CN109701644B - Catalyst composition and application thereof - Google Patents
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- CN109701644B CN109701644B CN201711011277.4A CN201711011277A CN109701644B CN 109701644 B CN109701644 B CN 109701644B CN 201711011277 A CN201711011277 A CN 201711011277A CN 109701644 B CN109701644 B CN 109701644B
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Abstract
The invention relates to a catalyst composition for ethylene trimerization, which comprises a ligand compound shown as a formula (I), a transition metal compound and an aluminum-containing cocatalyst;
in the formula R1Independently selected from alkyl, aryl, alkyl derivatives or aryl derivatives; r2Is C1～C15The alkylene group of (1). The invention also relates to the use of said catalyst composition. The catalyst composition of the invention has high activity; meanwhile, aromatic hydrocarbon solvent is avoided being used in the polymerization reaction, the toxicity in the production process is greatly reduced, the harm to the environment is reduced, and high-quality products can be obtained.
Description
Technical Field
The present invention relates to a catalyst composition for oligomerization of ethylene. The invention also relates to the use of a catalyst composition in an ethylene trimerisation process.
Background
The use of chromium-based catalysts for the oligomerization of olefins, primarily alpha-olefins, has been extensively studied. More specifically, a number of chromium-based catalysts have been developed and used for the oligomerization of olefins to produce alpha-olefins. Among them, the trimerization of ethylene to 1-hexene and the tetramerization of ethylene to 1-octene are of particular significance. Compared with the copolymer of 1-butene, the LLDPE resin copolymerized by 1-hexene and 1-octene has obviously excellent tensile strength, impact strength, tear resistance and durability, and is particularly suitable for packaging films, agricultural covering films for greenhouses, sheds and the like. In the context of alpha-olefins as comonomers, 1-hexene and 1-octene have been gradually substituted for 1-butene to produce high performance PE products.
The production method of alpha-olefin mainly includes wax cracking method, ethylene oligomerization method, extraction separation method, fatty alcohol dehydrogenation method and internal olefin isomerization method. Among them, the ethylene oligomerization method is one of the important ways of producing alpha-olefin because of its characteristics of high purity, good selectivity, high utilization rate of raw material, etc.
After a way of selectively preparing 1-hexene by ethylene trimerization by using a homogeneous ternary chromium-based catalyst is reported by John R.Briggs in J.chem.Soc., chem.Commun., 1989,674-675, a 1-hexene production technology is greatly developed. In order to make more rational use of petroleum feedstocks, efforts have been made to develop highly efficient oligomerization catalysts, with the expectation of obtaining high purity higher alpha-olefins. In many explorations, the interaction of heteroatom ligands with chromium-based compounds and their use for the oligomerization of olefins has become a new area of research in this field. CN1606539A discloses a coordination compound of multidentate ligand phosphine, arsenic and/or antimony containing aluminoxane and chromium salt, and the coordination compound is used in the ethylene oligomerization reaction process; WO2003053890 reports that a novel sulfur-nitrogen heteroatom ligand is used for olefin oligomerization, olefin oligomerization occurs under the action of a chromium compound and alkylaluminoxane, and the catalyst composition has the characteristics of high catalytic activity, high purity of 1-hexene product and the like. However, the catalysts obtained from the above patents generally have the disadvantages of high price and high product cost.
In the field of olefin polymerization, particularly metallocene catalysis, alkoxy aluminum such as Methyl Aluminoxane (MAO) or Modified Methyl Aluminoxane (MMAO) is generally used as a cocatalyst, and the price of MAO is dozens of times higher than that of other alkyl aluminum, so that the catalyst has long been a main bottleneck for restricting the industrialization of the field. In addition, MAO is very difficult to dissolve in alkane solvents, so commercially available MAO is generally an aromatic hydrocarbon solution such as toluene, which causes aromatic hydrocarbon residues in the reaction product, and even influences the exertion of catalyst activity and also seriously influences product quality. While the use of co-polymer grade a-olefins in the preparation of polyethylene tends to severely limit their aromatic content.
