CN105566026A - Ethylene tripolymerization method - Google Patents
Ethylene tripolymerization method Download PDFInfo
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- CN105566026A CN105566026A CN201410525752.XA CN201410525752A CN105566026A CN 105566026 A CN105566026 A CN 105566026A CN 201410525752 A CN201410525752 A CN 201410525752A CN 105566026 A CN105566026 A CN 105566026A
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Abstract
The present invention discloses an ethylene tripolymerization method, wherein a catalyst composition is used and comprises a diphosphine ligand represented by a formula I, a transition metal compound, an aluminum-containing co-catalyst and an aliphatic hydrocarbon adopted as an organic solvent, R' and R" are different and are independently selected from hydrogen and tert-butyl, R' and R" are different, and the existing 4 R are the same or different, and are respectively and independently selected from alkyl, cycloalkyl and aryl. The formula I is defined in the specification.
Description
Technical field
The present invention relates to a kind of method of ethylene oligomerization, particularly the method for ethylene trimerization, the present invention relates to a kind of novel catalyst composition and the application in ethylene oligomerization thereof specifically.
Background technology
Use chromium-based catalysts to carry out olefin oligomerization, mainly the oligomerisation of alpha-olefin has obtained and has studied widely.More precisely, developed many chromium-based catalysts, and prepared alpha-olefin for olefin oligomerization.Wherein, ethylene trimerization is made 1-hexene and ethylene tetramerization to make 1-octene aspect there is comparatively special meaning.By the LLDPE resin of 1-alkene, 1-octene copolymer compared with the multipolymer of 1-butylene, tensile strength, resistance to impact shock, tear strength and performance durable in use are all obviously excellent, are particularly suitable for packing film and the agricultural mulch films etc. such as greenhouse, canopy room.At alpha-olefin as in comonomer, 1-hexene and 1-octene progressively substitute 1-butylene and produce high performance PE product.
Traditional 1-hexene, 1-octene are obtained by methods such as wax cracking method, ethylene oligomerization method, Sasol extracting and reclaimings.JohnR.Briggs is at J.Chem.Soc., Chem.Commun., 1989, in 674-675 page, report and carry out with homogeneous phase ternary chromium-based catalysts the method that catalyzed ethylene trimerization selectivity prepares 1-hexene, produce for 1-hexene and open new era, wherein target product selectivity 1-hexene is more than 90%.And for 1-octene, the 1-octene obtained by ethylene oligomerization technique only accounts for 10% ~ 20% of oligomerization product, productive rate is relatively low, and this process also can produce a large amount of high carbon number, is unfavorable for the optimum utilization of resource.Have recently patent report with PNP be Cr (III) catalyzer of part under promotor effect, can the poly-1-octene processed of highly selective catalyzed ethylene four.These patent CN1741850A, CN101032695A, CN101291734A, CN1651142A openly report the method using PNP ligand catalyst ethene to carry out the poly-1-octene processed of selectivity four, and 1-octene yield reaches 70%.
In order to Appropriate application petroleum more, people are being devoted to develop efficient catalyst for oligomerization always, expect to obtain high purity high alpha-olefin.In numerous explorations, heteroatom ligand and chromium sub-group compound effect, and become the new study hotspot in this field for its olefin oligomerization.Disclose a kind of coordination compound of multiple tooth dentate phosphine, arsenic and/or antimony containing aikyiaiurnirsoxan beta and chromic salts in CN1606539A, and use it in ethylene oligomerization reaction process; WO2003053890 reports a kind of sulphur, nitrogen heteroatom part for olefin oligomerization, and this catalyst system activity is higher, and weak point can generate more polymkeric substance in oligomerization.
JunZhang, the biphosphine ligand that etal there was reported vinyl bridging has higher catalytic activity for ethylene tetramerization, weak point is this technology is take methylcyclohexane as solvent, solvent expensive and in product 1-hexene yield lower, the requirement of market to 1-hexene can not be met.
