CN107282120B - Catalyst composition for ethylene oligomerization and oligomerization method - Google Patents
Catalyst composition for ethylene oligomerization and oligomerization method Download PDFInfo
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- CN107282120B CN107282120B CN201610196234.7A CN201610196234A CN107282120B CN 107282120 B CN107282120 B CN 107282120B CN 201610196234 A CN201610196234 A CN 201610196234A CN 107282120 B CN107282120 B CN 107282120B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
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- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B01J2531/842—Iron
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- C07—ORGANIC CHEMISTRY
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- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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Abstract
The invention discloses a catalyst composition for an ethylene oligomerization reaction process, which comprises a main catalyst chlorinated 2, 8-diacetyl quinoline aminal iron (II) complex shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for an ethylene oligomerization reaction process.
Background
The linear alpha-olefin has wide application in the fields of ethylene comonomer, surfactant synthetic intermediate, alcohol for plasticizer, synthetic lubricating oil, oil additive and the like. In recent years, with the continuous development of the polyolefin industry, the worldwide demand for α -olefins has rapidly increased. At present, most of alpha-olefin is prepared by ethylene oligomerization. The catalysts used in the ethylene oligomerization method mainly comprise nickel-based, chromium-based, zirconium-based and aluminum-based catalysts, and in recent years, Brookhart group (Brookhart, M et al, J.Am.chem.Soc.,1998,120, 7143-containing 7144; WO99/02472,1999), Gibson group (Gibson, V.C. et al, chem.Commun.,1998, 849-containing 850; chem.Eur.J.,2000, 2221-containing 2231) respectively find that the tridentate pyridine imine complexes of Fe (II) and Co (II) can catalyze the ethylene oligomerization, and not only the catalytic activity of the catalyst is high, but also the selectivity of alpha-olefin is high.
At present, water and oxygen are generally considered to be very unfavorable for the ethylene oligomerization reaction process, and CN200810111717.8 discloses a method for ethylene oligomerization, which is strictly controlled to be performed in an anhydrous and oxygen-free environment, so that the current ethylene oligomerization reaction has very strict process requirements, resulting in very poor reaction initiation and repeatability of the oligomerization reaction process.
Disclosure of Invention
Aiming at the defects in the prior art, the inventor carries out extensive and intensive research in the field of catalysts for ethylene oligomerization, and surprisingly discovers that ethylene has higher oligomerization activity under the action of a catalyst composition comprising a main catalyst chlorinated 2, 8-diacetylquinoline aminal iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide, and the oligomerization is quick in initiation, stable in operation and good in repeatability; thereby overcoming the technical bias of the technicians in the field and achieving unexpected technical effects.
According to one aspect of the present invention, there is provided a catalyst composition for ethylene oligomerization, the composition comprising a procatalyst iron (II) chloride 2, 8-diacetylquinoline aminide complex represented by formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide:
in the formula (I), R1-R5Each independently selected from hydrogen and C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
According to the invention, the tert-butyl hydroperoxide is added into the catalyst composition, so that the reaction is promoted, and the obtained catalyst composition has high ethylene oligomerization activity and high alpha-olefin selectivity.
In the present invention, the term "C1-C6Alkyl "refers to a saturated straight or branched chain hydrocarbon group containing 1 to 6 carbon atoms. As C1-C6Alkyl, there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl and sec-hexyl; particular preference is given to methyl, ethyl, n-propyl and isopropyl.
In the present invention, the term "C1-C6Alkoxy "means C as defined above1-C6Alkyl groups are attached to an oxygen atom. As C1-C6Alkoxy, there may be mentioned methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, n-hexoxy and sec-hexoxy; methoxy and ethoxy are particularly preferred.
In the present invention, the term "halogen" means fluorine, chlorine, bromine and iodine, and fluorine, chlorine and bromine are particularly preferred.
In a preferred embodiment of the present invention, the molar ratio of aluminum in the cocatalyst to iron in the main catalyst is (30-900):1, such as (100): 700):1, such as (30-500): 1. Under the preferred conditions, the molar ratio of the aluminum in the cocatalyst to the iron in the main catalyst is (148- & lt 500-): 1, preferably (148-: 1. within the limited range, the ethylene oligomerization activity is better; and the ethylene oligomerization activity in the process is still high even in the lower molar ratio range provided.
In some preferred embodiments of the inventionWherein R in the main catalyst1-R5Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro. In one embodiment of the above process, R in the procatalyst1And R5Is methyl or hydrogen, R2-R4Are all hydrogen.
