and the hexane solution of slow dropping n-Butyl Lithium in 50mL hexane solution 7.86g) (39.30mmol, 21.36mL) ,-78 ℃ of reactions.After dropwising, reaction mixture continues to stir 6h, generates a large amount of white precipitates.Leave standstill, remove by filter solvent, with normal hexane (30mL * 2) washing gained white precipitate.Add dry ether and dissolve this precipitation.
With 6, (39.30mol 4.17g) is dissolved in the 20mL ether 6 '-dimethyl fulvene, and slowly is added drop-wise to-78 ℃ of reactions in the above-mentioned lithium salt solution, stirs, and generates a large amount of light-yellow precipitate.
Reaction mixture is poured in about 50mL frozen water, tells organic layer.Organic phase 15mL frozen water and the pickling of 4mL salt.Ether (30mL * 2) aqueous phase extracted.Water is as cold as-5 ℃, is adjusted to pH=13 with sodium hydroxide.Add ether (20mL * 2) aqueous phase extracted, merge organic phase, add anhydrous Na
2SO
4Dried overnight.Filter, underpressure distillation obtains part α, and alpha-alpha-dimethyl replaces adjacent N, and N dimethylamine base benzyl replaces (96～97 ℃/0.1mmHg) productive rate 11.24% of luxuriant 1.0034g.
1H?NMR(δ，ppm，CDCl
3)：7.34(dt，1H，Ph?o-H)，7.28(dd，1H，Ph?m-H)，7.22(dt，1H，Ph?m-H)，7.12(m，1H，Php-H)，6.25(m，3H，Cp?H)，2.96(m，1H，Cp?H)，2.35(s，6H，N(CH
3)
2)，1.67(s，6H，C(CH
3)
2).
(3) preparation catalyzer
Under the argon shield, at α, alpha-alpha-dimethyl replaces adjacent N, N dimethylamine base benzyl replace cyclopentadienyl ligand (0.95g, in 30mL tetrahydrofuran solution 4.18mmol), slowly drip the 2.27mL n-Butyl Lithium hexane solution (4.18mmol, 1.84mol/L), stirring is spent the night;
Above-mentioned lithium salt solution slowly is added drop-wise to CrCl at-78 ℃
3(THF)
3(4.18mmol in 50mL tetrahydrofuran solution 1.57g), rises to room temperature reaction 18h.Drain solvent,, filter with the toluene extraction with normal hexane washing three times (10mL * 3), the recrystallization room temperature is separated out the blackish green crystal.
Molecular structural formula is as follows:
Molecular formula: C
16H
20Cl
2CrN
EI-MS(m/e)：348.0(1，M)，312.0(100，M-Cl)，276.1(15，M-2Cl)，262.1(3，M-2Cl-CH
3)，226.1(11，M-2Cl-Cr)，196.1(50，M-2Cl-Cr-2CH
3).
Infrared data (cm
-1): 3110.0 (m), 3094.0 (m), 3080.8 (m), 3022.7 (m49), 2971.2 (m39), 2922.3 (m37), 2867.7 (m48), 28 19.4 (s57), 2779.2 (s59), 1635.5 (s50), 1482.5 (m33), 1465.2 (m30), 1441.5 (m33), 1402.3 (m45), 1368.0 (s51), 1290.7 (vs65), 1258.9 (vs62), 1114.5 (s54), 1065.0 (m45), 1038.2 (m47), 979.2 (s57), 902.9 (s56), 884.0 (s58)
Embodiment 2
Preparation α, α-cyclohexyl replaces adjacent N, and N dimethylamine base benzyl replaces luxuriant chromium cpd 2.
(1) 6, the preparation of 6 '-cyclohexyl fulvene: the preparation method is with 6, and 6 '-dimethyl fulvene is that raw material changes pimelinketone into by acetone;
(2) preparation ligand compound
Under the protection of inert gas, in adjacent N, N dimethylamine base bromobenzene (73.27mmol, and the hexane solution of slow dropping n-Butyl Lithium in 50mL hexane solution 14.66g) (73.27mmol, 39.82mL) ,-78 ℃ of reactions.After dropwising, reaction mixture continues to stir 6h, generates a large amount of white precipitates.Leave standstill, remove by filter solvent, with normal hexane (30mL * 2) washing gained white precipitate.Add dry ether and dissolve this precipitation.