Summary of the invention
For the deficiencies in the prior art, the present invention conducts in-depth research biphosphine ligand, ethene is under the catalyst composition effect formed with the part shown in formula (1), and its catalytic effect affects significantly by solvent effect, and dissimilar solvent causes products distribution widely different; And under the effect of aliphatic hydrocarbon, have higher ethylene trimerization selectivity, and catalytic activity is more than 3200kg product/(gCrh), the method has that cost is low, 1-hexene yield is high, the feature of a certain amount of 1-octene can be obtained simultaneously, greatly reduce production cost.
The present invention relates to a kind of method of ethylene trimerization, comprise use a kind of ethylene oligomerization catalyst composition, described composition comprise the biphosphine ligand shown in formula I, transistion metal compound, containing aluminum cocatalyst and the aliphatic hydrocarbon as organic solvent;
R ' and R in formula " not identical, and be selected from the tertiary butyl and hydrogen independently of one another, 4 R of existence may be the same or different, and are selected from alkyl, cycloalkyl and aromatic group independently of one another, are preferably aromatic group.
In the biphosphine ligand described in formula I of the present invention, when R ' is for H, R " be then the tertiary butyl, as R ' for the tertiary butyl time, R " be then H, the two can not be H or the tertiary butyl simultaneously.
In a preferred embodiment of the present invention, the described aliphatic hydrocarbon as organic solvent is selected from: at least one in hexane, heptane, decane, dodecane, 1-hexene and 1-octene.
In a preferred embodiment of the present invention, described alkyl refers to C
1~ C
20straight or branched saturated alkyl, preferred C
1~ C
10straight or branched saturated alkyl, more preferably C
1~ C
6straight or branched saturated alkyl.Concrete, described alkyl can be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, isopentyl, n-hexyl, Sec-Hexyl, isohexyl, n-heptyl and isomer thereof etc.; Preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-.
In a preferred embodiment of the present invention, described cycloalkyl refers to C
3~ C
10cycloalkyl, preferred C
3~ C
6cycloalkyl.Concrete, described alkyl can be selected from cyclopropyl, cyclopentyl or cyclohexyl.
In a preferred embodiment of the present invention, described aromatic group refers to C
6~ C
20monocycle or multiring aromatic group, and the carbon atom on wherein one or more rings of optional described aromatic group is selected from the hybrid atom MCM-41 of oxygen, nitrogen and sulphur; Preferably, described aromatic group is replaced by halogen or C1 ~ C20 alkyl.Concrete, described aromatic group can be selected from phenyl or substituted-phenyl, naphthyl or pyridyl, preferred phenyl or substituted-phenyl.
In preferred implementations more of the present invention, described transistion metal compound can be the transistion metal compound that this area is commonly used, as the compound of chromium, zirconium, molybdenum, iron, molybdenum, tungsten, titanium, nickel or tantalum, be preferably the chromium cpd of organic or inorganic, wherein the oxidation state of chromium is 0 ~ 6.Described chromium cpd is preferably from following compound: chromium acetylacetonate (Ш), chromium acetate, 2,2, the acid of 6,6-dipivaloylmethane chromium, three (2 ethyl hexanoic acid) chromium, chromium chloride, chromium acetate, chromium nitrate and chromium sulphate, the mixture of chromium trichloride-three-tetrahydrofuran (THF), tricarbonyl chromium, benzene tricarbonyl chromium or Chromium hexacarbonyl.
In certain embodiments of the present invention, the described aluminum cocatalyst that contains is selected from alkylaluminium cpd and/or alkoxy aluminum compound, is preferably alkoxy aluminum compound.
