KR102022686B1 - Metallocene compounds, catalyst compositions comprising the same, and method for preparing olefin polymers using the same - Google Patents
Metallocene compounds, catalyst compositions comprising the same, and method for preparing olefin polymers using the same Download PDFInfo
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- KR102022686B1 KR102022686B1 KR1020150101902A KR20150101902A KR102022686B1 KR 102022686 B1 KR102022686 B1 KR 102022686B1 KR 1020150101902 A KR1020150101902 A KR 1020150101902A KR 20150101902 A KR20150101902 A KR 20150101902A KR 102022686 B1 KR102022686 B1 KR 102022686B1
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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
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
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- C07—ORGANIC CHEMISTRY
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- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
- C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
According to the present invention, it is easy to support without fouling during the polymerization process, so that a polymer in powder form can be easily obtained, and there is no fine powder generation, and an olefin polymer having a high melting point of 150 ° C or higher at a high temperature polymerization condition of 70 ° C or higher can be prepared. Provided is a metallocene compound having excellent activity, a catalyst composition comprising the same, and a method for preparing an olefin polymer using the catalyst composition.
Description
The present invention provides a metallocene compound of a novel structure, a catalyst composition comprising the same, and an olefin polymer using the same, which has a high activity through effective induction of supported reactions and can easily prepare an olefin polymer having a high molecular weight without undergoing a prepolymerization process. It relates to a manufacturing method of.
Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial production process of conventional polyolefins. The Ziegler-Natta catalysts have high activity, but because they are multi-active catalysts, the molecular weight distribution of the resulting polymers is wide and comonomers are used. There is a limit in securing the desired physical properties because the composition distribution is not uniform.
Accordingly, recently, metallocene catalysts in which a ligand including a cyclopentadiene functional group and a transition metal such as titanium, zirconium, and hafnium have been developed have been widely used. Metallocene compounds are generally used by activation with aluminoxanes, boranes, borates or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator.
The metallocene catalyst has an advantage of controlling the microstructure of the polymer prepared unlike the heterogeneous Ziegler-Natta catalyst. However, the metallocene catalyst has a disadvantage in that it is difficult to synthesize and has a low melting point (Tm) compared to Ziegler-Natta.
In addition, the currently developed metallocene catalyst for polypropylene undergoes a supporting process to be applied to a bulk polymerization, and a process problem such as fouling occurs when the supporting process is difficult and poorly supported. .
In general, the metallocene supported catalyst has a problem of undergoing a pre-plymerzation process before the polymerization in order to avoid process problems.
Therefore, there is still a need to develop a catalyst for olefin polymerization that is easy to carry out without fouling and has excellent activity.
An object of the present invention is to provide a metallocene compound that can provide an olefin polymer having an easy support process, excellent activity, high molecular weight and high melting point without going through a prepolymerization process.
Another object of the present invention is to provide a catalyst composition comprising the metallocene compound.
Still another object of the present invention is to provide a method for preparing an olefin polymer using the catalyst composition.
The present invention provides a metallocene compound represented by the following formula (1).
[Formula 1]
(In Formula 1,
R 1 to R 9 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms,
R 10 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
R 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
A is silicon or carbon,
Each X is independently halogen or an alkyl group having 1 to 20 carbon atoms)
In Formula 1, R 10 may be an alkyl group having 1 to 20 carbon atoms substituted with tert-butoxy, and R 11 may be an alkyl group having 1 to 20 carbon atoms.
Preferably, R 10 is tert-butoxy-hexyl, and R 11 may be methyl.
In addition, it is preferable that said A is silicone.
X may be halogen.
In the present invention, the compound represented by Formula 1 preferably includes the following Formula 1a.
[Formula 1a]
(In Formula 1a,
A is an element of group 14,
R 10 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms,
R 11 is an alkyl group having 1 to 20 carbon atoms,
Each X is independently halogen)
The compound represented by Chemical Formula 1 may be preferably a compound represented by Chemical Formula 1b.
[Formula 1b]
In another aspect, the present invention provides a catalyst composition for olefin polymerization comprising the metallocene compound of Formula 1.
