CN120682400A - Active metallocene catalyst composition of olefin copolymer and its synthesis process - Google Patents
Active metallocene catalyst composition of olefin copolymer and its synthesis processInfo
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Abstract
本发明公开了一种烯烃共聚物的活性茂金属催化剂组合物及其合成方法，属于烯烃聚合催化剂领域。方法包括惰性气体保护下，桥联的茂金属催化剂与给电子体在有机溶剂中搅拌混合后，获得活性茂金属催化剂组合物；可选的，在搅拌混合后可加入有机金属试剂反应。本发明通过大位阻给电子体与活性中心的络合，使茂金属催化剂在含大量有机金属试剂的强碱性和强还原性条件下仍保持较高的稳定性。在此基础上，进一步通过与有机金属试剂的反应，获得具有良好溶解性和稳定性的茂金属催化剂组合物。该方法流程简单，制备而来的催化剂组合物表现出较高的催化活性，并且获得的催化剂组合物具有较好的溶解性，且长时间放置于室温能够保证催化活性不减。
The present invention discloses an active metallocene catalyst composition for olefin copolymers and a synthesis method thereof, and belongs to the field of olefin polymerization catalysts. The method comprises the following steps: under the protection of an inert gas, a bridged metallocene catalyst and an electron donor are stirred and mixed in an organic solvent to obtain an active metallocene catalyst composition; optionally, an organometallic reagent can be added for reaction after stirring and mixing. The present invention achieves high stability of the metallocene catalyst under strong alkalinity and strong reducing conditions containing a large amount of organometallic reagents by complexing a large sterically hindered electron donor with the active center. On this basis, a metallocene catalyst composition with good solubility and stability is obtained by further reacting with an organometallic reagent. The method has a simple process, the prepared catalyst composition exhibits high catalytic activity, and the obtained catalyst composition has good solubility, and the catalytic activity can be maintained even when placed at room temperature for a long time.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to an active catalyst composition of an olefin copolymer and a synthesis method thereof.
Background
The PBE (propylene-based elastomer) is a polymer with low crystallinity, which is obtained by taking propylene as a main raw material and adding a small amount of ethylene monomer through solution polymerization, and has a special microphase separation structure, namely a cross-linked network formed by a hard segment (a crystallization area) and a soft segment (an amorphous area), so that the PBE can obtain high rebound resilience without vulcanization, has good compatibility with olefin polymers, particularly polypropylene, and is widely used for blending modification so as to improve the processability of the olefin polymers, thus the PBE also becomes an important field of competitive layout of tap chemical enterprises. In recent years, metallocene catalysts have been used as the main catalysts for preparing propylene copolymers due to their high reactivity. A method of preparing propylene polymers using a diaryl silane bridged metallocene catalyst is reported in chinese patent CN119654331a, a method of preparing propylene copolymer compositions using a combination of metallocene catalyst and a pyridine diamine based catalyst is reported in chinese patent CN109563202a, a method of preparing propylene copolymers using a specific kind of metallocene complex in combination with a catalyst system of an organoboron compound and a methylaluminoxane compound is disclosed in chinese patent CN111902436a, and several different types of propylene copolymers are prepared using different metallocene catalysts in 2016, hsiao, b.s. et al. These are all sufficient to make metallocene catalysts play a significant role in the preparation of propylene-based elastomers, whereas the central metals of conventional metallocene catalysts are based on zirconium and hafnium and the coordinating groups are typically halogen atoms. The catalyst has the characteristics of small dissolving capacity, poor stability and the like, and the catalyst has certain trouble on the loading and large-scale production of the catalyst.
Disclosure of Invention
The invention aims to solve the problems of small dissolving capacity and poor stability of the existing metallocene catalyst, and provides an active catalyst composition of an olefin copolymer and a synthesis method thereof. The catalyst composition is particularly useful in synthetic applications in propylene copolymerization. By using the active catalyst composition, the solubility and stability of the catalyst in an organic solvent can be significantly improved, and a propylene copolymer can be obtained with higher activity.
Because the large steric hindrance electron donor containing nitrogen atom or oxygen atom in the catalyst composition is introduced and forms effective coordination with the central metal of the metallocene catalyst, the electron and the steric structure effect of the catalytic active center are regulated, the stability of the catalyst is macroscopically improved, the polymerization activity is improved, and the catalyst composition further reacts with the organic metal reagent on the basis to generate the active metallocene composition with better dissolving capacity.