In further preferred embodiment, described aluminum alkoxide is C1-C4 alkylaluminoxane, and wherein C1-C4 alkyl is the alkyl of straight or branched; Preferably, described aikyiaiurnirsoxan beta be selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, modification ethylaluminoxane and isobutyl aluminium alkoxide one or more; More preferably methylaluminoxane and/or modified methylaluminoxane (MMAO).In a preferred embodiment of the invention, in described catalyst composition, in promotor of the present invention, in aluminium and transistion metal compound, the mol ratio of metal is 1 ~ 5000:1, preferably 1 ~ 1500:1, is more preferably 1 ~ 800:1.
In a preferred embodiment of the invention, the temperature of reaction of described ethylene oligomerization reaction is 0 ~ 200 DEG C, and preferable reaction temperature is 10 ~ 160 DEG C, and more preferably temperature of reaction is 40 ~ 120 DEG C; Reaction pressure 0 ~ 20MPa, preferred 1-10MPa, more preferably 2-6MPa; Reaction time is 5 minutes-3 hours, preferably 10 minutes-2 hours, more preferably 20 minutes-1 hour.
Specifically, of the present invention by ethylene oligomerization method, the ethylene oligomerization catalyst composition prepared according to the present invention, makes ethene contact with the chromium coordination complex original position of catalytically effective amount and the trimerization reaction of ethene occurs.After reaction terminates, be cooled to room temperature, pressure release, collection gas phase, liquid-phase product carry out GC analysis.
In ethylene oligomerization of the present invention reaction, can be pre-mixed any to biphosphine ligand, transistion metal compound and promotor in described catalyst composition two or three, and then with another kind of or join in reaction system together with two kinds; Or biphosphine ligand, transistion metal compound, this three all component of promotor are directly joined in reaction system; Or after biphosphine ligand, transistion metal compound, promotor three components premix, directly add as a mixture in reaction system.
In above-mentioned ethylene oligomerization technique, also first described biphosphine ligand and transition metal can be formed metal complex (shown in II), then will join in reaction system respectively or as a mixture in described metal complex, promotor.
In the present invention, described metal complex (formula II), to be reacted by conventional chemical by the biphosphine ligand of formula I and transistion metal compound and prepare, wherein M is transition metal, and X is selected from halogen, and q is the integer of 1 ~ 3.Described halogen is selected from fluorine, chlorine, bromine and iodine, particularly preferably fluorine, chlorine and bromine.
Beneficial effect of the present invention:
In the present invention, under the effect of described organic solvent and catalyst composition, there is the catalytic activity of superelevation, solvent source is convenient, cheap, in product, 1-hexene yield is high, and meet market and can also produce a part of 1-octene to while 1-hexene demand, industrial prospect is good.
Method of the present invention also uses aliphatic hydrocarbon as solvent, and unique solvent effect makes the yield of 1-hexene in product very high, and a small amount of 1-octene of coproduction simultaneously, solvent source is convenient, cheap, has wide prospects for commercial application.
Embodiment
The following example only for the present invention is described in detail, but is understood that scope of the present invention is not limited to these embodiments.
In an embodiment of the present invention,
Nucleus magnetic resonance adopts Switzerland Bruker company AV400MHz nuclear magnetic resonance spectrometer to detect.
Gas-chromatography adopts Agilent 7890 chromatographic instrument to detect.Mass spectrum adopts U.S. Finnigan company's T raceDSQ type Gas Chromatography-mass Spectrometer (GCMS) to detect.
Embodiment 1:
Polyreaction adopts the stainless steel polymeric kettle of 500ml.First carry out pressurize test to this reactor, under determining that reactor seals intact condition, at 120 DEG C, vacuum-drying 4 hours, is then cooled to 80 DEG C and replaces three times with ethylene gas.The chromium complex solution 1ml that middle concentration is 0.001mmol/L is added to reactor, and 500 equivalent MMAO (n-heptane solution of 7wt%) and normal heptane solvent, be 100ml to reaction volume, introduce under ethene existent condition in reactor, open and stir, open ethylene feed valve, maintain reaction pressure 5.0MPa, initiation reaction, 30 minutes stopped reaction.After test terminates, pressure release, to normal pressure, drives still.After reaction solution is weighed, add mark nonane in 1.5mL, react with aqueous hydrochloric acid cancellation.