There is no doubt that there is still a need for a novel catalyst with excellent comprehensive performance in the field of olefin oligomerization. Attention is paid to how to obtain a cocatalyst with lower cost and more excellent performance, so that an ethylene oligomerization catalyst with high activity and selectivity is developed, and the attention is paid to the industry.
Disclosure of Invention
The inventors of the present application have found a catalyst composition when studying an ethylene oligomerization catalyst. The catalyst composition is used for catalyzing ethylene oligomerization reaction, especially ethylene trimerization reaction, and has the advantages of high activity and high selectivity.
According to one aspect of the present invention, there is provided a catalyst composition comprising a ligand compound represented by formula I, a transition metal compound, and an alkane solution containing an aluminum cocatalyst;
in the formula: r1Independently selected from alkyl, aryl, alkyl derivatives or aryl derivatives; r2Is C1～C15Alkylene of (3), preferably C2～C10An alkylene group of (a).
The preparation method of the alkane solution containing the aluminum cocatalyst comprises the following steps:
step a: reacting water with an aromatic hydrocarbon solution of aluminum alkyl; wherein the general formula of the alkyl aluminum is R1R2R3Al，R1、R2And R3Same or different, independently selected from C1-C20Alkyl groups of (a);
step b: in step aReacting the obtained solution with aromatic hydrocarbon solution of aluminoxane; alkyl groups and R in said aluminoxanes1、R2And R3Different;
step c: and c, reacting the solution obtained after the reaction in the step b with water, removing aromatic hydrocarbon, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst.
The catalyst composition has the advantages of simple preparation and low cost, can effectively catalyze ethylene oligomerization reaction, particularly ethylene trimerization reaction, and has high activity and high selectivity.
The catalyst composition according to the present invention, the preparation method thereof comprises: an alkane solution containing an aluminum promoter is first prepared by a process comprising the steps of:
step a: reacting water with an aromatic hydrocarbon solution of aluminum alkyl; wherein the general formula of the alkyl aluminum is R1R2R3Al，R1、R2And R3Same or different, independently selected from C1-C20Alkyl groups of (a);
step b: reacting the solution obtained after the reaction in the step a with an aromatic hydrocarbon solution of aluminoxane; alkyl groups and R in said aluminoxanes1、R2And R3Different;
step c: b, reacting the solution obtained after the reaction in the step b with water, removing aromatic hydrocarbon, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst;
then mixing the prepared alkane solution containing the aluminum cocatalyst with the ligand compound shown in the formula I and the transition metal compound, or mixing the prepared alkane solution containing the aluminum cocatalyst with the ligand compound shown in the formula I and the transition metal compound when in use.
According to some preferred embodiments of the invention, in the general formula of the aluminum alkyl, R1、R2And R3Same or different, independently selected from C1-C10Alkyl group of (1). In some preferred embodiments, R1、R2And R3And the same is selected from one of methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl and n-pentyl.
According to some preferred embodiments of the present invention, the aluminoxane is selected from at least one of methylaluminoxane and ethylaluminoxane.
According to some preferred embodiments of the present invention, the step a comprises adding water to the triisobutylaluminum aromatic hydrocarbon solution at a low temperature, stirring the mixture for a certain time, heating the mixture to reflux, and then cooling the mixture to room temperature for standby. Preferably, step a comprises reacting the water with an aromatic hydrocarbon solution of an aluminum alkyl at-20 ℃ to 10 ℃, such as-20 ℃ to 0 ℃, such as-10 ℃ to 0 ℃ for 5min to 60min, and then heating and refluxing for 5min to 60 min. In some preferred embodiments, the molar ratio of water to the aluminum alkyl in step a is (0.5-1): 1.
