CN104415790B - A kind of catalyst for ethylene tetramerization composition and application - Google Patents
A kind of catalyst for ethylene tetramerization composition and application Download PDFInfo
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Abstract
The present invention provides a kind of carbon monoxide-olefin polymeric for ethylene tetramerization, and the carbon monoxide-olefin polymeric includes the part shown in lower formula (I), transistion metal compound and co-catalyst.Method present invention also offers ethylene tetramerization is carried out using the carbon monoxide-olefin polymeric.Carbon monoxide-olefin polymeric of the present invention is used for ethylene tetramerization, can with high selectivity produce 1 octene, and the selectivity of 1 octene can be more than 80% more than the overall selectivity of 70%, 1 octene and 1 hexene in product, and catalyst activity is high.
Description
Technical field
The present invention relates to ethylene oligomerization field, and in particular to a kind of carbon monoxide-olefin polymeric for ethylene tetramerization.The present invention
Further relate to the application in the carbon monoxide-olefin polymeric.
Background technology
1- octenes as important Organic Ingredients and chemical intermediate, mainly for the production of high-quality polyethylene (PE).By
1- octenes can significantly improve the properties of PE with the LLDPE (LLDPE) of ethylene copolymer production, particularly right
The mechanical performance of polyethylene, optical property and tear strength and impact strength are all significantly increased, and are very suitable for packaging film
With the agricultural mulch films such as greenhouse, canopy room etc., while 1- octenes also serve as plasticizer, aliphatic acid, detergent alcohols and lubricating oil
The intermediate of additive.
Value although 1- octenes be it is well known that this area at present not as ethylene trimer production 1- hexenes
1- octenes are produced with high selectivity.Traditional 1- production of octenes methods are ethylene oligomerization methods, and ethylene oligomerization technology is according to Schulz-
Flory is distributed, and not only obtains 1- octene products, while also have other alpha-olefins and a small amount of solid superpolymer, and purpose product
The selectivity of 1- octenes is very low, no more than 30%.The SHOP methods that for example Shell companies use（US3676523）Urged using nickel metal
Agent system carries out ethylene oligomerization reaction, can obtain 11% 1- octenes；United States Patent (USP)（US6184428）Report uses a kind of nickel
Used as catalyst ethylene oligomerization, the yield of 1- octenes is 19% to compound.Japan Patent JP2002121157 is reported and used
Zirconium metal catalyzer carries out ethylene oligomerization reaction, and the content of wherein 1- octenes is about 15%.The ethylene tetramerization ternary reported recently
Catalyst system can with high selectivity synthesize 1- octenes, such as patent application CN1741850A（WO2004/056478A1）、
CN1741849A（WO2004/056479A1）、CN101032695A、CN101351424A、CN101415494A、
CN1651142A, CN101291734A and patent application US2006/0128910A1 are disclosed and matched somebody with somebody using P-N-P parts and chromium
Position catalysis ethylene tetramerization, can with high selectivity produce 1- octenes, and the content of 1- octenes can even be more than 70% in product.Patent Shen
Please CN101605605A disclose utilize containing P-C-C-P backbone structure ligands chromium-based catalysts be used for ethylene tetramerization so that high
1- octenes are optionally prepared for, selective highest can be more than 70%.
In view of the application containing Phosphine ligands in ethylene tetramerization, inventors herein have recognized that a kind of for ethylene tetramerization
Novel catalyst, the system includes asymmetric P-C (R)-C-P matrix types part, transistion metal compound and co-catalyst.
Ethylene tetramerization can be effectively catalyzed using the catalyst system and catalyzing to react, the features such as catalyst has high activity and high selectivity, wherein
The selectivity of 1- octenes is more than 70%.
The content of the invention
Object of the present invention is to provide the catalyst for ethylene tetramerization system comprising Novel Ligands, the caltalyst is used
When system carries out ethylene tetramerization reaction, energy high selectivity obtains 1- octenes.
