CN1398835A - N-P coordinating catalyst for oligomerization of nickel ethylene - Google Patents
N-P coordinating catalyst for oligomerization of nickel ethylene Download PDFInfo
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- CN1398835A CN1398835A CN 01120554 CN01120554A CN1398835A CN 1398835 A CN1398835 A CN 1398835A CN 01120554 CN01120554 CN 01120554 CN 01120554 A CN01120554 A CN 01120554A CN 1398835 A CN1398835 A CN 1398835A
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- ethene
- nickel
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- diphenylphosphino
- quinoline
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Abstract
The present invention discloses a kind of N-P coordination catalyst for oligomerization of post transition metal nickel ethylene. It is halogeno aryl (8-(diphneyl phospho) quinolyl nickel coordination compound. The catalyst of the present invention is a new type N-P heteroatom coordination catalyst system with high chemical stability for easy preservation and high repeatability in catalytic activity.
Description
Technical field:
The present invention relates to a kind of N-P coordinate rear transition metal catalyst for oligomerization of nickel ethylene.
Background technology:
The catalyzed ethylene oligomerisation can the scale operation normal olefine, and its product is important organic chemical industry's intermediate, has become an individual branches in the petrochemical industry.In recent years, the research of rear transition metal olefinic polymerization and catalyst for oligomerization has obtained developing rapidly (Angew.Chem.Int.Ed.1999,38,428～447; Chem.Rev.2000,100,1169～1203).In addition, the development of olefinic polymerization impels people that ethene and other olefin-copolymerization are obtained the polyolefine material of different structure, different performance, presses for preparation C
4, C
6, C
8Oligopolymer Deng ethene.
Since the seventies, polymerization of transition metal complex homogeneous catalytic olefin and oligomerisation research are subject to people's attention, and people make great efforts to study raw catalyst and improve existing catalyzer, improve the selectivity of activity of such catalysts and catalysate.In numerous metals that research is explored, research early, development soon, what relatively concentrate is nickel cation type catalyst system, as already the report United States Patent (USP): USPatent 3686351,19720711 and US Patent 3676523,19720822, developed into SHOP (the Shell Higher OlefinProcess) technological process of shell (Shell) company based on this patented technology.This is an O-P bridging type ligand catalyst, and the ethylene oligomerization catalysis activity is approximately 10
5Gram ethene/(mole Ni hour).Multiple patents such as O-O, P-N, P-P type and N-N type coordination nickel catalyzator had been developed afterwards again, wherein the nitrogen-atoms catalyzer of doing the coordination tooth is subjected to people's extensive attention, as recent patent: Jpn.Kokai Tokkyo Koho JP 11060627, A2 2 Mar 1999 Heisei; PCT Int.Appl.WO 9923096 A1 14 May 1999; PCT Int.Appl.WO 9951550 A1 14 Oct 1999.Yet above-mentioned catalyzer is subjected to the protection or the covering of foreign patent mostly, therefore, develops our olefin polymerization catalysis of intellecture property and has great importance for the polyolefine industry that develops China.
Summary of the invention:
Ethylene oligomerization after-trasition metal coordination catalyst of the present invention, i.e. halogenated aryl (8-(diphenylphosphino) quinoline) nickel complex, general structure is:
When wherein X was chlorine (Cl), R was a naphthyl; When X was bromine (Br), R was a phenyl.
It is with 8-(diphenylphosphino) quinoline part and trans-chlorination (1-naphthyl) (two (triphenylphosphine)) nickel or trans-bromination phenyl (two (triphenylphosphine)) nickel reactant and obtain that rear transition metal nickel of the present invention is joined preparation with the thing ethylene oligomerization catalyst.
The preparation of ethylene oligomerization after-trasition metal coordination catalyst of the present invention, raw material comprises: the 8-chloroquinoline, triphenylphosphine, lithium, tetrahydrofuran (THF), ether, toluene, normal hexane, and promotor trimethylammonium alumina alkane are commercially available analytical reagent; Trans-chlorination (1-naphthyl) (two (triphenylphosphine)) nickel, trans-the bromination phenyl (two (triphenylphosphine)) nickel is for according to document (J.van Soolingen, H.D.Verkruijsse, M.A.Keegstra and L.Brandsma, Syn.Commun., 20,3153 (1990)) synthetic.Purifying after catalyst ligand is synthetic adopts recrystallization; The catalyzer purifying is after the reaction, to add normal hexane and separate out post precipitation in methylene dichloride, washs with ether, obtains after the drying.
Ethylene oligomerization rear transition metal of the present invention is joined and the thing Preparation of catalysts, and step is carried out in the following order: 1. the preparation of catalyst ligand: see Fig. 1.