According to some preferred embodiments of the present invention, the step b comprises mixing the product of the step a with a methylaluminoxane aromatic hydrocarbon solution, heating the mixture to reflux for reaction, and cooling the mixture to room temperature for later use. Preferably, the solution obtained after the reaction of step a is mixed with an aromatic hydrocarbon solution of aluminoxane at 5 ℃ to 40 ℃, preferably at room temperature, and then heated under reflux for 0.1h to 1 h. In some preferred embodiments, the molar ratio of aluminoxane to aluminum alkyl in step b is (0.1-3):1, preferably (0.5-1): 1.
According to some preferred embodiments of the present invention, the step c comprises adding water to the aromatic hydrocarbon solution in the step b at a low temperature, stirring for a certain time, heating to reflux, and cooling to room temperature; preferably, the solution obtained after the reaction in step b is reacted with water at-20 ℃ to 10 ℃, preferably-10 ℃ to 0 ℃ for 5min to 60min, and then heated under reflux for 5min to 60 min. In some preferred embodiments, the molar ratio of water to the aluminoxane in step c is (0.1-0.3): 1.
According to the invention, the reflux temperature is the boiling temperature of the aromatic hydrocarbon solvent.
In the present invention, the term "aromatic hydrocarbon" refers to hydrocarbon compounds having a benzene ring structure, such as benzene, toluene, xylene, naphthalene, and phenyl derivatives substituted with halogen, nitro or alkyl.
In the present invention, the term "alkane" refers to a saturated hydrocarbon such as at least one of pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, and the like.
According to some preferred embodiments of the invention, R is1-R3Likewise, for isobutyl, the isobutane content in the gaseous product, measured by gas chromatography after hydrolysis of said aluminium-containing cocatalyst, is higher than 75% by weight, preferably from 78% by weight to 94% by weight.
According to some preferred embodiments of the present invention, the method for preparing the aluminum-containing cocatalyst comprises:
a. adding water into the triisobutyl aluminum aromatic hydrocarbon solution at a low temperature, stirring and reacting for a certain time, heating and refluxing, and then cooling to room temperature for later use;
b. mixing the product obtained in the step a with methylaluminoxane aromatic hydrocarbon solution, heating for reflux reaction, and cooling to room temperature for later use;
c. and (c) adding water into the aromatic hydrocarbon solution in the step (b) at a low temperature, stirring and reacting for a certain time, heating and refluxing, cooling to room temperature, removing aromatic hydrocarbon from the mixture under reduced pressure, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst. Triisobutyl aluminum is adopted in the step a, methylaluminoxane is adopted in the step b, and after the obtained aluminum-containing cocatalyst is hydrolyzed, the content of isobutane in a gas phase product is higher than 75 wt%, such as 78-94 wt%, and the balance is methane through gas chromatography detection.
According to a preferred embodiment of the invention, R1Independently selected from C1-C10Alkyl and phenyl groups of (a); r2Is C2～C10An alkylene group of (a). The alkyl group includes straight chain alkyl and branched chain alkyl; alkylene groups include straight chain alkylene groups and branched chain alkylene groups.
According to a preferred embodiment of the present invention, the transition metal compound is selected from at least one of compounds of chromium, molybdenum, iron, titanium, zirconium or nickel, preferably at least one of chromium acetylacetonate, chromium isooctanoate, chromium tris (tetrahydrofuran) trichloride or chromium bis (tetrahydrofuran) dichloride.
According to some preferred embodiments of the catalyst composition of the present invention, the amount of the transition metal compound is 0.1 to 10 moles, preferably 0.25 to 2 moles, more preferably 0.5 to 2 moles, relative to 1 mole of the ligand compound; the amount of the aluminum-containing cocatalyst is 1 to 1500 mol, preferably 10 to 800 mol, more preferably 100-260 mol.
According to the invention, the cocatalyst has good solubility in alkane, and the catalyst composition formed by the cocatalyst, the ligand and the metal salt has high activity.
According to another aspect of the present invention, there is provided a process for using the above catalyst composition, comprising carrying out an ethylene oligomerization, such as a trimerization reaction, in the presence of the above catalyst composition. In some preferred embodiments, the ethylene trimerization reaction is carried out in an organic solvent, preferably an alkane. The reaction conditions were as follows: the temperature is 0-200 ℃, preferably 0-100 ℃; the ethylene pressure is 1-20.0MPa, preferably 2.0-7.0 MPa. In general, the catalyst activity increases with increasing reaction pressure.