With 6, (73.27mol 10.70g) is dissolved in the 20mL ether 6 '-cyclohexyl fulvene, and slowly is added drop-wise to-78 ℃ of reactions in the above-mentioned lithium salt solution, and stirring is spent the night, and generates a large amount of light-yellow precipitate.
Reaction mixture is poured hydrolysis in about 50mL frozen water into, organic phase 15mL frozen water and the pickling of 6mL salt, ether (30mL * 2) aqueous phase extracted.Water is as cold as-5 ℃, is adjusted to pH=13 with sodium hydroxide.Add ether (20mL * 2) aqueous phase extracted, merge organic phase, add anhydrous Na
2SO
4Dried overnight.After removing by filter siccative, underpressure distillation obtains part α, and α-cyclohexyl replaces adjacent N, and N dimethylamine base benzyl replaces (138-140 ℃/1mmHg) productive rate 36.45% of luxuriant 7.1093g.
1H?NMR(δ，ppm，CDCl
3)：7.47(dd，1H)，7.21-7.12(m，3H)，6.35(m，1H)，6.25(m，1H)，6.01(m，1H)，2.93(m，1H)，2.46(m，2H)，2.28(s，6H)，2.18(m，2H)，1.53-1.42(m，6H).
MS(m/e)：267.2(100，M)，252.2(6，M-CH
3)，238.2(2，M-2CH
3)，223.1(1，M-N(CH
3)
2)，202.2(6，M-Cp)，65.0(1，Cp).
IR(cm
-1，KBr)：3057.17(m)，2931.28(vs)，2854.01(vs)，2817.49(s)，2776.88(s)，1593.55(w)，1512.53(w)，1485.46(s)，1451.24(s)，1375.58(w)，1354.42(m)，1291.43(m).
(3) preparation catalyzer
Under the argon shield, at part α, α-cyclohexyl replaces adjacent N; the replacement of N dimethylamine base benzyl is luxuriant, and (0.8009g in 30mL tetrahydrofuran solution 4.18mmol), slowly drips the hexane solution (4.18mmol of 2.27mL n-Butyl Lithium; 1.84mol/L), stirring is spent the night.
Above-mentioned lithium salt solution slowly is added drop-wise to CrCl at-78 ℃
3(THF)
3(4.18mmol in 50mL tetrahydrofuran solution 1.57g), rises to room temperature reaction 18h.Drain solvent, the toluene extraction is filtered, and the crystallization room temperature is separated out the blackish green crystal.
Molecular structural formula is as follows:
Molecular formula: C
19H
24Cl
2CrN
M.S.388.1(1，M)，352.1(100，M-Cl)，316.1(18，M-2Cl)，266.2(24，M-2Cl-Cr)，251.2(13，M-2Cl-Cr-CH
3)，222.1(5，M-2Cl-Cr-N(CH
3)
2)
Infrared data (cm
-1): 3 137.04 (m), 3087.64 (s), 2945.62 (vs), 2923.91 (vs), 2861.57 (m), 1490.82 (w), 1464.88 (s), 1444.39 (vs), 1402.58 (w), 1071.02 (m), 1010.94 (w), 977.97 (w).
Preparation α, Alpha-Methyl, ethyl replace adjacent N, and N dimethylamine base benzyl replaces luxuriant chromium cpd 3.
(1) preparation 6,6 '-methyl, the ethyl fulvene: the preparation method is with 6, and 6 '-dimethyl fulvene is that raw material changes methylethylketone into by acetone;
(2) preparation ligand compound:
Under the protection of inert gas, in adjacent N, N dimethylamine base bromobenzene (45.84mmol, and the hexane solution of slow dropping n-Butyl Lithium in 50mL hexane solution 9.16g) (45.84mmol, 24.91mL) ,-78 ℃ of reactions.After dropwising, reaction mixture continues to stir 6h, generates a large amount of white precipitates.Filter, with normal hexane (30mL * 2) washing.Add dry ether and dissolve this precipitation.
With 6,6 '-methyl, (39.30mol 4.17g) is dissolved in the 20mL ether ethyl fulvene, and slowly is added drop-wise to-78 ℃ of reactions in the above-mentioned lithium salt solution, and stirring is spent the night, and generates a large amount of light-yellow precipitate.