The catalyst composition may further include one or more selected from the group consisting of a carrier and a promoter.
The present invention also provides a method for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition for olefin polymerization.
The present invention includes a tether group in the catalyst backbone, and also contains tert-butyl groups specifically at the 3 and 5 positions of the phenyl group substituted with an indane group, thereby exhibiting structural stability, thereby effectively supporting the carrier by a simple method. Can be. In addition, the catalyst of the present invention is easy to support without fouling during the polymerization process to obtain a powdery polymer easily, there is no fine powder generation and to produce an olefin polymer having a high melting point of 150 ℃ or more at a high temperature polymerization conditions of 70 ℃ or more can do.
Hereinafter, the present invention will be described in more detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
In addition, the meaning of “comprising” as used in the specification of the present invention embodies a particular characteristic, region, integer, step, operation, element and / or component, and other characteristics, region, integer, step, operation, element and / or It does not exclude the presence or addition of ingredients.
Hereinafter, a metallocene compound according to embodiments of the present invention, a catalyst composition comprising the same, and a preferable method for preparing an olefin polymer using the catalyst composition will be described in detail.
According to one embodiment of the invention, a compound represented by the following Formula 1 may be provided.
[Formula 1]
(In Formula 1,
R 1 to R 9 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms,
R 10 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
R 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
A is silicon or carbon,
Each X is independently halogen or an alkyl group having 1 to 20 carbon atoms)
In the present invention, a novel catalyst of Chemical Formula 1 was synthesized in a form in which a tether group, which can induce a more effective supported reaction, was synthesized.
In addition, the metallocene compound of Chemical Formula 1 has a symmetrical structure in which two inindacene structures and a silicon or carbon bridge are connected, and includes a bulky phenyl group in the two inindacene structures, in particular, 3 of the phenyl group. , Tert-butyl group is specifically substituted in the 5 position, there is a characteristic that produces a polymer having excellent stereoregularity during polymerization. In addition, hafnium contained in the metallocene compound of Formula 1 of the present invention has the effect of producing a high molecular weight polymer.
In addition, the metallocene compound of Chemical Formula 1 according to the present invention can effectively support the cocatalyst on the carrier in two stages, one stage each under the influence of the tether in the catalyst skeleton.
When the metallocene compound of the present invention is used as a catalyst in the polymerization process of the olefin, it has excellent catalyst activity and can obtain a polymer in powder form without fouling, and there is almost no fine powder generation because there is no catalyst etched in the carrier.
In addition, an olefin polymer having a high melting point (Tm) of 150 ° C. or higher may be manufactured using a metallocene supported catalyst including Chemical Formula 1 under high temperature polymerization conditions of 70 ° C. or higher.
On the other hand, in the present invention, when described in detail for each substituent defined in the formula (1) as follows.
The alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl group, and the alkenyl group and alkynyl group having 2 to 20 carbon atoms may include a straight or branched alkenyl group and an alkynyl group, respectively.
The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.
The alkylaryl group refers to an aryl group having one or more linear or branched alkyl groups of 1 to 20 carbon atoms introduced therein, and the arylalkyl group refers to a straight or branched alkyl group having one or more aryl groups of 6 to 20 carbon atoms introduced thereto.
And a halogen group means fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).
In the ligand compound of the above embodiment, R 10 in Formula 1 may be an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms. In this case, R 10 may refer to an alkyl group having 1 to 20 carbon atoms substituted with a straight or branched alkoxy group having 1 to 20 carbon atoms. In addition, the alkoxy group in R 10 may be substituted at the terminal or side chain of the alkyl group, preferably at the terminal.
In addition, more preferably, R 10 is an alkyl group having 1 to 20 carbon atoms substituted with tert-butoxy, and R 11 may be an alkyl group having 1 to 20 carbon atoms. Preferably, R 10 is tert-butoxy-hexyl, and R 11 may be methyl.
In addition, it is preferable that said A is silicone.
X may be halogen. Preferably, X may be chlorine.