According to the invention, when the catalyst composition is used, the components in the composition can be mixed and then added into a reactor, or the components in the composition can be added into the reactor respectively.
According to the invention, when the catalyst composition is reacted in alkane, an aromatic hydrocarbon solvent can be avoided, aromatic hydrocarbon residue is not left in the product, the product quality is high, and high-quality alpha-olefin monomers can be provided for the chemical industry.
According to the invention, the organic solvents used, such as alkanes, are subjected to anhydrous treatment before use; the method for the anhydrous treatment of the organic solvent may employ a method commonly used in the art.
The catalyst composition containing the cocatalyst can effectively catalyze ethylene oligomerization reaction, especially ethylene trimerization reaction, and the catalyst activity can exceed 3 x 107g/(molCr·h)；C6Component selectivity>95%, 1-hexene in C6The content of the active ingredients is more than 99 percent; the others are small amount of alpha-olefin such as C4, C8, C10, C12, etc. Has the characteristics of high activity, high selectivity, few high molecular weight polymers and the like. Thus, according to the inventionThe catalyst composition has good industrial application prospect and economic value.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The ligand used in the invention is self-made in patent ZL 201204188829.4.
In the present invention, the aluminum content test was performed by inductively coupled plasma emission spectroscopy (ICP Optima8300, PE corporation, usa).
In the present invention, the gas phase components were detected using a Hewlett packard 5890 chromatograph. A chromatographic column: agilent HP-Al/KCL, the column length is 50m, and the inner diameter is 0.320 mm; column temperature: keeping the temperature at 100 ℃ for 10 minutes, heating the temperature to 160 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 10 minutes, keeping the temperature at a sample inlet of 250 ℃ and keeping the temperature at a detector of 250 ℃; carrier gas: nitrogen, FID detector.
Example 1
Slowly adding 10mmol of water into 15mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 30min, heating and refluxing for 1 hour, and then cooling to room temperature for later use; 15mmol of methylaluminoxane (1M toluene solution) is added into the solution, and then the solution is heated and refluxed for 1 hour and cooled to room temperature; and slowly adding 3mmol of water into the mixed solution under ice bath, stirring for reaction for 30min, heating and refluxing for 1h, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding a cyclohexane solvent to obtain the cocatalyst A (1M, cyclohexane solution) with the total volume of 30 mL.
And (3) product analysis: taking a quantitative cocatalyst A, slowly adding excessive water to decompose the cocatalyst A, and testing the content of aluminum in a liquid phase component to be 3.4 wt% by using ICP (inductively coupled plasma); gas phase composition test isobutane content 89 wt%, methane content 11 wt%.
Example 2
Slowly adding 5mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 30min, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; and slowly adding 2mmol of water into the mixed solution under ice bath, stirring for reaction for 30min, heating and refluxing for 1h, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding a cyclohexane solvent to obtain the cocatalyst B (1M, cyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst B (same as example 1), slowly adding excessive water to decompose the cocatalyst B, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 90 wt%, methane content 10 wt%.
Example 3
Slowly adding 10mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; and slowly adding 2mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding a cyclohexane solvent to obtain the cocatalyst C (1M, cyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst C (same as example 1), slowly adding excessive water to decompose the cocatalyst C, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 78 wt% and methane content 22 wt%.
Example 4
Slowly adding 7mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; and slowly adding 3mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding a cyclohexane solvent to obtain the cocatalyst D (1M, cyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst D (same as example 1), slowly adding excessive water to decompose the cocatalyst D, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 91 wt%, methane content 9 wt%.
Example 5
Slowly adding 7mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 10mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; slowly adding 1mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding the cyclohexane solvent to obtain the cocatalyst E (1M, cyclohexane solution) with the total volume of 20 mL.