Thus, in a first aspect the present invention provides a method of synthesizing a catalyst composition comprising:
The method 1 comprises the steps of stirring and mixing a bridged metallocene catalyst with a structure shown in a formula (2) and an electron donor in an organic solvent under the protection of inert gas to obtain an active metallocene catalyst composition shown in the formula (1);
The method 2 comprises the steps of stirring and mixing the bridged metallocene catalyst with the structure shown in the formula (3) with an electron donor and an organic metal reagent in an organic solvent for reaction under the protection of inert gas to obtain an active metallocene catalyst composition shown in the formula (1);
Wherein Cp 1 and Cp 2 are respectively a cyclopentadienyl group which is mono-substituted or poly-substituted by a hydrocarbon group of 1 to 10 carbon atoms, an indenyl group which is mono-substituted or poly-substituted by a methoxy group of 1 to 5 carbon atoms, an indenyl group which is unsubstituted or mono-substituted by a hydrocarbon group of 1 to 10 carbon atoms, a fluorenyl group which is mono-substituted or poly-substituted by a hydrocarbon group of 1 to 10 carbon atoms, or an fluorenyl group which is unsubstituted;
The central metal M is titanium, zirconium or hafnium;
X 1 and X 2 are hydrocarbon groups of 1 to 10 carbon atoms, X 3 and X 4 are halogen atoms;
L is a radical linking Cp 1 and Cp 2, is a bridging group-CR 2-,-CR2-CR2-,-SiR2-,-SiR2-SiR2-,-GeR2 -wherein each R group is independently a hydrogen atom and a hydrocarbyl group of 1 to 10 carbon atoms, optionally two R groups together may form a ring;
D is the electron donor.
In the method 2, the feeding sequence of the electron donor and the organometallic reagent is not limited, for example, the electron donor can be firstly added into the bridged metallocene catalyst with the structure shown in the formula (3) and stirred and mixed in an organic solvent, then the organometallic reagent is added for reaction, or the organometallic reagent can be firstly added and then the electron donor can be added, and the electron donor and the organometallic reagent can be simultaneously added according to the requirement on the premise of not influencing the yield of the final product shown in the formula (1).
Preferably, the metallocene catalyst is selected from the group consisting of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, di-p-toluylene (cyclopentadienyl) (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (tetramethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylbis (indenyl) zirconium dichloride, rac-vinylbis (indenyl) zirconium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-vinylbis (4, 5,6, 7-tetrahydro-1-indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) hafnium dichloride, diphenylmethylenebis (cyclopentadienyl) (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis (cyclopentadienyl) hafnium dichloride, and p-xylylene (hafnium dichloride, at least one of dimethylsilylbis (cyclopentadienyl) hafnium dichloride, dimethylsilylbis (tetramethylcyclopentadiene) hafnium dichloride, rac-dimethylsilylbis (indenyl) hafnium dichloride, rac-vinylbis (indenyl) hafnium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride, rac-vinylbis (4, 5,6, 7-tetrahydro-1-indenyl) hafnium dichloride.
The electron donor D is at least one of linear siloxane compound shown in the formula (4), cyclic siloxane compound shown in the formula (5), cage polysilsesquioxane shown in the formula (6) or crown ether compound,
Wherein the R 2、R3、R4 group is a hydrocarbon group of 1 to 10 carbon atoms.
Further, the molar ratio of the electron donor to the metallocene catalyst represented by the formula (2) or the formula (3) is 1 (1-100).
The organic metal reagent is at least one of an organomagnesium reagent, an organolithium reagent, an alkylaluminoxane, an organoaluminum reagent and an organozinc reagent. Further, the organic metal reagent is at least one of organic lithium reagent, organic magnesium reagent and alkyl aluminoxane, the mol ratio of the metallocene catalyst shown in the formula (3) to the organic metal reagent is 1 (2-5),
Further, the organic solvent is at least one of alkane, aromatic hydrocarbon and ether solvents, preferably at least one of hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran and methyltetrahydrofuran.
According to a second aspect of the present invention there is provided an active metallocene catalyst composition prepared by the synthetic method.