The invention provides a kind of carbon monoxide-olefin polymeric of ethylene tetramerization, comprising diphosphine ligand shown in formula I, transition gold
Category three components of compound and co-catalyst；
Wherein, R and R ' are each independently selected from alkyl, cycloalkyl, monocyclic and polyaromatic in Formulas I.
In a preferred embodiment of the present invention, the alkyl is C1~C20Straight chain or branched saturated alkyl, preferably
C1~C10Straight chain or branched saturated alkyl, more preferably C1~C6Straight chain or branched saturated alkyl.
In further preferred embodiment of the invention, the alkyl may be selected from following group：Methyl, ethyl, just
It is propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, different
Hexyl, n-heptyl and its isomers etc.；It is preferred that methyl, ethyl, n-propyl, isopropyl, normal-butyl or isobutyl group.
In a preferred embodiment of the present invention, the cycloalkyl is C3~C10Cycloalkyl, preferably C3~C6Cycloalkanes
Base.
In further preferred embodiment of the invention, the cycloalkyl may be selected from cyclopropyl, cyclopenta or hexamethylene
Base.
In a preferred embodiment of the present invention, described monocyclic and polyaromatic is C6~C20Monocyclic or polycyclic aromatic
Group, preferably wherein the carbon atom on one or more rings by oxygen, nitrogen and/or sulphur hetero atom replace, it is described monocyclic and polycyclic
Aryl can also be by halogen and/or C1~C20Alkyl replaces.
In further preferred embodiment of the invention, described monocyclic and polyaromatic is selected from phenyl or substituted benzene
Base, naphthyl or pyridine radicals, more preferably phenyl or substituted-phenyl.
In carbon monoxide-olefin polymeric of the invention, the transistion metal compound can be transition metal commonly used in the art
Compound, such as can be the compound selected from chromium, molybdenum, iron, titanium, zirconium or nickel, preferably chromium chloride, chromium acetylacetonate, isooctyl acid chromium
Or three (tetrahydrofuran) chromium trichlorides.
In inventive catalyst composition, the co-catalyst can be organo-aluminum compound commonly used in the art, such as
Can be alkyl aluminum compound or aluminium alkoxide compound, preferably trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three
In octyl aluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane or modified methylaluminoxane one
Plant or several, most preferably modified methylaluminoxane, MAO and/or triethyl aluminum.
In a preferred embodiment of carbon monoxide-olefin polymeric of the invention, the part, transistion metal compound and
The mol ratio of co-catalyst is 1：0.1~10：1~1000, preferably 1：0.25~2：50~700, more preferably 1：0.5~2：
100~500.
Present invention also offers a kind of method that ethylene tetramerization is carried out using above-mentioned carbon monoxide-olefin polymeric, it is included in described
In the presence of carbon monoxide-olefin polymeric and organic solvent, ethene is carried out into four poly- reactions.
In the method for ethylene tetramerization of the invention, the reaction temperature of the ethylene tetramerization is 0~200 DEG C；Reaction pressure
0.1~20MPa.
Ethylene tetramerization organic solvent is the organic solvent selected from aliphatic hydrocarbon or aromatic hydrocarbons, wherein, arene compounds are selected from
At least one in following compound：Benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and
Its derivative；Aliphatic hydrocarbon compound is selected from least one in following compound：Linear paraffin, branched paraffin or cycloalkane,
It is preferred that pentane, heptane, hexamethylene or hexane.Solvent load is fully dissolved or disperseed ensureing reactant.
In above-mentioned ethylene tetramerization technique, can be by part, transistion metal compound and co-catalyst in carbon monoxide-olefin polymeric
In any two kinds be pre-mixed, be then added to reaction system together with another kind again；Or by part, transition metal compound
Thing and co-catalyst these three components carry out fabricated in situ in being added directly into reaction system；Or component part, transition is golden
After category compound and co-catalyst premix, directly as a mixture in addition reaction system.