Reaction mixture is poured hydrolysis in about 50mL frozen water into, tells organic layer.Organic phase 15mL frozen water and the pickling of 4mL salt.Ether (30mL * 2) aqueous phase extracted.Water is as cold as-5 ℃, is adjusted to pH=13 with sodium hydroxide.Add ether (20mL * 2) aqueous phase extracted, merge organic phase, add anhydrous Na
2SO
4Dried overnight.After removing by filter siccative, extract solvent to doing, underpressure distillation obtains part α, and Alpha-Methyl, ethyl replace adjacent N, and N dimethylamine base benzyl replaces (78～82 ℃/0.1mmHg) productive rate 20.24% of luxuriant 2.2350g.
MS(m/e)：242.3(100，M
+)
IR(cm
-1，KBr)：3059.31(m)，3012.15(vs)，2968.44(vs)，2931.53(s)，2875.35(s)，2618.41(w)，2778.11(m)，1598.61(m)，1573.66(w)，1485.52(s)，1452.72(vs)，1378.05(m)，1354.61(m)，1290.95(m)，1190.41(m)，1161.70(w)，1142.17(w)，1083.63(w).
(3) preparation catalyzer
Under the argon shield, at α, Alpha-Methyl; ethyl replaces adjacent N, and N dimethylamine base benzyl replaces cyclopentadienyl ligand, and (3.65mmol is in 30mL tetrahydrofuran solution 0.8786g); slowly the hexane solution of dropping 2.27mL n-Butyl Lithium (3.65mmol, 1.98mL), spend the night by stirring.
Above-mentioned lithium salt solution slowly is added drop-wise to CrCl at-78 ℃
3(THF)
3(3.65mmol in 50mL tetrahydrofuran solution 1.35g), rises to room temperature reaction 18h.The color of solution becomes blueness by purple gradually.Drain solvent,, filter with the toluene extraction with normal hexane washing three times (10mL * 3), filtrate adds normal hexane crystallization room temperature and separates out the blackish green crystal.
Molecular structural formula is as follows:
Molecular formula: C
17H
22Cl
2CrN
M.S.362.1(1，M)，326.1(69，M-Cl)，311.1(8，M-Cl-CH
3)，290.1(17，M-2Cl)，276.1(4，M-2Cl-CH
3)，239.2(23，M-2Cl-Cr)，225.2(6，M-2Cl-Cr-CH
3)，210.1(44，M-2Cl-Cr-2CH
3)，196.1(100，M-2Cl-Cr-CH
3-CH
2CH
3)
Infrared data (cm
-1): 3137.04 (m), 3087.64 (s), 2945.62 (vs), 2923.91 (vs), 2861.57 (m), 1490.82 (w), 1464.88 (s), 1444.39 (vs), 1402.58 (w), 1071.02 (m), 1010.94 (w), 977.97 (w)
Embodiment 4
Mouth of 150mL there-necked flask is loaded onto the head of bleeding, the intermediary mouth load onto have the emulsion tube plug the agitator sleeve pipe as charging opening, another mouthful then loaded onto the agitator sleeve pipe that has the ethene conduit, at first there-necked flask taken out roasting 10 minutes, fill the ethene cooling, and take out and fill three times; Add 10.10mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, logical ethene is saturated, adds the catalyzer 5.05 μ mol of preparation among the embodiment 1 then, and making the Al/Cr ratio is 2000, temperature of reaction is 25 ℃, polymerization pressure keeps 0.1Mpa with magnetic valve, stirs ethylene polymerization 30min down, after reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.455g catalytic activity 1.8 * 10 of polymkeric substance
5Gmol
-1h
-1
Embodiment 5
Mouth of 150mL there-necked flask is loaded onto the head of bleeding, the intermediary mouth load onto have the emulsion tube plug the agitator sleeve pipe as charging opening, another mouthful then loaded onto the agitator sleeve pipe that has the ethene conduit, at first there-necked flask taken out roasting 10 minutes, fill the ethene cooling, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, logical ethene is saturated, adds the catalyzer 25.2 μ mol of preparation among the embodiment 1 then, and making the Al/Cr ratio is 100, temperature of reaction is 25 ℃, polymerization pressure keeps 0.1Mpa with magnetic valve, stirs ethylene polymerization 30min down, and reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.807g catalytic activity 0.64 * 10 of polymkeric substance
5Gmol
-1h
-1
Embodiment 6
Mouth of 150mL there-necked flask is loaded onto the head of bleeding, the intermediary mouth load onto have the emulsion tube plug the agitator sleeve pipe as charging opening, another mouthful then loaded onto the agitator sleeve pipe that has the ethene conduit, at first there-necked flask taken out roasting 10 minutes, fill the ethene cooling, and take out and fill three times.Add 5.05mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, logical ethene is saturated, adds the catalyzer 5.05 μ mol of preparation among the embodiment 1 then, and making the Al/Cr ratio is 1000, temperature of reaction is 0 ℃, polymerization pressure keeps 0.1Mpa with magnetic valve, stirs ethylene polymerization 30min down, and reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.381g catalytic activity 1.51 * 10 of polymkeric substance