According to a third aspect of the present invention, the use of the active metallocene catalyst composition in the polymerization of olefins.
Further, the olefin polymerization reaction includes propylene homopolymerization reaction and propylene copolymerization reaction.
Preferably, the copolymerization of propylene is a copolymerization of propylene and an alpha-olefin, more preferably, the alpha-olefin is ethylene.
Further, adding the active metallocene catalyst composition and a cocatalyst in the olefin polymerization reaction, wherein the cocatalyst is at least one of an organoboron compound, an alkylaluminoxane and an organoaluminium compound, and the olefin polymerization reaction adopts at least one of aliphatic hydrocarbon solvents as an organic solvent;
When propylene copolymerization is carried out, an aliphatic hydrocarbon solvent, a metallocene catalyst composition and a cocatalyst are added into a polymerization reaction kettle, stirring is carried out, after the temperature is increased to a target temperature, propylene is introduced for reaction for a period of time, and then alpha-olefin is introduced for pressurization reaction, so that a product is obtained.
Further, the organic solvent is at least one of an alkane solvent and an arene solvent.
The invention has the following advantages:
According to the synthesis method of the active metallocene catalyst composition, disclosed by the invention, the metallocene catalyst still maintains higher stability under the conditions of strong alkalinity and strong reducibility containing a large amount of organic metal reagents through complexing of the large-steric-hindrance electron donor and the active center. On this basis, a metallocene catalyst composition having good solubility and stability is further obtained by reaction with an organometallic reagent. The method has simple flow, the prepared catalyst composition has higher catalytic activity, the obtained catalyst composition has better solubility, and the catalyst composition can be placed at room temperature for a long time to ensure that the catalytic activity is not reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a nuclear magnetic resonance spectrum of a metallocene compound 2b obtained in the step (1) of example 1 of the present invention;
Detailed Description
In the prior art, the conventional metallocene catalyst has poor dissolving capacity in an organic solvent, usually only has the solubility of 10 mu mol/mL at most, so that a large amount of solvent is required for dissolving in large-scale polymer production by adopting the metallocene catalyst, the conventional metallocene catalyst has poor stability after being prepared into a solution and needs to be stored at a low temperature for a long time, the catalyst solution is often prepared at present, however, the preparation takes a large amount of time due to the poor solubility, and the complexity of actual operation is increased.
The embodiment of the invention provides two synthetic methods of active metallocene catalyst compositions:
Under the protection of inert gas, stirring and mixing the bridged metallocene catalyst with the structure shown in the formula (2) and an electron donor in an organic solvent to obtain a metallocene catalyst composition shown in the formula (1);
Under the protection of inert gas, stirring and mixing the bridged metallocene catalyst with the structure shown in the formula (3) with an electron donor and an organic metal reagent in an organic solvent for reaction to obtain a metallocene catalyst composition shown in the formula (1);
Wherein, the structural formulas of the formulas (1), (2) and (3) are as follows:
in the formula (1), the formula (2) and the formula (3):
Cp 1 and Cp 2 are each a cyclopentadienyl group which is mono-or poly-substituted by a hydrocarbon group of 1 to 10 carbon atoms, an indenyl group which is mono-or poly-substituted by a methoxy group of 1 to 5 carbon atoms, a fluorenyl group which is mono-or poly-substituted by a hydrocarbon group of 1 to 10 carbon atoms, or an fluorenyl group which is unsubstituted;
The central metal M is titanium, zirconium or hafnium;
X 1 and X 2 are hydrocarbon groups of 1 to 10 carbon atoms, X 3 and X 4 are halogen atoms;
L is a radical linking Cp 1 and Cp 2, which may be a bridging group of-CR 2-,-CR2-CR2-,-SiR2-,-SiR2-SiR2-,-GeR2 -wherein each R group is independently a hydrogen atom or a hydrocarbyl group of 1 to 10 carbon atoms, optionally two R groups together may form a ring.
And D is an electron donor which is at least one of a linear siloxane compound (comprising an amino siloxane compound) shown in a formula (4), a cyclic siloxane compound shown in a formula (5) and a cage polysilsesquioxane or crown ether compound shown in a formula (6), wherein the R 2、R3、R4 group is a hydrocarbon group with 1-10 carbon atoms.