In some preferred embodiments of the present invention, the catalyst composition further comprises an organic solvent. In some preferred embodiments, the t-butyl hydroperoxide is present in an amount of 5 to 1750ppm by weight based on the weight of the organic solvent (i.e., the composition contains (5 to 1750). times.10 based on 1g of the organic solvent)-6g of t-butyl hydroperoxide), for example from 25 to 1750ppm, such as from 35 to 1750 ppm. In one embodiment, the tert-butyl hydroperoxide is present in an amount of 100-1300ppm by weight, preferably 250-1000ppm by weight, and more preferably 250-500ppm by weight, based on the weight of the organic solvent. Within the content range of the tert-butyl hydroperoxide, the catalyst composition has higher ethylene oligomerization activity.
According to the catalyst composition of the present invention, the amounts of the main catalyst and the cocatalyst can be selected according to the process conditions for specific applications such as scale of production and production equipment. In one embodiment of the catalyst composition, the procatalyst is present in an amount of 2 to 500. mu. mol/L based on the volume of the composition containing the organic solvent (i.e., 2 to 500X 10 in the composition based on 1L of the composition)-6mol procatalyst), preferably 20-100. mu. mol/L, such as 50. mu. mol/L.
In some preferred embodiments of the present invention, the organic solvent is selected from at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and dichloromethane, such as one or a mixture of toluene and xylene.
In some preferred embodiments of the present invention, the aluminum-containing cocatalyst is selected from the group consisting of aluminoxanes and alkyl aluminum compounds, preferably alkyl aluminum compounds. In the present invention, the alkyl aluminum compound has the general formula AlRnXmWherein R is each independentlyIs straight chain or branched C1-C8An alkyl group; each X is halogen, such as chlorine or bromine; n is an integer from 1 to 3, m is an integer from 0 to 2, and m + n is equal to 3. Specific examples of the alkyl aluminum compound include, but are not limited to: at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride, such as triethylaluminum.
In the present invention, the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group. Specific examples of the aluminoxane include, but are not limited to: at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; such as methylaluminoxane.
The main catalyst chlorinated 2, 8-diacetyl quinoline amine iron (II) complex shown as the general formula (I) can be prepared by a preparation method reported in the literature (Organometallics2010, 29, 1168-.
According to another aspect of the invention, an ethylene oligomerization method is provided, which comprises carrying out an oligomerization reaction under the action of the catalyst composition to obtain an oligomerization product.
According to a particular embodiment of the process according to the invention, the oligomerization reaction is carried out at a temperature of from-20 to 150 deg.C, such as from-20 to 80 deg.C, for example from-20 to 40 deg.C. Milder reaction temperatures are from 5 to 30 ℃. The reaction pressure of the oligomerization reaction is 0.1-30 MPa.
In a specific embodiment, the following steps may be included: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding a catalyst composition comprising a main catalyst, a cocatalyst and tert-butyl hydroperoxide (and an organic solvent) into a reaction system, and fully stirring; (4) introducing ethylene to start oligomerization reaction, and reacting for 30-100min under the reaction conditions such as reaction pressure of 0.1-30MPa and reaction temperature of-20-150 ℃; (5) the reaction was stopped and the reaction product was analyzed by Gas Chromatography (GC).
In the invention, the main catalyst and the cocatalyst can be dissolved by an organic solvent and then added into the reaction system. In the oligomerization reaction process, the main catalyst and the cocatalyst are mixed in an ethylene atmosphere. The temperature of the oligomerization reaction is-20 to 150 ℃. The pressure of the reaction is 0.1-30MPa, and the oligomerization activity is increased along with the increase of the ethylene pressure.
The catalyst composition is used for ethylene oligomerization, and the obtained ethylene oligomerization product comprises C4、C6、C8、C10、C12、C14、C16、C18、C20、C22Etc.; the selectivity of alpha-olefin can reach more than 96 percent. After the ethylene oligomerization reaction was completed, GC analysis was performed. The result shows that the oligomerization activity can reach 107g·mol(Fe)-1·h-1The above. In addition, the remaining reaction mixture was neutralized with a 5% diluted hydrochloric acid acidified ethanol solution, and no polymer was obtained.