As a preferable example of the metallocene compound represented by the said Formula (1), the compound represented by following formula (1a) is mentioned.
[Formula 1a]
(In Formula 1a,
A is an element of group 14,
R 10 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms,
R 11 is an alkyl group having 1 to 20 carbon atoms,
Each X is independently halogen)
Most preferably, the compound represented by Formula 1 may be a compound represented by Formula 1b.
[Formula 1b]
On the other hand, the compound of Formula 1 may be obtained using a ligand compound represented by the following formula (2).
[Formula 1]
(In Formula 2,
R 1 to R 9 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms,
R 10 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
R 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
A is silicon or carbon)
The ligand compound of Formula 2 has a symmetrical crosslinked structure in which two inindacene groups are connected to a silicon or carbon bridge in order to provide the structure of Formula 1 described above, and in particular, an alkyl group at a specific position of the indacene group, By introducing a functional group such as an alkoxy group, the ligand compound may exhibit high activity during olefin polymerization, and in particular, may provide a catalyst capable of producing a polyolefin having a high melting point and a low fine content.
In particular, the ligand compound of the embodiment has an electron donating effect because a tert-butyl group is bonded at the 3,5-position of phenyl together with phenyl which is a bulky group at a specific position of an indane group. Can be further enhanced to increase the electron density around the metal, thus exhibiting high activity during olefin polymerization.
In addition, the ligand compound includes a alkyl group having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms in the bridge group (indacene) linking group, of the metallocene compound comprising a ligand compound The supported yield can be increased, and the activity of the catalyst can also be increased.
Meanwhile, a preferable example of the ligand compound represented by Formula 2 may have a structure included in the substituent definition of Formula 1 described above.
That is, R 10 may be an alkyl group having 1 to 20 carbon atoms substituted with tert-butoxy, and R 11 may be an alkyl group having 1 to 20 carbon atoms. Preferably, R 10 is tert-butoxy-hexyl, and R 11 may be methyl. In addition, A may be silicon.
Meanwhile, the metallocene compound represented by Chemical Formula 1 and the ligand compound represented by Chemical Formula 2 may be synthesized by the same method as in Schemes 1 to 2, but is not limited thereto. The method for producing the compound represented by Formulas 1 and 2 will be described in more detail in the Examples to be described later.
Scheme 1
Scheme 2
In Schemes 1 and 2, A, R 1 to R 211 and X are the same as defined in the formula (1).
In addition, the ligand compound of Formula 2 may be a ligand compound capable of forming a chelate with the metal.
Specifically, as shown in Scheme 1, the metallocene compound represented by Formula 2 is a ligand compound of Formula 2 and Cl 2 AR 10 R 11 It can be formed by reacting a compound. It is preferable that the reaction conditions use alkyl lithium (for example, n-butyllithium), and reaction temperature is -200-0 degreeC, More preferably, it is -150-0 degreeC. Toluene, THF, etc. can be used as a solvent. At this time, after separating the organic layer from the product, the step of vacuum drying the separated organic layer and removing the excess reactant may be further performed.
In addition, as shown in Scheme 2, the metallocene compound represented by Formula 1 may be formed by reacting Formula 2 with a Cl 2 ZrX 2 compound. It is preferable to use the said reaction degree alkyllithium (for example, n-butyllithium), and reaction temperature is -200-0 degreeC, More preferably, it is -150-0 degreeC. Ether, hexane, etc. can be used as a solvent.
Further, according to another preferred embodiment of the present invention, a catalyst composition for olefin polymerization including the metallocene compound represented by Formula 1 may be provided.
Preferably, the catalyst composition may further include one or more selected from the group consisting of a carrier and a promoter. More preferably, the catalyst composition may include a metallocene compound of Formula 1, a promoter and a carrier.
In the present invention, the catalyst composition for olefin polymerization may mean a metallocene catalyst for olefin polymerization. Therefore, the metallocene catalyst may be a metallocene compound of Formula 1 itself, or may be in a form supported on the carrier together with the metallocene compound of Formula 1 or a promoter.