The organic metal reagent in the method 2 can be at least one of an organic magnesium reagent, an organic lithium reagent, an alkyl aluminoxane, an organic aluminum reagent and an organic metal zinc reagent, and further the organic metal reagent is at least one of an organic lithium reagent, an organic magnesium reagent and an alkyl aluminoxane.
In one embodiment of the present invention, in formula (2), cp 1 and Cp 2 are each a hydrocarbyl group of 1 to 8 carbon atoms and are each a mono-or polysubstituted indenyl group, the central metal M is zirconium or hafnium, the above hydrocarbyl group is more preferably an alkyl group of 1 to 6 carbon atoms or an aryl group of 6 to 8 carbon atoms, further preferably an alkyl group of 1 to 6 carbon atoms, and X 1 and X 2 are each independently a hydrocarbyl group, further preferably a methyl group, an ethyl group or a benzyl group.
In one embodiment of the present invention, in formula (3), cp 1 and Cp 2 are each a hydrocarbyl group of 1 to 8 carbon atoms and are each a mono-or polysubstituted indenyl group, the central metal M is zirconium or hafnium, and X 3 and X 4 are each independently a halogen atom, and as the above-mentioned hydrocarbyl group, an alkyl group of 1 to 6 carbon atoms or an aryl group of 6 to 8 carbon atoms is more preferable, and an alkyl group of 1 to 6 carbon atoms is further preferable.
In one embodiment of the present invention, the electron donor is a linear siloxane compound represented by formula (4), a cyclic siloxane compound represented by formula (5), or a cage polysilsesquioxane represented by formula (6). The linear siloxane compounds include dicyclopentyl dimethoxy silane, phenyl triethoxy silane, t-butyl trimethoxy silane, (dimethylamino) dimethoxy silane, dipiperidyl dimethoxy silane, etc., the cyclic siloxane compounds include hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, etc., and the cage polysilsesquioxane compounds include POSS MS0825, POSS 01460, POSS 01440, etc.
In one embodiment of the invention, the molar ratio of the electron donor to the metallocene catalyst having the formula (2) or the formula (3) is 1 (1-100). Preferably, the molar ratio of the electron donor to the metallocene catalyst having formula (2) or formula (3) is 1:40.
In one embodiment of the invention, the organometallic reagent is an alkyllithium, an alkyl grignard reagent, an alkylaluminoxane, or an alkylaluminum. The alkyl lithium comprises methyl lithium, butyl lithium and the like, the alkyl Grignard reagent comprises methyl magnesium bromide, methyl magnesium chloride, isopropyl magnesium chloride, phenyl magnesium bromide and the like, the alkyl aluminoxane comprises modified methyl aluminoxane, methyl aluminoxane and the like, and the alkyl aluminum reagent comprises trimethyl aluminum, triisobutyl aluminum and the like.
In one embodiment of the present invention, the molar ratio of the metallocene catalyst having the formula (3) to the organometallic reagent is 1 (2-5). Preferably, the molar ratio of the metallocene catalyst and the organometallic reagent having the formula (3) is 1:1.9-2.2.
Specifically, the organic solvent comprises at least one of alkane, aromatic hydrocarbon or ether compounds. In one embodiment of the invention, the aromatic hydrocarbon and alkane solvents are aliphatic hydrocarbon solvents, and the metallocene catalyst with the formula (3) has poor solubility in the solvents, and usually exists in a form of turbid liquid. Preferably, the organic solvent comprises at least one of hexane, cyclohexane and toluene.
Specifically, the reaction temperature is-78 ℃ to 100 ℃, preferably-78 ℃ to 40 ℃, specifically, the reaction time is 1 to 24 hours, preferably 1 to 12 hours, and specifically, the inert gas comprises at least one of nitrogen, helium and argon. The inert gas is protected in a glove box in an inert argon atmosphere, and the content of water and oxygen is less than 0.1ppm.
An embodiment of the invention also provides an active metallocene catalyst composition prepared by any one of the synthetic methods.
The active metallocene catalyst composition prepared by the method provided by the embodiment of the invention is a fluorescent green solid, has good dissolving capacity in aromatic hydrocarbon, halogenated hydrocarbon and ether solvents, has good stability in solution, can be stored for a long time in an inert atmosphere at room temperature, and has basically no influence on polymerization activity.
