CN107286278B - Catalyst composition for ethylene oligomerization and oligomerization method - Google Patents

Catalyst composition for ethylene oligomerization and oligomerization method Download PDF

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CN107286278B
CN107286278B CN201610200414.8A CN201610200414A CN107286278B CN 107286278 B CN107286278 B CN 107286278B CN 201610200414 A CN201610200414 A CN 201610200414A CN 107286278 B CN107286278 B CN 107286278B
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catalyst composition
oligomerization
weight
butyl hydroperoxide
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刘珺
郑明芳
王怀杰
张海英
吴红飞
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/69—Chromium, molybdenum, tungsten or compounds thereof
    • C08F4/69008—Chromium, molybdenum, tungsten or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/69206—Tridentate ligand
    • C08F4/69215—Neutral ligand
    • C08F4/69232—NNO
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract

The invention discloses a catalyst composition for an ethylene oligomerization reaction process, which comprises a main catalyst chlorinated 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinochromium (III) complex shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide.

Description

Catalyst composition for ethylene oligomerization and oligomerization method
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for an ethylene oligomerization reaction process.
Background
Linear α -olefins have found widespread use in the fields of ethylene comonomers, intermediates for surfactant synthesis, alcohols for plasticizers, synthetic lubricating oils and oil additives, etc. in recent years, with the continuous development of the polyolefin industry, there is a rapidly increasing worldwide demand for α -olefins, the vast majority of α -olefins are currently prepared by ethylene oligomerization, catalysts for ethylene oligomerization are mainly nickel-, chromium-, zirconium-and aluminum-based, etc., and in recent years, the Brookhart group (Brookhart, M et al, J.Am.Chem.Soc.,1998,120,7143 + 7144; WO99/02472,1999), the Gibson group (Gibson, V.C. et al, chem.Commun.,1998,849 + 850; chem.Eur.J.,2000,2221 + 2231) found therein tridentate pyridine complexes of Fe (II), (II) and Co (II), respectively, and the high selectivity of ethylene oligomerization catalysts for ethylene, α -olefin catalysis.
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 carried out 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 is subjected to oligomerization under the action of a catalyst composition comprising a main catalyst shown as a formula (I), namely chlorinated 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinolato chromium (III), an aluminum-containing cocatalyst and tert-butyl hydroperoxide, so that the catalyst composition has higher oligomerization activity, and has the advantages of quick initiation of oligomerization, stable operation and good repeatability; thereby overcoming the technical prejudice of the technicians in the field about the anaerobic reaction condition and achieving the unexpected technical effect.
According to one aspect of the invention, the catalyst composition for ethylene oligomerization is provided, and comprises a main catalyst, namely 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinolato chromium chloride (III), an aluminum-containing cocatalyst and tert-butyl hydroperoxide, shown as a formula (I):
Figure BDA0000955630060000021
in the formula (I), R1-R5Each independently selected from hydrogen and C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
The catalyst composition provided by the invention contains tert-butyl hydroperoxide, can improve the ethylene oligomerization reaction activity, and can keep the high selectivity of α -olefin.
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.
According to a preferred embodiment of the invention, the catalyst composition further comprises an organic solvent, wherein the weight content of the tert-butyl hydroperoxide is 5-1750ppm (based on 1g of the organic solvent, the composition contains 5-1750 × 10)-6g of t-butyl hydroperoxide), e.g. 25-1750ppm, e.g. 35-1300 ppm, preferably 100-1300 ppm. In one embodiment, the tert-butyl hydroperoxide is present in an amount of 250-1000ppm, 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 a preferred embodiment of the present invention, the amounts of the main catalyst and the cocatalyst can be selected according to the process conditions of the specific application, such as the scale of production and the production equipment. In the catalysisIn one embodiment of the catalyst composition, the amount of the main catalyst is 2 to 500. mu. mol/L (i.e., 2 to 500 × 10 based on 1L of the composition) based on the volume of the composition containing the organic solvent-6mol of main catalyst), preferably 20 to 100 μmol/L, such as 50 μmol/L.
According to a preferred embodiment of the present invention, the molar ratio of aluminum in the cocatalyst to chromium in the main catalyst is (30-900):1, such as (30-500):1, and further such as (100): 700): 1. In one embodiment of the above process, the molar ratio of aluminum in the cocatalyst to chromium in the main catalyst is (100-. 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.
According to a preferred embodiment of the present invention, R in the procatalyst1-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 ethyl, methyl or hydrogen, and R2-R4Is hydrogen.
According to a preferred embodiment of the present invention, the catalyst composition further comprises an organic solvent. The organic solvent is an organic solvent commonly used in the art. For example, the organic solvent is selected from at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and dichloromethane, preferably from one of toluene and xylene or a mixture thereof.