5Gmol
-1h
-1
Embodiment 7
Mouth of 150mL there-necked flask is loaded onto the head of bleeding, the intermediary mouth load onto have the emulsion tube plug the agitator sleeve pipe as charging opening, another mouthful then loaded onto the agitator sleeve pipe that has the ethene conduit, at first there-necked flask taken out roasting 10 minutes, fill the ethene cooling, and take out and fill three times.Add 5.05mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, logical ethene is saturated, adds the catalyzer 5.05 μ mol of preparation among the embodiment 2 then, and making the Al/Cr ratio is 1000, temperature of reaction is 0 ℃, polymerization pressure keeps 0.1Mpa with magnetic valve, stirs ethylene polymerization 30min down, and reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.500g catalytic activity 1.98 * 10 of polymkeric substance
5Gmol
-1h
-1
Embodiment 8
Mouth of 150mL there-necked flask is loaded onto the head of bleeding, the intermediary mouth load onto have the emulsion tube plug the agitator sleeve pipe as charging opening, another mouthful then loaded onto the agitator sleeve pipe that has the ethene conduit, at first there-necked flask taken out roasting 10 minutes, fill the ethene cooling, and take out and fill three times.Add 5.05mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, and logical ethene is saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 2 then, making the Al/Cr ratio is 1000, and 0 ℃ of polymerization temperature, polymerization pressure keep 0.1Mpa with magnetic valve, stirs ethylene polymerization 30min down.Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.396g catalytic activity 1.57 * 10 of polymkeric substance
5Gmol
-1h
-1, the molecular weight M of polymkeric substance
w=6.8 * 10
5, molecular weight distribution (M
w/ M
n=5.63).
Embodiment 9
With exsiccant 150ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to propylene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled the propylene cooling, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, and logical propylene is saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 1 then, making the Al/Cr ratio is 500, and 25 ℃ of polymerization temperatures, polymerization pressure keep 0.1Mpa with magnetic valve, stirs propylene polymerization 30min down; Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.0381g catalytic activity 1.51 * 10 of polymkeric substance
4Gmol
-1h
-1
Embodiment 10
With exsiccant 150ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to propylene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled the propylene cooling, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, and logical propylene is saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 1 then, making the Al/Cr ratio is 500, and 0 ℃ of polymerization temperature, polymerization pressure keep 0.1Mpa with magnetic valve, stirs propylene polymerization 30min down.Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.0437g catalytic activity 1.73 * 10 of polymkeric substance
4Gmol
-1h
-1
Embodiment 11
With exsiccant 150ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to propylene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled the propylene cooling, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, and logical propylene is saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 2, making the Al/Cr ratio is 500, and 25 ℃ of polymerization temperatures, polymerization pressure keep 0.1Mpa with magnetic valve, stirs logical propylene polymerization 30min down.Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.0450g catalytic activity 1.78 * 10 of polymkeric substance
4Gmol
-1h
-1
Embodiment 12
With exsiccant 150ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to propylene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled the propylene cooling, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, and logical propylene is saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 3, making the Al/Cr ratio is 500, and 25 ℃ of polymerization temperatures, polymerization pressure keep 0.1Mpa with magnetic valve, stirs propylene polymerization 30min down.Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.0414g catalytic activity 1.64 * 10 of polymkeric substance
4G mol
-1h
-1The molecular weight M of polymkeric substance
w=5.7 * 10
4, molecular weight distribution (M
w/ M
n=2.73).