An embodiment of the present invention also provides the use of the above-described active metallocene catalyst composition in olefin polymerization reactions.
Specifically, the olefin polymerization reaction includes propylene homopolymerization reaction and propylene copolymerization reaction.
Preferably, the copolymerization of propylene is a copolymerization of propylene and an alpha-olefin, more preferably, the alpha-olefin is ethylene.
In an embodiment of the invention, the metallocene catalyst composition prepared by the method in the embodiment of the invention improves the stability of the cationic center of the catalyst due to the addition of the electron donor, not only improves the stability of the catalyst solution, but also improves the polymerization activity.
In one embodiment of the invention, the organic solvent, the active metallocene catalyst composition and the cocatalyst are added into a reaction kettle, and after the reaction temperature is raised, propylene is added for reaction for a period of time, and then alpha-olefin is introduced for pressurized reaction, so that the product is obtained.
In one embodiment of the invention, it is preferred that the copolymerization is carried out in an inert organic solvent. The inert solvent may be one or a mixture of several of linear aliphatic hydrocarbon, branched aliphatic hydrocarbon, substituted or unsubstituted cyclic aliphatic hydrocarbon and substituted or unsubstituted aromatic hydrocarbon. Specific examples of the inert organic solvent include hexane, heptane, cyclohexane, toluene and xylene. In addition, the amount of organic solvent may be dependent on the reactivity, ensuring that good dissolution of the resulting polymer in the system is achieved, at least without affecting the dispersion.
In one embodiment of the present invention, the polymerization conditions may be those commonly used in the art for the synthesis of polyolefins. Preferably, the temperature of the copolymerization is 0-200 ℃, the time of the copolymerization is 1-300 minutes, more preferably, the temperature of the copolymerization is 50-120 ℃, and the time of the copolymerization is 5-60 minutes.
In one embodiment of the invention, the olefin preferably has a partial pressure of 0.1 to 10MPa, preferably 0.1 to 4.0MPa. In one embodiment of the present invention, the olefin is preferably propylene, or propylene or a second olefin as a comonomer, preferably the second olefin as a comonomer is at least one of ethylene, 1-butene, 1-hexene, 1-octene, more preferably ethylene.
Specifically, the cocatalyst is at least one of an organoboron compound, an organoaluminum compound and alkylaluminoxane, wherein the organoboron compound can be various organoboron compounds used as cocatalysts in the field, including but not limited to tris (pentafluorophenyl) borane, triphenylmethyl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and the like, and the organoaluminum compound can be various organoaluminum compounds used as cocatalysts in the field, including but not limited to triisobutylaluminum, trimethylaluminum, triethylaluminum and the like, and the alkylaluminoxane comprises modified methylaluminoxane, ethylaluminoxane and the like. Wherein the cocatalyst is added in the form of a solution, and the concentration of the cocatalyst can be 0.01-0.5mol/L.
Specifically, the molar ratio of the catalyst center metal to the anion center in the cocatalyst is 1 (1-2000), preferably, when the cocatalyst is a combination of organoboron compound boron and organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1 (1-5), preferably 1 (1-2), the molar ratio of the metallocene compound to the organoaluminum compound is 1 (10-1000), preferably 1 (50-500), and when the cocatalyst is alkylaluminoxane, the molar ratio of the metallocene catalyst composition to the alkylaluminoxane calculated as aluminum is 1 (100-10000), more preferably 1 (500-2000).
Specifically, the device required by the reaction is vacuumized in advance and then replaced by nitrogen for at least 3 times for reuse. The arrangement can lead the interior of the reaction device to be basically in a water-free and oxygen-free environment, which is beneficial to the reaction.
Specifically, after the reaction is finished, the polymerization solution is poured into ethanol to terminate the reaction, and the polymerization product is obtained through ethanol washing and vacuum drying.
The invention will be described in detail with reference to examples.