And (3) product analysis: taking a certain amount of cocatalyst E (same as example 1), slowly adding excessive water to decompose the cocatalyst E, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 87 wt% and methane content 13 wt%.
Example 6
Slowly adding 7mmol of water into 10mmol of triisobutylaluminum (1M toluene solution) in an ice bath under the protection of nitrogen, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, and then cooling to room temperature for later use; adding 5mmol of methylaluminoxane (1M toluene solution) into the solution, heating and refluxing for 1 hour, and cooling to room temperature; slowly adding 1mmol of water into the mixed solution under ice bath, stirring for reaction for 0.5 hour, heating and refluxing for 1 hour, cooling to room temperature, removing the toluene solvent under reduced pressure, and adding a cyclohexane solvent to obtain the cocatalyst F (1M, cyclohexane solution) with the total volume of 15 mL.
And (3) product analysis: taking a certain amount of cocatalyst F (same as example 1), slowly adding excessive water to decompose the cocatalyst F, wherein the content of aluminum in the liquid-phase component is 3.4 wt% by ICP test; gas phase composition test isobutane content 94 wt%, methane content 6 wt%.
Example 7 (polymerization example)
Ethylene oligomerizationThe reaction is carried out in a stainless steel polymerization kettle. The autoclave is heated to 80 ℃, vacuumized, replaced by nitrogen for a plurality of times, cooled to room temperature, and then filled with ethylene for replacement for a plurality of times. Cyclohexane was then added at 40 ℃ with 2.5. mu. mol of chromium acetylacetonate and 5. mu. mol of ligand (R)1SR2)2N ligand (wherein R1Is ethyl, R2Ethylene) and 750 mu mol of cocatalyst A, the total volume of the mixed solution is 100mL, wherein the molar ratio of the chromium, the ligand compound and the cocatalyst is 1: 2: and 240, controlling the reaction pressure to be 5MPa, and introducing ethylene to carry out ethylene trimerization.
And after the reaction is finished, cooling the system to room temperature, collecting the gas-phase product in a gas metering tank, collecting the liquid-phase product in a conical flask, and adding 1mL of ethanol as a terminator to terminate the ethylene oligomerization reaction. And (4) carrying out gas chromatographic analysis after the gas-liquid phase product is measured. The reaction results are shown in Table 1.
Example 8 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst B; the reaction results are shown in Table 1.
Example 9 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst C; the reaction results are shown in Table 1.
Example 10 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst D; the reaction results are shown in Table 1.
Example 11 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst E; the reaction results are shown in Table 1.
Example 12 (polymerization example)
The same as example 7 except that cocatalyst A was changed to cocatalyst F; the reaction results are shown in Table 1.
Example 13 (polymerization example)
The same as example 7, except that the reaction pressure was changed from 4MPa to 2 MPa; the reaction results are shown in Table 1.
Example 14 (polymerization example)
The difference from example 7 is that R1Changing the position into a decyl group; the reaction results are shown in Table 1.
Example 15 (polymerization example)
The difference from example 7 is that R1To phenyl; the reaction results are shown in Table 1.
Comparative example 1 (polymerization example)
The same as example 7 except that the cocatalyst A was changed to methylaluminoxane (1.5M in toluene); the reaction results are shown in Table 1.
Comparative example 2 (polymerization example)
The same as example 7 except that the solvent cyclohexane was changed to toluene and the cocatalyst A was changed to methylaluminoxane (1.5M in toluene); the reaction results are shown in Table 1.
Comparative example 3 (polymerization example)
An equal amount (as in example 1) of methylaluminoxane (1.5M in toluene) was taken, the solvent was removed in vacuo, and the residue was a white powdery solid which was not dissolved by addition of cyclohexane. The resulting polymer was used in polymerization reaction under the same conditions as in example 7, and the reaction did not proceed normally.
Comparative example 4 (polymerization example)
The same as example 7 except that cocatalyst A was changed to modified methylaluminoxane (aluminum content 3.4% by weight, heptane solution, isobutane content 63% by weight, methane content 37% by weight). The modified methylaluminoxane is prepared by adding heptane into a 7 wt% heptane solution of commercial MMAO-3A and diluting. The reaction results are shown in Table 1.