Embodiment 13
With exsiccant 150ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to propylene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled ethene: the mixed gas cooling of propylene=61: 39, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, logical above-mentioned ethene, propylene mixed gas are saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 1, making the Al/Cr ratio is 500,25 ℃, stir under second third copolymerization, polymerization pressure keeps 0.1Mpa with magnetic valve, reaction 30min.Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.303g catalytic activity 1.20 * 10 of polymkeric substance
5Gmol
-1h
-1
Embodiment 14
With exsiccant 150ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to propylene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled ethene: the mixed gas cooling of propylene=70: 30, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, and logical above-mentioned ethene, propylene mixed gas are saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 2, making the Al/Cr ratio is 500, at 25 ℃, polymerization pressure 0.1Mpa, stirs the second third copolyreaction 30min down.Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.339g catalytic activity 1.34 * 10 of polymkeric substance
5Gmol
-1h
-1
Embodiment 15
With exsiccant 150ml there-necked flask, load onto two agitator sleeve pipes, sleeve pipe is loaded onto emulsion tube and plug as charging opening, and another sleeve pipe leads to propylene, and another of there-necked flask mouthful seals with vacuum stopper.At first there-necked flask was taken out roasting 10 minutes, and filled ethene: the mixed gas cooling of propylene=68: 32, and take out and fill three times.Add 2.52mmolMAO, adding toluene then, to make the polymerization cumulative volume be 50ml, logical above-mentioned ethene, propylene mixed gas are saturated, the catalyzer 5.05 μ mol that add preparation among the embodiment 3, making the Al/Cr ratio is 500, at 25 ℃, polymerization pressure maintenance 0.1Mpa, stir the second third copolymerization 30min down.Reaction finishes, with the ethanolic soln termination reaction of 5% hcl acidifying, after the filtration with polymkeric substance in vacuum drier 40 ℃ drain more than 4 hours.Get the weight 0.316g catalytic activity 1.25 * 10 of polymkeric substance
5Gmol
-1h
-1
Embodiment 16
In the 250mL there-necked flask, add 100mL toluene, add comonomer 1-hexene 5ml and 3.3ml MAO, be placed in the oil bath, feeding ethene is saturated, stablized two minutes, and added the catalyzer 5.05 μ mol of preparation among the embodiment 1, at 25 ℃, polymerization pressure maintenance 0.1Mpa, behind the polymerization 1h, with 50ml 3%HCl ethanolic soln termination reaction.Filter, polymkeric substance is 60 ℃ of following vacuum-dryings, constant weight, the weight 2.701g of polymkeric substance, catalytic activity 5.35 * 10
5Gmol
-1h
-1Measure the molecular weight M of polymkeric substance with GPC
w=1.01 * 10
5And molecular weight distribution (M
w/ M
n=2.43), and use
13C NMR measures the content 5.34 of comonomer.
Claims (8)
1. a side group that is used for olefinic polymerization contains heteroatomic metallocene chrome catalysts, and its structure has following general formula:
R in the formula (I)
1Cp is cyclopentadienyl or substituted cyclopentadienyl, R
1Be selected from hydrogen, C
1-C
12Alkyl, C
1-C
12Alkoxyl group or C
6-C
12Aryl, R
2And R
3Be C
1-C
12Straight chained alkyl, branched-chain alkyl, cycloalkyl, alkoxyl group or C
6-C
12Aryl; Y is a nitrogen, and two other group that links to each other with Y in the structural formula is an alkyl, and X is a halogen atom.
2. the side group that is used for olefinic polymerization according to claim 1 contains heteroatomic metallocene chrome catalysts, it is characterized in that R in the formula (I)
1Be hydrogen or C
1-C
4Alkyl, R
2And R
3Be hydrogen or C
1-C
4Alkyl, X is a chlorine.
3. the side group that is used for olefinic polymerization according to claim 1 contains heteroatomic metallocene chrome catalysts, it is characterized in that R
1Be hydrogen, R
2And R
3Be hydrogen, methyl or ethyl.