In above-mentioned ethylene tetramerization technique, reaction condition can be reaction condition commonly used in the art.Optimal conditions are as follows：Will
Ethene, organic solvent and described carbon monoxide-olefin polymeric are added in reactor, are then 1~6Mpa, reaction temperature in ethylene pressure
Spend to be reacted at 0~100 DEG C, catalyst concn is 0.05~0.3mmol Cr/L.Reaction terminate after, be cooled to room temperature, take gas,
Liquid-phase product carries out chromatography.
Beneficial effects of the present invention：
When the carbon monoxide-olefin polymeric provided using the present invention carries out ethylene tetramerization reaction, can be pungent with high selectivity production 1-
Alkene, 1- Octenes selectivities can be more than 70%, and the overall selectivity of 1- octenes and 1- hexenes can be more than 80% in product, the activity of catalyst
It is high.
Specific embodiment
The present invention is described in detail with reference to embodiments.But the present invention is not limited to following examples.
In an embodiment of the present invention：
Nuclear magnetic resonance is detected using Bruker companies of Switzerland AV400MHz nuclear magnetic resonance chemical analysers.
Gas-chromatography is detected using the chromatograph of Hewlett-Packard 5890.
The synthesis of part：
Embodiment 1：Ligand L1（R=CH in Formulas I3,R’=Ph）Synthesis
The part used in the present embodiment is synthesized as follows path and is synthesized.
Wherein：
By MsCl（2.15mL, 55.2mmol）It is dissolved in 5mL dichloromethane, at 0 DEG C, is slowly added dropwise triethylamine
（4mL）And propane diols（26.3mmol）Dichloromethane mixed solution in, after reaction 1 hour, be warmed to room temperature continuation and stir 2 small
When.After reaction terminates, add 1M aqueous hydrochloric acid solutions, water to be extracted with dichloromethane, organic phase is removed into solvent, obtain intermediate.
At -78 DEG C, by LiPPh2（10mmol）THF (5mL) solution slowly instill above-mentioned intermediate（10mmol）THF（5mL）
In solution.After 10min, reaction is warmed to room temperature overnight.After reaction terminates, solvent is removed, add suitable quantity of water, there is a large amount of precipitations, mistake
Filter precipitation.Column chromatography purification obtains final product ligand L 1.1H NMR(400MHz,CDCl3):δ=7.41~7.21 (m, 25H, Ph-H),
2.38~2.23 (m, 2H, CHH, CHMe), 1.94~1.81 (m, 2H, CH2), 1.28 (dd, 3H, CH3);31P NMR(CDCl3)
δ=1.7;-20.6.
Embodiment 2：Ligand L2（R=R '=Ph in Formulas I）Synthesis
With embodiment 1, difference is that propane diols is replaced with into styrene glycol to preparation method, and other conditions are constant.
Yield 75%.1H NMR(400MHz,CDCl3):δ=7.4~7.0 (m, 25H, Ph-H), 3.3~3.4 (m, 1H, CH), 2.4~2.5
(m,2H,CH2);31P NMR(CDCl3)δ=22.2;-2.3.
Part synthetic example 3：Ligand L3（R=Cy,R’=Ph）Synthesis
With embodiment 1, difference is that propane diols is replaced with into hexamethylene ethyl glycol to preparation method, and other conditions are not
Become.Yield 75%.1H NMR(400MHz,CDCl3):δ=7.24~7.15 (m, 20H), 2.20-2.16 (m, 1H), 2.02-1.98
(m,2H),1.83-1.79(m,1H),1.60-1.03(m,10H);31P NMR(CDCl3)δ=2.7;–22.1.
Embodiment 3：Complex C1Synthesis
The part that the present embodiment is used is synthesized by following synthetic route：
By CrCl3(THF)3(1.5mmol) adds ligand L1The CH of (1.5mmol)2Cl2In (3mL) solution.Stirring 4 hours
Afterwards, concentrated solvent, it is to be settled out a large amount of blue solids to add n-hexane.After being washed with n-hexane, drain solvent and obtain blueness
Cr complexs C1, yield 95%.