Gas after reaction in difference metering kettle and liquid, with the composition of chromatographic liquid and gas, solid phase prod is weighed after filtration and after at room temperature drying, and oligomerisation reaction the results are shown in subordinate list 1.Wherein, catalyst activity definition: the total amount of the ethylene oligomerization product of every gram of chromium metal generation per hour, Kg product/gCrh.
Embodiment 2:
Concrete steps are with embodiment 1, and difference is that the add-on of catalyzer be 3ml, Al/Cr ratio is 800, and the reaction times is 1 hour.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 3
Concrete steps are with embodiment 1, and difference is that the add-on of catalyzer be 3ml, Al/Cr ratio is 300, and temperature of reaction is 50 DEG C, pressure 4.0MPa.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 4
Concrete steps are with embodiment 1, and difference is that solvent used is dodecane, catalyst charge be 3ml, Al/Cr than 200, pressure 4.0MPa.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 5
Concrete steps with embodiment 1, difference solvent for use be normal hexane, chromium solution 2ml, Al/Cr than 300, temperature of reaction 60 DEG C, pressure 3MPa.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 6
Concrete steps with embodiment 1, difference in reaction system normal heptane and each 50ml of dodecane, chromium solution 3ml, Al/Cr than 300, temperature of reaction 60 DEG C, pressure 5MPa.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 7
Concrete steps with embodiment 1, temperature of reaction 60 DEG C, pressure 2MPa.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 8
Concrete steps are with embodiment 1, and difference is temperature of reaction 120 DEG C.Ethylene oligomerization reaction result sees attached list 1.
Comparative example 1
Concrete operation step is with embodiment 3, and difference is that the solvent adopted is methylcyclohexane, and reaction pressure 4MPa, ethylene oligomerization reaction result sees attached list 1.
Can be seen by the data of table 1, the difference of solvent makes product slates have a great impact.The more 1-hexene product that described catalyst composition is got under aliphatic solvents effect, and coproduction a certain amount of octene product, meet the demand in market.
Claims (10)
1. an ethylene trimerization method, comprise and use a kind of ethylene oligomerization catalyst composition, described composition comprises: the biphosphine ligand shown in formula I, transistion metal compound, containing aluminum cocatalyst and the aliphatic hydrocarbon as organic solvent;
R ' and R in formula " not identical, and be selected from the tertiary butyl and hydrogen independently of one another, 4 R of existence may be the same or different, and are selected from alkyl, cycloalkyl and aromatic group independently of one another.
2. method according to claim 1, is characterized in that, the described aliphatic hydrocarbon as organic solvent is selected from: at least one in hexane, heptane, decane, dodecane, 1-hexene and 1-octene.
3. method according to claim 1 and 2, is characterized in that, described alkyl is C
1~ C
20the saturated alkyl of straight or branched, preferred C
1~ C
10the saturated alkyl of straight or branched, more preferably C
1~ C
6the saturated alkyl of straight or branched; Preferably, described alkyl is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, isopentyl, n-hexyl, Sec-Hexyl, isohexyl, n-heptyl and isomer thereof; Preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-.
4. the method according to any one of claim 1-3, is characterized in that, cycloalkyl is C
3~ C
10cycloalkyl, preferred C
3~ C
6cycloalkyl, most preferably cyclopropyl, cyclopentyl or cyclohexyl.
5. the method according to any one of claim 1-4, is characterized in that, described aromatic group is selected from phenyl or substituted-phenyl, naphthyl or pyridyl, preferred phenyl or substituted-phenyl.