The diphenylphosphine lithium is by relevant document (Drago, R.S.; Desmond, M.J.; Wrden, D.B.J.Am.Chem.Soc.1983,105,2287) utilize triphenylphosphine and metallic lithium reaction, utilize tertiary butyl chloride to react away phenyl lithium then and obtain.
The preparation of part then is by relevant document (R.D.Felthem and H.G.Metzger, J.Organomet.Chem., 33,347 (1971)) react in tetrahydrofuran (THF) by 8-chloroquinoline and diphenylphosphine lithium, slough a part lithium chloride, formation contains 8-(diphenylphosphino) the quinoline part of nitrogen phosphine bidentate, and is confirmed through nuclear-magnetism, mass spectroscopy.2. the preparation of chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel complex: see Fig. 2.
Under the room temperature, 8-(diphenylphosphino) quinoline and trans-chlorination (1-naphthyl) (two (the triphenylphosphine)) nickel that make were reacted in methylene dichloride in 1: 1 in molar ratio, form title complex, separate out precipitation after adding normal hexane, with the ether washing for several times, promptly obtain chlorination (1-naphthyl) (8-(diphenylphosphino quinoline)) nickel complex.Its structure is confirmed through single crystal diffraction.3. the preparation of bromination phenyl (8-(diphenylphosphino) quinoline) nickel complex: see Fig. 2.
Under the room temperature, trans-bromination phenyl (two (triphenylphosphine)) nickel and 8-(diphenylphosphino) quinoline are reacted in methylene dichloride, form title complex.Solvent is removed in underpressure distillation, adds the triphenylphosphine that anhydrous diethyl ether is washed unreacted 8-(diphenylphosphino) quinoline and generation off then, promptly obtains bromination phenyl (8-(diphenylphosphino) quinoline) nickel complex.
When catalyzer of the present invention was used for ethylene oligomerization catalysis, used catalytic reaction kettle was carried out nitrogen, ethylene gas displacement successively, and reaction system is in the ethylene gas environment.Then, add solvent toluene and promotor trimethylammonium alumina alkane in turn, the catalyst complexes solution that reinjects carries out the reaction of ethene normal pressure oligomerization catalysis under specified criteria.Reaction finishes, and adds acidifying ethanol termination reaction, and formed oligomerization product is present in the toluene solvant phase.The output of ethylene oligomerization product and distribution are tested with the chromatograph-mass spectrometer coupling technology.
Catalyzer of the present invention, overcome the weakness of catalyzer synthesis step complexity, preparation difficulty in the prior art, open up novel N-P heteroatoms coordination catalyst system, invented halogenated aryl (8-(diphenylphosphino) quinoline) nickel complex as catalyst agent, preparation is simple, the productive rate height, purifying is easy, compound stability is better, is convenient to produce in enormous quantities, and preservation and the catalyst activity reproducibility of being convenient to catalyzer are good.Catalyzer of the present invention and promoter aluminium alkyl oxygen alkane (as methylaluminoxane (MAO) etc.) form catalyst system, first Application has obtained high content of alpha-alkene oligomer in vinyl polymerization, and catalyst activity is higher, is about 10
5Gram ethene/mol catalyst hour; Opened up the frontier of post-transition metal ethylene polymerization catalyst.
Description of drawings: Fig. 1 is that part synthetic reaction scheme Fig. 2 is that the composite diagram 3 of joining with thing is the crystalline structure of chlorination among the embodiment 1 (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel complex
Embodiment: part 8-(diphenylphosphino) quinoline synthetic:
Under nitrogen protection, (5.25 grams 0.02mol) dissolve in (30mL) in the anhydrous tetrahydrofuran solution, and (0.28 gram 0.04mol), stirs under the room temperature, up to the completely dissolve of lithium sheet to add the sheet metal lithium with triphenylphosphine.Solution is cooled to 0 ℃, stirs and drip trimethyl carbinol chlorine (1.85 grams, anhydrous tetrahydrofuran solution 0.02mol) (10mL) in following half an hour.After dripping off, be warming up to room temperature, continue to stir 0.5 hour, get a red solution.Solution is cooled to-78 ℃, (3.26 grams, anhydrous tetrahydrofuran solution 0.02mol) (10mL) drip and finish, and solution is warming up to room temperature, react 12 hours slowly to drip the 8-chloroquinoline under stirring.Then solution is poured into (30mL) in the frozen water, and the usefulness extracted with diethyl ether (3 * 30mL), remove most of solvent under reduced pressure, the product mother liquor is placed in the refrigerator and spends the night, and separates out white crystal 5g, yield: 80%.