Example 1a process for the preparation of an active metallocene catalyst composition (Cp 1 and Cp 2 are indenyl; X 3 and X 4 are chloride; L is dimethylsilyl) comprising the steps of:
(1) Under the protection of inert gas, placing a compound 1a (260 mg,0.59 mmol) in a 25mL reaction tube at room temperature, adding 5mL of toluene solution, adding 1mL of methyl lithium diethyl ether solution (1.3M, 2.2 equiv.) into the reaction solution, stirring for 1h at room temperature, changing the solution from orange-yellow turbid liquid into pale yellow solution, adding n-hexane to quench the reaction after the reaction is finished, then drying the solvent under vacuum, dissolving with toluene, filtering to remove lithium salt, taking filtrate, drying the solvent under vacuum, obtaining fluorescent green solid 2a with a yield of 28%, and performing nuclear magnetic characterization, wherein the result can be seen in FIG. 1, and we can find that a single peak with a peak area of 3 appears at 0.91ppm, which proves that chloride ions on central metallic zirconium have been successfully replaced by methyl.
(2) The toluene solution of hexamethylcyclotrisiloxane and the solid 2a obtained in step (1) are formulated into a toluene solution of the active metallocene catalyst composition. Wherein the solid 2a has better dissolution capacity in toluene (the solubility in toluene exceeds 0.1 mmol/mL) and has better stability after being configured into an active metallocene catalyst composition solution, and the catalytic activity is kept unchanged after being placed for 14 days at room temperature.
Example 2A process for preparing an active metallocene catalyst composition (Cp 1 and Cp 2 are indenyl; X 3 and X 4 are chloride; L is dimethylsilyl) comprising the steps of:
(1) 1b (260 mg,0.59 mmol) and octamethyltetrasiloxane were dissolved in 25mL of toluene under inert gas at room temperature and mixed with stirring for 10h.
(2) To the toluene solution obtained in step (1), 0.44mL of a tetrahydrofuran solution (3 m,2.2 equiv.) of methyl magnesium chloride was added, and the mixture was stirred at room temperature for 1 hour, and after the reaction was completed, the solution was turned from orange-yellow turbid liquid to pale yellow solution, and after the reaction was completed, the reaction was quenched by adding n-hexane, and then after the solvent was dried under vacuum, it was dissolved with toluene, the magnesium salt was removed by filtration, and the filtrate was taken, and after the solvent was dried under vacuum, a fluorescent green solid 2b was obtained in 40% yield. Wherein the solid 2b has better dissolution capability in toluene, and has better stability after being prepared into an active metallocene catalyst composition solution, and the catalytic activity is kept unchanged after the solid 2b is placed for 14 days at room temperature.
Example 3A process for preparing an active metallocene catalyst composition (Cp 1 and Cp 2 are indenyl; X 3 and X 4 are chloride; L is dimethylsilyl) comprising the steps of:
(1) 1c (334 mg,0.59 mmol) and octamethyltetrasiloxane were dissolved in 25mL of toluene under inert gas at room temperature and mixed with stirring for 10h.
(2) To the toluene solution obtained in step (1), 1mL of an ether solution of methyllithium (1.3 m,2.2 equiv.) was added, and the mixture was stirred at room temperature for 1 hour, the solution was changed from orange-yellow turbid liquid to pale yellow solution, after the reaction was completed, the reaction was quenched by adding n-hexane, then the solvent was dried under vacuum, then the solution was dissolved with toluene, the magnesium salt was removed by filtration, and the filtrate was taken, and after the solvent was dried under vacuum, a fluorescent green solid 2c was obtained in a yield of 38%. Wherein the solid 2c has better dissolution capability in toluene, and has better stability after being prepared into an active metallocene catalyst composition solution, and the catalytic activity is kept unchanged after the solid 2c is placed for 14 days at room temperature.
Example 4 a process for preparing an active metallocene catalyst composition (Cp 1 and Cp 2 are 2-methyl-indenyl; X 3 and X 4 are chloride; L is dimethylsilyl) comprising the steps of:
(1) Under the protection of inert gas, 1d (281mg, 0.59 mmol) and octamethyltetrasiloxane were dissolved in a 25mL reaction tube using 5mL toluene and mixed with stirring for 10h.
(2) To the toluene solution obtained in step (1), 0.44mL of a tetrahydrofuran solution (3 m,2.2 equiv.) of methyl magnesium chloride was added, and the mixture was stirred at room temperature for 1 hour, and after the reaction was completed, the solution was turned from orange-yellow turbid liquid to pale yellow solution, and after the reaction was completed, the reaction was quenched by adding n-hexane, and then after the solvent was dried under vacuum, it was dissolved with toluene, the magnesium salt was removed by filtration, and the filtrate was taken, and after the solvent was dried under vacuum, a fluorescent green solid 2d was obtained in a yield of 36%.