Polymerization experiment：
Embodiment 4
Using 300mL stainless steel polymeric kettles.Autoclave is heated to 80 DEG C, after vacuumizing with nitrogen displacement for several times, then
It is filled with ethene displacement once, is down to design temperature.Hexahydrotoluene is added at 40 DEG C, while adding 3.3 μm of ol parts synthesis
3.3 μm of ol of part and chromium trichloride and co-catalyst modified methylaluminoxane (MMAO) in embodiment 1, the cumulative volume of mixed liquor
It is 100mL, wherein the mol ratio of part, chromic salts and co-catalyst is 1：1：500, reaction pressure 4.0MPa is controlled, ethene is passed through,
Carry out ethylene tetramerization reaction.
After reaction 0.5 hour, system is cooled to room temperature, and gaseous products are collected in aerometer measuring tank, and liquid-phase product is received
Collection adds 1mL ethanol as terminator in conical flask, terminates ethylene tetramerization reaction.The laggard promoting the circulation of qi phase of liquid phase gauging of products
Chromatography.
Measure reaction result as shown in table 1：Catalysis activity is 1577kg/gCrh, and 1- Octenes selectivities are 68.7%, 1-
The selectivity of hexene is 14.6%.
Embodiment 5
The pressure of polymerisation is replaced with into 1.0MPa, other conditions are with Polymerization Example 1；Measure reaction result such as table 1
It is shown：Catalysis activity is 899kg/gCrh, and 1- Octenes selectivities are 16.8% for the selectivity of 60.6%, 1- hexenes.
Embodiment 6
The pressure of polymerisation is replaced with into 6.0MPa, other conditions are with Polymerization Example 1；Measure reaction result such as table 1
It is shown：Catalysis activity is 1903kg/gCrh, and 1- Octenes selectivities are 12.9% for the selectivity of 71.5%, 1- hexenes.
Embodiment 7
The temperature of polymerisation is replaced with 0 DEG C, other conditions are with Polymerization Example 1；Measure the reaction result such as institute of table 1
Show：Catalysis activity is 652kg/gCrh, and 1- Octenes selectivities are 26.3% for the selectivity of 48.3%, 1- hexenes.
Embodiment 8
The temperature of polymerisation is replaced with 80 DEG C, other conditions are with Polymerization Example 1；Measure the reaction result such as institute of table 1
Show：Catalysis activity is 1150kg/gCrh, and 1- Octenes selectivities are 17.0% for the selectivity of 63.4%, 1- hexenes.
Embodiment 9
The addition of Cr is same as Example 1, and Al/Cr mol ratios are changed into 100 by the addition for changing aluminium, other
Part is with Polymerization Example 1；Measure reaction result as shown in table 1：Catalysis activity is 708kg/gCrh, and 1- Octenes selectivities are
The selectivity of 55.1%, 1- hexene is 15.4%.
Embodiment 10
It is three-(tetrahydrofuran) chromium trichloride (Cr (THF) that chromium trichloride in Polymerization Example 1 is changed3Cl3), other
Condition is with Polymerization Example 1；Measure reaction result as shown in table 1：Catalysis activity is 1836kg/gCrh, 1- Octenes selectivities
The selectivity for being 70.2%, 1- hexenes is 19.7%.
Embodiment 11
It is chromium acetylacetonate (Cr (acac) that chromium trichloride in Polymerization Example 1 is changed3), other conditions are with the reality that is polymerized
Apply example 1；Measure reaction result as shown in table 1：Catalysis activity is 1697kg/gCrh, 1- Octenes selectivities be 69.8%, 1- oneself
The selectivity of alkene is 20.4%.