TABLE 1
The selectivity refers to the mass percentage of the component in the product.
As can be seen from table 1: the cocatalyst can be completely dissolved in an alkane solvent, and has ultrahigh catalytic activity in the reaction; the commercially available methylaluminoxane can only be dissolved in an aromatic hydrocarbon solvent, and when the methylaluminoxane is used for oligomerization reaction, the catalytic activity is obviously reduced no matter the methylaluminoxane solvent is an alkane solvent or an aromatic hydrocarbon solvent; the commercially available methylaluminoxane can not be effectively used for the reaction because the white powder solid obtained by removing the solvent can not be dissolved in the alkane solvent; commercially available modified methylaluminoxanes are used for the trimerisation of ethylene with a significantly lower catalytic activity than the catalyst composition of the present invention.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are used for explaining the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to the exemplary embodiments illustrated above, but it is understood that all 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 (28)
1. A catalyst composition comprising a ligand compound represented by the formula (1), a transition metal compound, and an alkane solution containing an aluminum cocatalyst;
in the formula, R1Selected from alkyl, aryl, alkyl derivatives and aryl derivatives; r2Is C1～C15Alkylene groups of (a);
the preparation method of the alkane solution containing the aluminum cocatalyst comprises the following steps:
step a: reacting water with an aromatic hydrocarbon solution of aluminum alkyl; wherein the general formula of the alkyl aluminum is R1R2R3Al，R1、R2And R3Same or different, independently selected from C1-C20Alkyl groups of (a); the molar ratio of water to the aluminum alkyl in step a is (0.5-1): 1;
step b: heating and refluxing the solution obtained after the reaction in the step a and the aromatic hydrocarbon solution of the aluminoxane; alkyl groups and R in said aluminoxanes1、R2And R3Different;
step c: b, reacting the solution obtained after the reaction in the step b with water, removing aromatic hydrocarbon, and adding alkane to obtain an alkane solution containing the aluminum cocatalyst; the molar ratio of water to the aluminoxane in step c is (0.1-0.3): 1.
2. The catalyst composition of claim 1, wherein R is1Is selected from C1-C10Alkyl and phenyl groups of (a); r2Is C2-C10An alkylene group of (a).
3. The catalyst composition of claim 1, wherein the aluminum alkyl has the formula wherein R1、R2And R3Same or different, independently selected from C1-C10Alkyl group of (1).
4. The catalyst composition of claim 3, wherein the aluminum alkyl has the formula wherein R1、R2And R3Same, selected from methyl, ethylOne of n-propyl, isopropyl, butyl, isobutyl, tert-butyl and n-pentyl.
5. The catalyst composition of any of claims 1-4, wherein the aluminoxane is selected from at least one of methylaluminoxane and ethylaluminoxane.
6. The catalyst composition of any one of claims 1 to 4, wherein the step a comprises reacting the water with an aromatic hydrocarbon solution of an aluminum alkyl at-20 ℃ to 10 ℃ for 5 to 60min, and then heating and refluxing for 5 to 60 min.
7. The catalyst composition of claim 6, wherein the step a comprises reacting the water with an aromatic hydrocarbon solution of aluminum alkyl at-10 ℃ to 0 ℃ for 5 to 60min, and then heating and refluxing for 5 to 60 min.
8. The catalyst composition of any one of claims 1 to 4, wherein the step b comprises mixing the solution obtained after the reaction in the step a with an aromatic hydrocarbon solution of aluminoxane at a temperature of 5 ℃ to 40 ℃, followed by heating and refluxing for 0.1h to 1 h.
9. The catalyst composition of claim 8, wherein the step b comprises mixing the solution obtained after the reaction of the step a with an aromatic hydrocarbon solution of aluminoxane at room temperature, and then heating and refluxing for 0.1 to 1 hour.