Comparative example 1a process for the preparation of an active metallocene catalyst (Cp 1 and Cp 2 are indenyl; X 3 and X 4 are chloride; L is dimethylsilyl) comprising the steps of:
under the protection of inert gas, placing a compound 1e (260 mg,0.59 mmol) in a 25mL reaction tube at room temperature, adding 5mL of toluene solution, adding 1mL of methyl lithium diethyl ether solution (1.3M, 2.2 equiv.) into the reaction solution, stirring for 1h at room temperature, changing the solution from orange turbid liquid to light yellow solution, adding n-hexane to quench the reaction after the reaction is finished, then pumping the solvent under vacuum, dissolving with toluene, filtering to remove lithium salt, taking filtrate, pumping the solvent under vacuum, and obtaining fluorescent green solid 2e with 28% yield;
Experimental example 1 propylene-ethylene polymerization
(1) The reaction device is repeatedly vacuumized and replaced by nitrogen at 120 ℃ for 3 times in advance, the interior of the reaction device can be basically considered as anhydrous and anaerobic,
(2) 200ML of dehydrated and deoxidized n-hexane by refluxing with metallic sodium was added to the reaction vessel (500 mL), followed by 0.02mL (0.1 mmol/mL) of toluene solution of the active metallocene catalyst composition (2 a), 1.33mL (1.5M) of toluene solution of MAO,
(3) Continuously introducing 0.8Mpa propylene under stirring when the temperature of the reaction kettle is increased to 60 ℃,
(4) After stirring for 5 minutes, introducing ethylene with the pressure of 1.0MPa into a reaction kettle, reacting for 20 minutes,
(5) After the reaction is finished, pouring the polymerization solution into ethanol to terminate the reaction, washing the reaction product by the ethanol, and drying the reaction product in vacuum to obtain a polymerization product.
Test examples 2-4 propylene-ethylene polymerization
The difference from test example 1 is that in step (2) of test examples 2 to 4, active metallocene catalyst compositions 2b, 2c, 2d, 2a were added, respectively.
Test examples 5-8 propylene-ethylene polymerization (reaction temperature 100 ℃ C.)
The difference from test example 1 is that in step (2) of test examples 2 to 4, active metallocene catalyst compositions 2a, 2b, 2C, 2d were added, respectively, and the reaction vessel temperature in step (3) was 100 ℃.
Experimental examples 9-12 propylene-ethylene polymerization (catalysts 2a, 2b, 2c, 2d were allowed to stand for 14 days before use)
The difference from test example 1 is that, in step (2) of test examples 2 to 4, active metallocene catalyst compositions 2a, 2b, 2c, 2d (labeled 2a-14, 2b-14, 2c-14, 2 d-14) which have been stored in a glove box for 14 days are added, respectively.
In the case of comparative test example 1,
The difference from test example 1 is that in step (2) of test examples 2 to 4, an active metallocene catalyst composition 1e was added in place of 2a, respectively.
In the case of comparative test example 2,
The difference from test example 1 is that in step (2) of test examples 2 to 4, an active metallocene catalyst composition 2e was added in place of 2a, respectively.
In the case of comparative test example 3,
The difference from test example 1 is that in step (2) of test examples 2 to 4, an active metallocene catalyst composition 2e was added in place of 2a, respectively, and the reaction vessel temperature in step (3) was 100 ℃.
In the case of comparative test example 4,
The difference from test example 1 is that in step (2) of test examples 2 to 4, an active metallocene catalyst composition 2e which had been stored in a glove box for 14 days was added in place of 2a, respectively. (labeled 2 e-14)
The data obtained for the above test examples are shown in Table 1 below.
TABLE 1
From the polymerization data of table 1, after the metallocene catalyst was treated with the organometallic reagent and the electron donor was added, an active metallocene catalyst composition was produced, which exhibited more excellent polymerization activity, and the molecular weight distribution was also decreased (test examples 1 to 8 and comparative test examples 1 to 3), and at the same time, the reactivity of the catalyst was significantly improved with an increase in the reaction temperature. After 14 days, the catalytic activity of the four active metallocene catalyst compositions is not changed basically, which shows that the metallocene catalyst composition has better stability, while the metallocene catalyst without an electron donor is reduced in polymerization activity to a certain extent after 14 days (test examples 9-12 and comparative test example 4).