1H?NMR(CDCl
3)：δ1.27(24H，d，J＝6.8Hz)，1.49(9H，s)，3.04-3.14(4H，m)，7.24(6H，m)，7.5(1H，br)，8.37-8.80(3H，br)；EI-MS(m/z)：524(M
+，7.8％)，509(5.1％)，349(23.6％)，348(100％)，319(5.5％)；176(12.3％)。The preparation of chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel complex:
Under the room temperature, trans-chlorination (1-naphthyl) (two (triphenylphosphine)) nickel (1.49g, 2 mmol) is dissolved in the 10mL methylene dichloride, stir and slowly drip 8-(diphenylphosphino) quinoline (0.63 gram down, methylene dichloride 2mmol) (10mL) solution dropwises, and continues reaction after 10 minutes, add anhydrous n-hexane (50mL), separate out a large amount of yellow mercury oxides, filter, with ether washing (3 * 10mL), get a yellow powder, yield is more than 99%.It can stable in the airly exist.Decomposition temperature: 237.7 ℃.The preparation of bromination phenyl (8-(diphenylphosphino) quinoline) nickel complex:
Under the room temperature, (1.06g 2mmol) is dissolved in the 10mL methylene dichloride with trans-bromination phenyl (two (triphenylphosphine)) nickel, stir and slowly drip 8-(diphenylphosphino) quinoline (0.63 gram down, methylene dichloride 2mmol) (10mL) solution dropwises, and continues reaction 10 minutes.Solvent is removed in underpressure distillation, adds the triphenylphosphine that anhydrous diethyl ether (20mL) dissolves unreacted 8-(diphenylphosphino) quinoline and generation then, filter, with the ether washing (3 * 10mL), a brown ceramic powder, yield is more than 99%.It can stable in the airly exist.Polymerizing condition is selected:
Under the normal pressure, change the consumption of MAO, test MAO under the room temperature respectively: chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel=50: 1,100: 1,300: 1,500: 1,1000: 1 o'clock activity was respectively 0.13 * 10
5, 0.42 * 10
5, 1.63 * 10
5, 0.93 * 10
5, 0.91 * 10
5G ethene/(molNih); At MAO: chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel equals at 300: 1 o'clock, changes temperature, tests 80 ℃ respectively, and 50 ℃, 0 ℃, the activity in the time of-10 ℃ is respectively 0,0.49 * 10
5, 2.05 * 10
5, 1.31 * 10
5G ethene/(molNih).
Embodiment one:
The oligomerisation of ethene normal pressure: at normal temperatures and pressures, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (0.47mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (7.0mg, 13.1 μ mol) and MAO under stirring successively.React after 30 minutes, add acidifying ethanol termination reaction, get product 0.085 gram, activity is 0.13 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
4＞99% (α-C
492.7%).
Embodiment two:
The oligomerisation of ethene normal pressure: at normal temperatures and pressures, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (0.3mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (2.2mg, 4.1 μ mol) and MAO under stirring successively.React after 30 minutes, add acidifying ethanol termination reaction, get product 0.087 gram, activity is 0.42 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
488.4% (α-C
8＞99%) C,
611.6% (α-C
657.9%).
Embodiment three:
The oligomerisation of ethene normal pressure: at normal temperatures and pressures, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (2.3mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (5.9mg, 11.1 μ mol) and MAO under stirring successively.React after 30 minutes, add acidifying ethanol termination reaction, get product 0.896 gram, activity is 1.63 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
477.3% (α-C
4＞99%) C,
622.7% (α-C
665.1%).
Embodiment four:
The oligomerisation of ethene normal pressure: at normal temperatures and pressures, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (1.5mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (2.2mg, 4.1 μ mol) and MAO under stirring successively.Behind the reaction 1h, add acidifying ethanol termination reaction, get product 0.384 gram, activity is 0.93 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
493.1% (α-C
4＞99%) C,
66.9% (α-C
693.7%) %.
Embodiment five:
The oligomerisation of ethene normal pressure: at normal temperatures and pressures, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (5.5mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (4.1mg, 7.7 μ mol) and MAO under stirring successively.Behind the reaction 1h, add acidifying ethanol termination reaction, get product 0.701 gram, activity is 0.91 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
496.3% (α-C
8＞99%) C,
63.7% (α-C
694.1%).
Embodiment six:
The oligomerisation of ethene normal pressure: at 80 ℃, under the normal pressure, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (1mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (2.5mg, 4.7 μ mol) and MAO under stirring successively.React after 30 minutes, add acidifying ethanol termination reaction, get product 0 gram, activity is 0.