4. the described side group that is used for olefinic polymerization of claim 1 contains the preparation method of heteroatomic metallocene chrome catalysts, comprises the steps:
(1) ligand compound α, α-dialkyl group replaces adjacent N, and N-dialkyl amino benzyl replaces luxuriant synthesizing;
Under the protection of inert gas, alkali alkyl compound solution and adjacent N, N-dialkyl amino bromobenzene removes by filter solvent-78～25 ℃ of following stirring reactions 4～8 hours, with organic solvent washing gained precipitation, add organic solvent and obtain the alkali alkyl salts solution after with this resolution of precipitate; 6,6 '-dialkyl group fulvene solution and abovementioned alkyl alkali metal salt soln were-78～25 ℃ of following stirring reactions 4～24 hours; Reaction mixture is told organic layer after the hydrolysis in frozen water; Organic phase frozen water and salt acid elution; And use the organic solvent extraction water, at 0～5 ℃, under pH 12～14 conditions, add organic solvent aqueous phase extracted once more; Merge organic phase, add anhydrous Na
2SO
4Dry 12～24 hours, to filter, underpressure distillation obtains part;
(2) ligand compound and the alkali alkyl compound shown in the formula (II) reacted in organic medium, temperature of reaction mol ratio such as is pressed and was under agitation reacted 12～24 hours for-78～25 ℃, generates an alkali metal salt of ligand compound, R in the formula (II)
1Cp is cyclopentadienyl or substituted cyclopentadienyl, R
1Be selected from hydrogen, C
1-C
12Alkyl, C
1-C
12Alkoxyl group or C
6-C
12Aryl, R
2And R
3Be C
1-C
12Straight chained alkyl, branched-chain alkyl, cycloalkyl, alkoxyl group or C
6-C
12Aryl, Y is a nitrogen, two other group that links to each other with Y in the structural formula is an alkyl;
(3) an alkali metal salt with part reacts with chromium trichloride or four chromium chlorides in organic medium, by chromium/part molar ratio computing is 1～3, reaction times is 12～20 hours, temperature of reaction is-78～25 ℃, remove and desolvate, after resistates organic solvent washing, the filtration, will obtain catalyst prod behind the filtrate recrystallization; Wherein (1), in the reaction of (2) step, described alkali alkyl compound is a n-Butyl Lithium; Organic medium described in the reaction or organic solvent are selected from tetrahydrofuran (THF), ether, toluene, benzene, normal hexane, sherwood oil or their mixture.
5. the side group that is used for olefinic polymerization according to claim 4 contains the preparation method of heteroatomic metallocene chrome catalysts, it is characterized in that chromium cpd is a chromium trichloride, is 1～1.2 by chromium/part molar ratio computing in the reaction in (3) step.
6. alpha-olefine polymerizing method, it is characterized in that with the described catalyzer of claim 1 be Primary Catalysts, with the alkylaluminoxane is promotor, make alpha-olefin at 10～110 ℃, 0.1 polymerization under the～1.0MPa, aluminium during polymerization in the promotor and the chromium metal mol ratio in the Primary Catalysts are 50～4000: 1.
7. alpha-olefine polymerizing method according to claim 6, aluminium when it is characterized in that polymerization in the promotor and the chromium metal mol ratio in the Primary Catalysts are 100～2000: 1.
8. according to the described alpha-olefine polymerizing method of claim 6, it is characterized in that described alpha-olefin is selected from ethene, one or more in propylene or the 1-hexene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049849A (en) * | 1989-08-31 | 1991-03-13 | 陶氏化学公司 | Addition polymerization catalyzer with constrained geometry, the parent of its preparation method, using method and the new polymers that obtains thus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049849A (en) * | 1989-08-31 | 1991-03-13 | 陶氏化学公司 | Addition polymerization catalyzer with constrained geometry, the parent of its preparation method, using method and the new polymers that obtains thus |
Non-Patent Citations (4)
| Title |
|---|
| Dornor-Ligand-Substituted Cyclopentadienylchromium(III)Complexes:A New Class of Alkene Polymerization Catalyst.2.Phosphinoalkyl-Substituted Systems. Vindar R.Organometallics,No.20. 2001 |
| Dornor-Ligand-Substituted Cyclopentadienylchromium(III)Complexes:A New Class of Alkene Polymerization Catalyst.2.Phosphinoalkyl-Substituted Systems. Vindar R.Organometallics,No.20. 2001 * |
| 均相铬系催化剂的合成与催化α－烯烃聚合的进展. 张浩.有机化学，第22卷第12期. 2002 |
| 均相铬系催化剂的合成与催化α－烯烃聚合的进展. 张浩.有机化学，第22卷第12期. 2002 * |
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