Therefore, the invention provides a synthetic method of the active metallocene catalyst composition, which reduces the complexity of actual operation, improves experimental repeatability and lays a foundation for the loading and large-scale industrial production of the active metallocene catalyst. The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A method of synthesizing an active metallocene catalyst composition for an olefin copolymer, characterized in that the method of synthesis is either method 1 or method 2:
The method 1 comprises the steps of stirring and mixing a bridged metallocene catalyst with a structure shown in a formula (2) and an electron donor in an organic solvent under the protection of inert gas to obtain an active metallocene catalyst composition shown in the formula (1);
The method 2 comprises the steps of stirring and mixing the bridged metallocene catalyst with the structure shown in the formula (3) with an electron donor and an organic metal reagent in an organic solvent for reaction under the protection of inert gas to obtain an active metallocene catalyst composition shown in the formula (1);
Wherein Cp 1 and Cp 2 are respectively a cyclopentadienyl group which is mono-substituted or poly-substituted by a hydrocarbon group of 1 to 10 carbon atoms, an indenyl group which is mono-substituted or poly-substituted by a methoxy group of 1 to 5 carbon atoms, an indenyl group which is unsubstituted or mono-substituted by a hydrocarbon group of 1 to 10 carbon atoms, a fluorenyl group which is mono-substituted or poly-substituted by a hydrocarbon group of 1 to 10 carbon atoms, or an fluorenyl group which is unsubstituted;
The central metal M is titanium, zirconium or hafnium;
X 1 and X 2 are hydrocarbon groups of 1 to 10 carbon atoms, X 3 and X 4 are halogen atoms;
L is a radical linking Cp 1 and Cp 2, is a bridging group-CR 2-,-CR2-CR2-,-SiR2-,-SiR2-SiR2-,-GeR2 -wherein each R group is independently a hydrogen atom and a hydrocarbyl group of 1 to 10 carbon atoms, optionally two R groups together may form a ring;
D is the electron donor.
2. The synthesis method according to claim 1, wherein,
The electron donor is at least one of linear siloxane compound shown as a formula (4), cyclic siloxane compound shown as a formula (5), cage polysilsesquioxane shown as a formula (6) or crown ether compound,
Wherein the R 2、R3、R4 group is a hydrocarbon group of 1 to 10 carbon atoms.
3. The synthesis method according to claim 1, wherein,
The molar ratio of the electron donor to the metallocene catalyst shown in the formula (2) or the formula (3) is 1 (1-100).
4. The synthesis method according to claim 1, wherein,
The organic metal reagent is at least one of an organomagnesium reagent, an organolithium reagent, an alkylaluminoxane, an organoaluminum reagent and an organozinc reagent.
5. The synthesis method according to claim 1, wherein,
The molar ratio of the metallocene catalyst shown in the formula (3) to the organic metal reagent is 1 (2-5).
6. The synthesis method according to claim 1, wherein
The organic solvent is at least one of alkane, aromatic hydrocarbon and ether solvents.
7. An active metallocene catalyst composition prepared by the synthetic method of any one of claims 1-6.
8. Use of the active metallocene catalyst composition of claim 7 in olefin polymerization reactions.
9. The use according to claim 8, wherein,
The olefin polymerization reaction is a homopolymerization reaction of propylene or a copolymerization reaction of propylene and alpha-olefin.
10. The use according to claim 8 or 9, characterized in that,
Adding the active metallocene catalyst composition and a cocatalyst which are at least one of an organoboron compound, an alkylaluminoxane and an organoaluminium compound into the olefin polymerization reaction, wherein at least one of aliphatic hydrocarbon solvents is adopted as an organic solvent in the olefin polymerization reaction;
When propylene copolymerization is carried out, an aliphatic hydrocarbon solvent, a metallocene catalyst composition and a cocatalyst are added into a polymerization reaction kettle, stirring is carried out, after the temperature is increased to a target temperature, propylene is introduced for reaction for a period of time, and then alpha-olefin is introduced for pressurization reaction, so that a product is obtained.
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