According to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of a composition comprising a main catalyst chlorinated 2, 8-diacetylquinoline amine iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide (which can further comprise an organic solvent), and the catalyst composition has the advantages of higher oligomerization reaction activity, high alpha-olefin selectivity, quick initiation of oligomerization reaction, stable operation and good repeatability. According to the invention, the oligomerization reaction activity is better even under the condition of very low Al/Fe ratio. According to the invention, the oligomerization activity is still high when the reaction is carried out at a relatively low temperature. According to the invention, the technical bias of technicians in the field is overcome, and unexpected technical effects are achieved; the catalytic effect and the cost are well balanced, so that the ethylene oligomerization reaction cost is greatly reduced, the practicability is high, and the industrialization prospect is wide.
Detailed Description
The invention is further illustrated and described with reference to specific examples, which are not intended to be limiting.
Example 1
1. Synthesis of catalyst chlorinated 2, 8-diacetyl quinoline aminal iron (II) complex
The 2, 8-diacetyl quinoline aminal iron (II) chloride complex, R, is prepared according to a preparation method reported in the literature (Organometallics2010, 29, 1168-1173)1-R5Are all hydrogen.
2. The ethylene oligomerization reaction specifically comprises the following steps: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding tert-butyl hydroperoxide and toluene solvent into a reaction kettle, adding 1.37ml of triethyl aluminum toluene solution (the concentration is 715 mu mol/ml), adding 2ml of toluene solution (the concentration is 2.5 mu mol/ml) of 2, 8-diacetyl quinoline condensed 2, 6-dimethyl amine iron (II) complex, and then making the total amount of the composition be 100ml, wherein the weight content of the tert-butyl hydroperoxide is 25ppm and Al/Fe is 196 based on the weight of the organic solvent (toluene), fully stirring, and introducing ethylene to start oligomerization; (4) keeping the ethylene pressure at 1MPa and the reaction temperature at 30 ℃ for reacting for 30 minutes; (7) the reaction was stopped and a small amount of the reaction product was taken out for analysis by Gas Chromatography (GC): the oligomerization activity is 0.63 multiplied by 107g·mol(Fe)-1·h-1The oligomer content is respectively C4 38.59％，C6～C10 49.71％，C6～C1860.30% (containing 97.16% of linear alpha-olefins), C20～C280.88 percent. The remaining mixture was neutralized with 5% hydrochloric acid acidified ethanol solution, no polymer was obtained. The analytical results are shown in Table 1.
Example 2
The same as in example 1, except that the content of t-butyl hydroperoxide was 100ppm by weight. The data are shown in Table 1.
Example 3
The same as in example 1, except that the content of t-butyl hydroperoxide was 250ppm by weight. The data are shown in Table 1.
Example 4
The same as in example 1, except that the content of t-butyl hydroperoxide was 500ppm by weight. The data are shown in Table 1.
Example 5
The same as in example 1, except that the content by weight of t-butyl hydroperoxide was 1000 ppm. The data are shown in Table 1.
Example 6
The difference from example 1 is that the t-butyl hydroperoxide content was 1300ppm by weight. The data are shown in Table 1.
Example 7
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 1750ppm by weight, the data being shown in Table 1.
Example 8
The same as in example 1, except that the t-butyl hydroperoxide was contained in an amount of 500ppm by weight and the reaction temperature was 0 ℃. The data are shown in Table 1.
Example 9
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-10 ℃. The data are shown in Table 1.
Example 10
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-20 ℃. The data are shown in Table 1.
Example 11
The same as in example 1, except that the t-butyl hydroperoxide content was 500ppm by weight and the reaction temperature was 40 ℃. The data are shown in Table 1.
Example 12
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and that Al/Fe is 500. The data are shown in Table 1.
Example 13
The procedure is as in example 1, except that the tert-butyl hydroperoxide content is 500ppm by weight and Al/Fe is 148. The data are shown in Table 1.
Example 14
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and Al/Fe is 100. The data are shown in Table 1.
Example 15
The procedure is as in example 1, except that the tert-butyl hydroperoxide content is 500ppm by weight and Al/Fe is 30. The data are shown in Table 1.
Comparative example 1
The same as example 1, except that t-butyl hydroperoxide was not present in the composition. The data are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, according to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of the composition comprising the main catalyst chlorinated 2, 8-diacetylquinoline amine iron (II) complex shown in the formula (I), the aluminum-containing cocatalyst, tert-butyl hydroperoxide and the organic solvent, so that the catalyst composition has high oligomerization reaction activity, high alpha-olefin selectivity, quick initiation of the oligomerization reaction, stable operation and good repeatability. According to the invention, the oligomerization reaction activity is better even under the condition of very low Al/Fe ratio. According to the invention, the oligomerization activity is still high when the reaction is carried out at a relatively low temperature.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (25)
1. A catalyst composition for ethylene oligomerization comprises a main catalyst chlorinated 2, 8-diacetyl quinoline aminal iron (II) complex shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide:
in the formula, R1-R5Each independently selected from hydrogen and C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
2. The catalyst composition of claim 1, wherein the t-butyl hydroperoxide is present in the catalyst composition in an amount of 5 to 1750ppm by weight.