Embodiment 12
It is MAO (MAO) that modified methylaluminoxane in Polymerization Example 1 is changed, and other conditions are with the reality that is polymerized
Apply example 1；Measure reaction result as shown in table 1：Catalysis activity is 1344kg/gCrh, 1- Octenes selectivities be 66.0%, 1- oneself
The selectivity of alkene is 18.6%.
Embodiment 13
It is triethyl aluminum (AlEt that MAO in Polymerization Example 1 is changed3), the same Polymerization Example of other conditions
1；Measure reaction result as shown in table 1：Catalysis activity is 438kg/gCrh, and 1- Octenes selectivities are the choosing of 61.5%, 1- hexenes
Selecting property is 16.5%.
Embodiment 14
The part of part synthetic example 1 is changed to the part in part synthetic example 2, other conditions are with the implementation that is polymerized
Example 1；Measure reaction result as shown in table 1：Catalysis activity is 937kg/gCrh, and 1- Octenes selectivities are 70.8%, 1- hexenes
Selectivity is 19.8%.
Embodiment 15
The part of part synthetic example 1 is changed to the part in part synthetic example 3, other conditions are with the implementation that is polymerized
Example 1；Measure reaction result as shown in table 1：Catalysis activity is 1097kg/gCrh, and 1- Octenes selectivities are 72.2%, 1- hexenes
Selectivity be 20.5%.
Embodiment 16
Using 300mL stainless steel polymeric kettles.Autoclave is heated to 80 DEG C, after vacuumizing with nitrogen displacement for several times, then
It is filled with ethene displacement once, is down to design temperature.Hexahydrotoluene is added at 40 DEG C, while adding 3.3 μm of ol complexs to close
Into the complex C in embodiment1And co-catalyst modified methylaluminoxane (MMAO), the cumulative volume of mixed liquor is 100mL, wherein
The mol ratio of complex and co-catalyst is 1：500, reaction pressure 4.0MPa is controlled, ethene is passed through, carry out ethylene tetramerization reaction.
After reaction 0.5 hour, system is cooled to room temperature, and gaseous products are collected in aerometer measuring tank, and liquid-phase product is received
Collection adds 1mL ethanol as terminator in conical flask, terminates ethylene tetramerization reaction.The laggard promoting the circulation of qi phase of liquid phase gauging of products
Chromatography.
Measure reaction result as shown in table 1：Catalysis activity is 1720kg/gCrh, and 1- Octenes selectivities are 70.1%, 1-
The selectivity of hexene is 21.3%.
Table 1
Claims (27)
1. it is a kind of to be used for catalyst for ethylene tetramerization composition, comprising diphosphine ligand shown in formula I, transistion metal compound and help
Catalyst；
Wherein, in Formulas I, R is selected from cyclohexyl or phenyl；R' is selected from alkyl, cycloalkyl, monocyclic and polyaromatic.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the alkyl is C1~C20Straight chain is branched full
And alkyl.
3. carbon monoxide-olefin polymeric according to claim 2, it is characterised in that the alkyl is C1~C10Straight chain is branched full
And alkyl.
4. carbon monoxide-olefin polymeric according to claim 3, it is characterised in that the alkyl is C1~C6Straight chain is branched full
And alkyl.
5. carbon monoxide-olefin polymeric according to claim 4, it is characterised in that the alkyl is selected from following group：Methyl, second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, it is secondary oneself
Base and isohesyl.
6. carbon monoxide-olefin polymeric according to claim 5, it is characterised in that the alkyl is selected from methyl, ethyl, positive third
Base, isopropyl, normal-butyl or isobutyl group.
7. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the cycloalkyl is C3~C10Cycloalkyl.
8. carbon monoxide-olefin polymeric according to claim 7, it is characterised in that the cycloalkyl is C3~C6Cycloalkyl.
9. carbon monoxide-olefin polymeric according to claim 8, it is characterised in that the cycloalkyl be cyclopropyl, cyclopenta or
Cyclohexyl.
10. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that described monocyclic and polyaromatic is C6~C20
Monocyclic or polycyclic aromatic group.
11. carbon monoxide-olefin polymerics according to claim 10, it is characterised in that in described monocyclic and polyaromatic one or
Carbon atom on multiple rings is replaced by the hetero atom of oxygen, nitrogen and/or sulphur.
12. carbon monoxide-olefin polymerics according to claim 11, it is characterised in that described monocyclic and polyaromatic is selected from benzene
Base, substituted-phenyl, naphthyl or pyridine radicals.
13. carbon monoxide-olefin polymerics according to claim 12, it is characterised in that described monocyclic and polyaromatic is selected from phenyl
Or substituted-phenyl.
14. carbon monoxide-olefin polymerics according to claim 1, it is characterised in that the transistion metal compound be selected from chromium,
The compound of molybdenum, iron, titanium, zirconium or nickel.
15. carbon monoxide-olefin polymerics according to claim 14, it is characterised in that the transistion metal compound is selected from chlorination
Chromium, chromium acetylacetonate, isooctyl acid chromium or three (tetrahydrofuran) chromium trichlorides.
16. carbon monoxide-olefin polymerics according to claim 1, it is characterised in that the co-catalyst is selected from alkyl aluminum chemical combination
Thing or aluminium alkoxide compound.
17. carbon monoxide-olefin polymerics according to claim 16, it is characterised in that the co-catalyst be selected from trimethyl aluminium,
Triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO,
One or more in ethylaluminoxane or modified methylaluminoxane.
18. carbon monoxide-olefin polymerics according to claim 17, it is characterised in that the co-catalyst is selected from modified methyl aluminium
Oxygen alkane, MAO and/or triethyl aluminum.
19. carbon monoxide-olefin polymeric according to any one of claim 1-18, it is characterised in that the part, transition gold
The mol ratio of category compound and co-catalyst is 1：0.1~10：1~1000.
20. carbon monoxide-olefin polymerics according to claim 19, it is characterised in that the part, transistion metal compound and
The mol ratio of co-catalyst is 1：0.25~2：50~700.
21. carbon monoxide-olefin polymerics according to claim 20, it is characterised in that the part, transistion metal compound and
The mol ratio of co-catalyst is 1：0.5~2：100~500.
The method that a kind of carbon monoxide-olefin polymeric of 22. uses according to any one of claim 1-21 carries out ethylene tetramerization,
It is included in the presence of the carbon monoxide-olefin polymeric and organic solvent, ethene is carried out into four poly- reactions.
23. methods according to claim 22, it is characterised in that the reaction temperature of the ethylene tetramerization is 0~200 DEG C；
0.1~20MPa of reaction pressure.
24. method according to claim 22 or 23, it is characterised in that the organic solvent is selected from aliphatic hydrocarbon chemical combination
The organic solvent of thing or arene compounds.
25. methods according to claim 24, it is characterised in that the aliphatic hydrocarbon compound is selected from following compound
At least one：Linear paraffin, branched paraffin or cycloalkane.
26. methods according to claim 25, it is characterised in that the aliphatic hydrocarbon compound is selected from pentane, heptane, ring
Hexane or hexane.
27. methods according to claim 24, it is characterised in that the arene compounds are selected from following compound
It is at least one：Benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene.
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| CN107282125B (en) * | 2016-03-31 | 2020-05-12 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and application thereof |
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| CN113583053B (en) * | 2020-04-30 | 2023-12-08 | 中国石油化工股份有限公司 | Metal complex, catalyst for ethylene oligomerization and application thereof |
| CN113600244A (en) * | 2021-08-06 | 2021-11-05 | 山东京博石油化工有限公司 | Catalyst for synthesizing 1-octene and application thereof |
| CN116328832A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Organic polymer carrier, main catalyst, ethylene polymerization catalyst composition and application thereof |
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