6. the method according to any one of claim 1-5, it is characterized in that, described transistion metal compound can be selected from least one in the compound of chromium, zirconium, molybdenum, iron, molybdenum, tungsten, titanium, nickel or tantalum, and be preferably the chromium cpd of organic or inorganic, wherein the oxidation state of chromium is 0 ~ 6; Described chromium cpd is preferably from following compound: chromium acetylacetonate (Ш), chromium acetate, 2,2, the acid of 6,6-dipivaloylmethane chromium, three (2 ethyl hexanoic acid) chromium, chromium chloride, chromium acetate, chromium nitrate and chromium sulphate, the mixture of chromium trichloride-three-tetrahydrofuran (THF), tricarbonyl chromium, benzene tricarbonyl chromium or Chromium hexacarbonyl.
7. the method according to any one of claim 1-6, is characterized in that, the described aluminum cocatalyst that contains is selected from alkylaluminium cpd and/or alkoxy aluminum compound, preferably from alkoxy aluminum compound.
8. the method according to any one of claim 7, is characterized in that, described alkoxy aluminum compound be selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, modification ethylaluminoxane and isobutyl aluminium alkoxide one or more; Be preferably methylaluminoxane and/or modified methylaluminoxane.
9. the method according to any one of claim 1-8, is characterized in that, in described promotor, in aluminium and transistion metal compound, the mol ratio of metal is 1 ~ 5000:1, preferably 1 ~ 1500:1, is more preferably 1 ~ 800:1.
10. the method according to any one of claim 1-9, is characterized in that, the temperature of reaction of described ethylene trimerization reaction is 0 ~ 200 DEG C, preferably 10 ~ 160 DEG C, more preferably 40 ~ 120 DEG C; Reaction pressure 0 ~ 20MPa, preferred 1-10MPa, more preferably 2-7MPa; Reaction time is 5 minutes-3 hours, preferably 10 minutes-2 hours, more preferably 20 minutes-1 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109701662A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of carbon monoxide-olefin polymeric and its application |
| CN112742483A (en) * | 2021-01-21 | 2021-05-04 | 华东理工大学 | Catalyst system for selective oligomerization of ethylene, preparation and application thereof |
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| CN1867401A (en) * | 2003-10-10 | 2006-11-22 | 国际壳牌研究有限公司 | Catalytic trimerization of olefinic monomers |
| CN102083867A (en) * | 2007-08-16 | 2011-06-01 | Sk能源株式会社 | Ethylene oligomerization catalyst systems having enhanced selectivity |
| WO2013137676A1 (en) * | 2012-03-16 | 2013-09-19 | Sk Innovation Co., Ltd. | Catalyst systems for preparing 1-hexene and/or 1-octene from ethylene |
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Patent Citations (3)
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| CN1867401A (en) * | 2003-10-10 | 2006-11-22 | 国际壳牌研究有限公司 | Catalytic trimerization of olefinic monomers |
| CN102083867A (en) * | 2007-08-16 | 2011-06-01 | Sk能源株式会社 | Ethylene oligomerization catalyst systems having enhanced selectivity |
| WO2013137676A1 (en) * | 2012-03-16 | 2013-09-19 | Sk Innovation Co., Ltd. | Catalyst systems for preparing 1-hexene and/or 1-octene from ethylene |
Non-Patent Citations (1)
| Title |
|---|
| JUN ZHANG ET AL.: "Switchable Ethylene Tri-/Tetramerization with High Activity: Subtle Effect Presented by Backbone-Substituent of Carbon-Bridged Diphosphine Ligands", 《ACS CATALYSIS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701662A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of carbon monoxide-olefin polymeric and its application |
| CN109701662B (en) * | 2017-10-26 | 2021-12-21 | 中国石油化工股份有限公司 | Catalyst composition and application thereof |
| CN112742483A (en) * | 2021-01-21 | 2021-05-04 | 华东理工大学 | Catalyst system for selective oligomerization of ethylene, preparation and application thereof |
| CN112742483B (en) * | 2021-01-21 | 2024-04-02 | 华东理工大学 | Catalyst system for ethylene selective oligomerization and preparation and application thereof |
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Application publication date: 20160511 |