3. The catalyst composition as claimed in claim 2, wherein the weight content of t-butyl hydroperoxide in the catalyst composition is 100-1300 ppm.
4. The catalyst composition as claimed in claim 3, wherein the weight content of t-butyl hydroperoxide in the catalyst composition is 250-1000 ppm.
5. The catalyst composition as claimed in claim 4, wherein the content of t-butyl hydroperoxide in the catalyst composition is 250-500ppm by weight.
6. The catalyst composition of any of claims 1-5, wherein the molar ratio of aluminum in the cocatalyst to iron in the procatalyst is (30-900): 1.
7. The catalyst composition as recited in claim 6, wherein the molar ratio of aluminum in the cocatalyst to iron in the main catalyst is (100): 700: 1.
8. The catalyst composition of claim 7, wherein the molar ratio of aluminum in the cocatalyst to iron in the procatalyst is (148- & 500) & 1.
9. The catalyst composition of claim 8 wherein the molar ratio of aluminum in the cocatalyst to iron in the procatalyst is (148- & 196) & 1.
10. The catalyst composition of any of claims 1-5, wherein R in the procatalyst is1-R5Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro.
11. The catalyst composition of claim 10, wherein R is1And R5Is methyl or hydrogen, R2-R4Is hydrogen.
12. The catalyst composition of any one of claims 1-5, wherein the aluminum-containing cocatalyst is selected from at least one of an aluminoxane and an alkyl aluminum compound.
13. The catalyst composition according to claim 12, characterized in that the alkylaluminum compound has the general formula AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; x is halogen; n is an integer from 1 to 3, m is an integer from 0 to 2, and m + n is equal to 3.
14. The catalyst composition of claim 13, wherein X is chlorine or bromine.
15. The catalyst composition of claim 13, wherein the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, and ethylaluminum dichloride.
16. The catalyst composition of claim 12, wherein the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group.
17. The catalyst composition of claim 16, wherein the aluminoxane is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
18. The catalyst composition of any one of claims 1-5, further comprising an organic solvent.
19. The catalyst composition of claim 18, wherein the organic solvent is selected from at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride.
20. The catalyst composition of claim 18 wherein the procatalyst is present in an amount of 2 to 500 μmol/L based on the volume of the composition.
21. The catalyst composition of claim 20 wherein the procatalyst is present in an amount of from 20 to 100 μmol/L based on the volume of the composition.
22. A process for oligomerization of ethylene, comprising carrying out the oligomerization under the action of the catalyst composition of any of claims 1-21 to obtain an oligomerization product.
23. The ethylene oligomerization method of claim 22, wherein the oligomerization reaction is carried out at a reaction temperature of-20 to 150 ℃; and/or the reaction pressure is 0.1-30 MPa.
24. The ethylene oligomerization process of claim 23, wherein the oligomerization reaction is at a reaction temperature of from-20 to 40 ℃.
25. The process for oligomerization of ethylene according to claim 24, wherein the reaction temperature of said oligomerization reaction is from 5 to 30 ℃.
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| CN101210061A (en) * | 2006-12-27 | 2008-07-02 | 华东理工大学 | Functional olefin copolymers and its preparing process and application |
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| CN101605605A (en) * | 2007-01-18 | 2009-12-16 | Sk能源株式会社 | Ethene four gathers catalyst systems and uses this catalyst system to prepare the method for 1-octene |
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| US6392041B1 (en) * | 1999-02-25 | 2002-05-21 | Ciba Specialty Chemicals Corporation | Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith |
| EP2742135B2 (en) * | 2011-08-11 | 2020-06-10 | Ionis Pharmaceuticals, Inc. | Linkage modified gapped oligomeric compounds and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101210061A (en) * | 2006-12-27 | 2008-07-02 | 华东理工大学 | Functional olefin copolymers and its preparing process and application |
| CN101605605A (en) * | 2007-01-18 | 2009-12-16 | Sk能源株式会社 | Ethene four gathers catalyst systems and uses this catalyst system to prepare the method for 1-octene |
| CN101450982A (en) * | 2007-11-29 | 2009-06-10 | 上海富元塑胶科技有限公司 | Couple method of polyolefin molecular chain |
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