According to a preferred embodiment of the present invention, the aluminium-containing cocatalyst is selected from the group consisting of aluminoxanes and alkyl aluminium compounds, preferably alkyl aluminium compounds. The general formula of the alkyl aluminum compound is AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; each X is halogen, such as chlorine or bromine; n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3. The alkyl aluminumThe compound may be selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride, such as triethylaluminum. The aluminoxane is C1-C4Linear or branched alkylaluminoxanes. The aluminoxane may be selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; such as methylaluminoxane.
The main catalyst chlorinated 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinolato chromium (III) shown in the general formula (I) can be prepared by a preparation method reported in the literature (Organometallics 2011,30, 3001-3009).
According to another aspect of the invention, an ethylene oligomerization method is provided, which comprises carrying out oligomerization reaction under the action of the catalyst composition to obtain an oligomerization product,
by adopting the oligomerization method, the oligomerization activity of the ethylene can be improved under the action of the catalyst composition containing the tert-butyl hydroperoxide, and the technical bias of anaerobic reaction is overcome.
In a preferred embodiment of the invention, the oligomerization temperature is from-20 to 150 deg.C, such as from-20 to 80 deg.C. In a particular embodiment, the oligomerization temperature is from-20 to 40 ℃, and the milder reaction temperature is from 5 to 35 ℃, such as from 5 to 30 ℃. The reaction pressure 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、C22α -olefin selectivity can reach 96%, after the ethylene oligomerization reaction is finished, GC analysis shows that the oligomerization activity can reach 107g·mol(Cr)-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.
In a preferred embodiment of the present invention, the oligomerization process is carried out in an ethylene atmosphere by mixing the main catalyst and the cocatalyst.
In a particular embodiment, a particular embodiment may include the steps of: (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, tert-butyl hydroperoxide and an organic solvent into a reaction system, and fully stirring; (4) introducing ethylene to start oligomerization reaction, and reacting for 30-100 min at the reaction pressure of 0.1-30MPa and the 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 in the step (3) can be dissolved by an organic solvent and then added into the reaction system.
According to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of a main catalyst chlorinated 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinolato chromium (III) shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide (which can further contain an organic solvent), and the catalyst composition has high oligomerization reaction activity, α -olefin has high selectivity, and the oligomerization reaction is quick to initiate, stable to operate and good in repeatability.
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- (1H-2-benzimidazolyl) -8-acetanilinoquinolinecarboxylic acid chromium (III)
The 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinecarboxylic chromium (III) chloride complex R is prepared according to a preparation method reported in the literature (Organometallics 2011,30, 3001-3009)1-R5Are all hydrogen.
2. Ethylene oligomerization reaction, which comprises (1) replacing the reaction system by high-temperature drying and vacuum replacement to ensure water and oxygen free in the reaction system, (2) replacing the reaction system with ethylene to make the reaction system in ethylene environment, (3) adding tert-butyl hydroperoxide and toluene solvent into a reaction kettle, adding 1.37ml of triethylaluminum toluene solution (with a concentration of 715. mu. mol/ml), adding 2ml of toluene solution of 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinolato chromium (III) chloride (with a concentration of 2.5. mu. mol/ml), making the total amount of the composition to be 100ml, wherein the weight of the organic solvent (toluene) is taken as a calculation reference, the weight content of tert-butyl hydroperoxide is 25ppm, Al/Cr is 196, after fully stirring, introducing ethylene to start oligomerization reaction, (4) keeping the ethylene pressure to be 1MPa and the reaction temperature to be 30 ℃ for 30 minutes, (7) stopping the reaction, taking out a small amount of the reaction product, and analyzing the activity by Gas Chromatography (GC) ×.10) for oligomerization reaction7g·mol(Cr)-1·h-1The oligomer content is respectively C442.34％，C6-C1046.86％，C6-C1856.46% (containing 96.7% of linear α -olefin), C20-C281.06 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 500ppm 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/Cr 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/Cr is 30. 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/Cr 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/Cr 148. 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
Figure BDA0000955630060000071
Figure BDA0000955630060000081
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- (1H-2-benzimidazolyl) -8-acetanilinoquinolinolato chromium (III) complex shown in the formula (I), the aluminum-containing cocatalyst, tert-butyl hydroperoxide and the organic solvent, and the catalyst composition has higher oligomerization reaction activity, the selectivity of α -olefin is kept at a higher level, the initiation of the oligomerization reaction is rapid, the running is stable, and the repeatability is good.
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 (18)