10. The catalyst composition of any of claims 1-4, wherein the molar ratio of the aluminoxane to the aluminum alkyl in step b is (0.1-3): 1.
11. The catalyst composition of claim 10, wherein the molar ratio of the aluminoxane to the aluminum alkyl in step b is (0.5-1): 1.
12. The catalyst composition according to any one of claims 1 to 4, wherein the step c comprises reacting the solution obtained after the reaction in the step b with water at-20 ℃ to 10 ℃ for 5min to 60min, and then heating under reflux for 5min to 60 min.
13. The catalyst composition of claim 12, wherein the step c comprises reacting the solution obtained after the reaction in the step b with water at-10 ℃ to 0 ℃ for 5min to 60min, and then heating and refluxing for 5min to 60 min.
14. The catalyst composition of any of claims 1-4, wherein the molar ratio of water to the aluminoxane in step c is (0.1-0.3): 1.
15. The catalyst composition of any one of claims 1-4, wherein the alkane is selected from one or more of hexane, heptane, cyclohexane, cyclopentane, dodecane, tetradecane, and methylcyclohexane; and/or, the arene comprises a substituted or unsubstituted arene.
16. The catalyst composition of claim 15, wherein the aromatic hydrocarbon is selected from one or more of toluene, xylene, or nitrobenzene.
17. The catalyst composition of any one of claims 1-4, wherein R is1-R3And when the catalyst is isobutyl, the content of isobutane in the gas-phase product is higher than 75 wt% measured by gas chromatography after the aluminum-containing cocatalyst is hydrolyzed.
18. The catalyst composition of claim 17, wherein R is1-R3And when the catalyst is isobutyl, the content of the isobutane in the gas-phase product is 78-94 wt% measured by gas chromatography after the aluminum-containing cocatalyst is hydrolyzed.
19. A catalyst composition according to any one of claims 1 to 4, characterized in that the transition metal compound is selected from at least one of compounds of chromium, molybdenum, iron, titanium, zirconium or nickel.
20. The catalyst composition of claim 19, wherein the transition metal compound is at least one of chromium acetylacetonate, chromium isooctanoate, chromium tris (tetrahydrofuran) trichloride, or chromium bis (tetrahydrofuran) dichloride.
21. The catalyst composition according to any one of claims 1 to 4, wherein the amount of the transition metal compound is 0.1 to 10 moles with respect to 1 mole of the ligand compound; the amount of the aluminum-containing cocatalyst is 1 to 1500 mol.
22. The catalyst composition according to claim 21, wherein the amount of the transition metal compound is 0.25 to 2 moles with respect to 1 mole of the ligand compound; the amount of the aluminum-containing cocatalyst is 10 to 800 mol.
23. The catalyst composition according to claim 21, wherein the amount of the transition metal compound is 0.5 to 2 moles with respect to 1 mole of the ligand compound; the amount of the aluminum-containing cocatalyst is 100-260 mol.
24. A method of using a catalyst composition comprising conducting an ethylene trimerization reaction in the presence of the catalyst composition of any one of claims 1-23.
25. Use according to claim 24, characterized in that the ethylene trimerization reaction is carried out in an organic solvent.
26. Use according to claim 24, characterized in that the ethylene trimerization reaction is carried out in an alkane.
27. Use according to any one of claims 24 to 26, wherein in the ethylene trimerization reaction the reaction temperature is between 0 and 200 ℃; the ethylene pressure is 0.5-20.0 MPa.
28. The use according to claim 27, characterized in that, in the ethylene trimerization reaction, the reaction temperature is 0-100 ℃; the ethylene pressure is 2.0-7.0 MPa.
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| Title |
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| Cp2ZrCl2 /异丁基铝氧烷催化乙烯聚合;范志强等;《高等学校化学学报》;19980731;第19卷(第7期);第1178-1180页 * |
| 烷基改性甲基铝氧烷的合成及在乙烯聚合中的应用;陈雪蓉等;《石化技术与应用》;20080731;第26卷(第4期);第326-328页 * |
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