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, no product.
Embodiment seven:
The oligomerisation of ethene normal pressure: at 50 ℃, under the normal pressure, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (0.9mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (2.2mg, 4.1 μ mol) and MAO under stirring successively.React after 30 minutes, add acidifying ethanol termination reaction, get product 0.101 gram, activity is 0.49 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
4＞99% (α-C
843%).
Embodiment eight:
The oligomerisation of ethene normal pressure: at 0 ℃, under the normal pressure, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (1.1mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (2.6mg, 4.9 μ mol) and MAO under stirring successively.React after 30 minutes, add acidifying ethanol termination reaction, get product 0.500 gram, activity is 2.05 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
483.6% (α-C
4＞99%) C,
616.4% (α-C
1083.6%).
Embodiment nine:
The oligomerisation of ethene normal pressure: at-10 ℃, under the normal pressure, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (0.9mL 1.4M), kept the ethene malleation in the reaction process to add chlorination (1-naphthyl) (8-(diphenylphosphino) quinoline) nickel catalyzator (2.2mg, 4.1 μ mol) and MAO under stirring successively.React after 15 minutes, add acidifying ethanol termination reaction, get product 0.134 gram, activity is 1.31 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
4＞99% (α-C
4＞99%).
Embodiment ten:
The oligomerisation of ethene normal pressure: at normal temperatures and pressures, with 250ml there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement three times makes to be in the reaction flask in the ethene atmosphere.Add 50ml toluene then, after toluene absorption ethene was saturated, (1.1mL 1.4M), kept the ethene malleation in the reaction process to add bromination phenyl (8-(diphenylphosphino) quinoline) nickel catalyzator (2.6mg, 4.9 μ mol) and MAO under stirring successively.React after 30 minutes, add acidifying ethanol termination reaction, get product 0.417 gram, activity is 1.70 * 10
5Gram ethene/(mole Ni hour).
Product analysis: get the toluene clear liquid, carry out the chromatography-mass spectroscopy analysis, products distribution is: C
477.0% (α-C
4＞99%) C,
623.0% (α-C
665.1%).
Claims (1)
1. N-P coordinate catalyst for oligomerization of nickel ethylene, general structure is:
When wherein X was chlorine (Cl), R was a naphthyl; When X was bromine (Br), R was a phenyl.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01120554 CN1398835A (en) | 2001-07-20 | 2001-07-20 | N-P coordinating catalyst for oligomerization of nickel ethylene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01120554 CN1398835A (en) | 2001-07-20 | 2001-07-20 | N-P coordinating catalyst for oligomerization of nickel ethylene |
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ID=4664231
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747375B (en) * | 2008-12-08 | 2013-08-14 | 中国科学院福建物质结构研究所 | Cooper (I) phosphorescent complexes using 8-phosphinoquinoline derivative as ligand and application thereof |
| CN106432336A (en) * | 2016-09-13 | 2017-02-22 | 中国科学院上海有机化学研究所 | PNN ligand based on quinoline skeleton and iron complex, preparing method and application thereof |
| CN106632507A (en) * | 2016-12-30 | 2017-05-10 | 中国石油天然气股份有限公司 | Metal complex, preparation method thereof and preparation method of olefin binary copolymer |
| US10287373B2 (en) | 2015-10-21 | 2019-05-14 | Lg Chem, Ltd. | Ligand compound, catalyst system for olefin oligomerization, and method for oligomerizing olefins using the same |
-
2001
- 2001-07-20 CN CN 01120554 patent/CN1398835A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747375B (en) * | 2008-12-08 | 2013-08-14 | 中国科学院福建物质结构研究所 | Cooper (I) phosphorescent complexes using 8-phosphinoquinoline derivative as ligand and application thereof |
| US10287373B2 (en) | 2015-10-21 | 2019-05-14 | Lg Chem, Ltd. | Ligand compound, catalyst system for olefin oligomerization, and method for oligomerizing olefins using the same |
| CN106432336A (en) * | 2016-09-13 | 2017-02-22 | 中国科学院上海有机化学研究所 | PNN ligand based on quinoline skeleton and iron complex, preparing method and application thereof |
| CN106632507A (en) * | 2016-12-30 | 2017-05-10 | 中国石油天然气股份有限公司 | Metal complex, preparation method thereof and preparation method of olefin binary copolymer |
| CN106632507B (en) * | 2016-12-30 | 2019-03-12 | 中国石油天然气股份有限公司 | A kind of preparation method of the metal complex and preparation method thereof with alkene bipolymer |
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