1. A catalyst composition for ethylene oligomerization comprises a main catalyst chlorinated 2- (1H-2-benzimidazolyl) -8-acetanilinoquinolinochromium (III) shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide:
Figure FDA0002391761200000011
in the formula, R1-R5The catalyst composition further comprises an organic solvent, the weight content of the tert-butyl hydroperoxide is 5-1750ppm by weight based on the weight of the organic solvent,
the molar ratio of the aluminum in the cocatalyst to the chromium in the main catalyst is (100) -700) 1,
the content of the main catalyst is 2-500 mu mol/L by taking the volume of the composition as a calculation reference.
2. The catalyst composition as claimed in claim 1, wherein the tert-butyl hydroperoxide is present in the catalyst composition in an amount of 100-1300ppm by weight, based on the weight of the organic solvent.
3. The catalyst composition as claimed in claim 1, wherein the tert-butyl hydroperoxide is present in an amount of 250-1000ppm by weight, based on the weight of the organic solvent.
4. The catalyst composition as claimed in claim 1, wherein the tert-butyl hydroperoxide is present in an amount of 250-500ppm by weight, based on the weight of the organic solvent.
5. The catalyst composition as claimed in any one of claims 1 to 4, wherein the molar ratio of aluminum in the cocatalyst to chromium in the procatalyst is (100-.
6. The catalyst composition of claim 5 wherein the molar ratio of aluminum in the cocatalyst to chromium in the procatalyst is (148- & 196): 1.
7. The catalyst composition of any of claims 1-4, wherein the aluminum-containing cocatalyst is selected from at least one of an aluminoxane and an alkyl aluminum compound.
8. The catalyst composition according to claim 7, 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.
9. The catalyst composition of claim 8, wherein X is chlorine or bromine.
10. The catalyst composition of claim 8, 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.
11. The catalyst composition of claim 7, wherein the aluminoxane is C1-C4Linear or branched alkylaluminoxanes.
12. The catalyst composition of claim 11, wherein the aluminoxane is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
13. The catalyst composition according to any one of claims 1 to 4, wherein the amount of the procatalyst is 20 to 100. mu. mol/L, based on the volume of the composition.
14. The catalyst composition of any one of claims 1-4, wherein the organic solvent is selected from at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride.
15. A process for oligomerization of ethylene, comprising carrying out the oligomerization under the action of the catalyst composition of any of claims 1-14 to obtain an oligomerization product.
16. The process of claim 15, wherein the oligomerization reaction is carried out at a reaction temperature of-20 to 150 ℃ and a reaction pressure of 0.1 to 30 MPa.
17. The process of claim 15, wherein the oligomerization reaction is carried out at a reaction temperature of from-20 to 40 ℃.
18. The process of claim 15, wherein the oligomerization reaction is carried out at a reaction temperature of from 5 to 30 ℃.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7176158B2 (en) * 2002-10-25 2007-02-13 Exxonmobil Chemical Patents Inc. Polymerization catalyst composition
CN102199173A (en) * 2011-04-07 2011-09-28 中国科学院化学研究所 2-benzimidazolyl-8-methanamide quinoline chromium complexes, its preparation method and application
CN104974281A (en) * 2014-04-11 2015-10-14 中国石油化工股份有限公司 Catalyst component used for ethylene polymerization reaction, catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7176158B2 (en) * 2002-10-25 2007-02-13 Exxonmobil Chemical Patents Inc. Polymerization catalyst composition
CN102199173A (en) * 2011-04-07 2011-09-28 中国科学院化学研究所 2-benzimidazolyl-8-methanamide quinoline chromium complexes, its preparation method and application
CN104974281A (en) * 2014-04-11 2015-10-14 中国石油化工股份有限公司 Catalyst component used for ethylene polymerization reaction, catalyst and preparation method thereof

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