In this case, the compound of the formula (1) of the present invention can be effectively supported on the carrier in only two steps when supported on the carrier with the promoter, due to the structural characteristics. Therefore, the present invention does not need to go through the pre-polymerization process that must be preceded before the present polymerization, and can provide an olefin polymer having excellent activity and having a high molecular weight and a high melting point.
The cocatalyst is not particularly limited since the conventional one can be used in the art to which the present invention belongs, but preferably alkylaluminoxane having a linear or branched alkyl group having 1 to 10 carbon atoms can be used. Here, the alkyl aluminoxane may be at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane and isobutyl aluminoxane.
In addition, the catalyst composition may further include a solvent.
As the solvent, a solvent known to be usable in the catalyst composition for olefin polymerization can be used without particular limitation, and examples thereof include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene, xylene, benzene; Or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. The content of the solvent in the catalyst composition can be appropriately adjusted according to the characteristics of the catalyst composition used and the conditions of the production process of the olefin polymer to be applied.
The carrier is not particularly limited, since a conventional one can be used in the art to which the present invention pertains. Preferably, one or more carriers selected from the group consisting of silica, silica-alumina, and silica-magnesia may be used. In addition, the carrier may be used by drying at a high temperature.
On the other hand, when the compound of Formula 1 is supported on a carrier such as silica, since the silica carrier and the functional group of the compound of Formula 1 are supported by chemical bonding, there are almost no catalysts liberated from the surface in the olefin polymerization process, and thus slurry or gas phase polymerization is carried out. As a result, when the polyolefin is prepared, there may be less fouling phenomenon in which the reactor wall or polymer particles are entangled with each other.
Such carriers may be preferably silica dried at high temperature, silica-alumina and the like, and these are usually oxides, carbonates, sulfates, such as Na 2 O, K 2 CO 3 , BaSO 4 , Mg (NO 3 ) 2 , Nitrate components may be contained.
In the present invention, when the catalyst composition includes the carrier and the promoter, the amount thereof is not limited.
On the other hand, according to another preferred embodiment of the invention, in the presence of the catalyst composition for olefin polymerization, there may be provided a method for producing a polyolefin comprising the step of polymerizing an olefin monomer.
The polymerization reaction of the olefin monomer may be used without limitation, a polymerization process known to be used in the polymerization reaction of the olefin monomer, such as a continuous solution polymerization process, bulk polymerization process, suspension polymerization process, slurry polymerization process or emulsion polymerization process.
Examples of the olefin monomer polymerizable using the metallocene compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, and the like, and a diene olefin monomer or a triene olefin monomer having two or more double bonds. And the like can also be polymerized. Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, etc., These monomers may be mixed and copolymerized. When the polyolefin is a copolymer of ethylene and other comonomers, the monomer constituting the copolymer is one selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene It is preferable that it is the above comonomer.
Here, the polymerization conditions of the olefin may be carried out by reacting for 1 to 24 hours at a temperature of 25 to 500 ℃ and a pressure of 1 to 100 kgf / ㎠. At this time, 25-200 degreeC is preferable and, as for the said polymerization reaction temperature, 50-100 degreeC is more preferable. Moreover, 1-70 kgf / cm <2> is preferable and, as for the said polymerization reaction pressure, 5-40 kgf / cm <2> is more preferable. The polymerization reaction time is preferably 1 to 5 hours.
The polymerization process can control the molecular weight range of the resulting polymer product in accordance with hydrogenation or no addition conditions. In particular, a high molecular weight polyolefin can be produced under the condition that hydrogen is not added, and low molecular weight polyolefin can be produced even by adding a small amount of hydrogen when hydrogen is added. At this time, the hydrogen content added to the polymerization process is in the range of 0.07 L to 4 L under 1 atmosphere of the reactor conditions, or is supplied at a pressure of 1 bar to 40 bar or 168 ppm to 8,000 ppm in the hydrogen mole content range relative to the olefin monomer Can be.
Hereinafter, preferred embodiments of the present invention will be described in detail. However, these examples are only for illustrating the present invention, it will not be construed that the scope of the present invention is limited by these examples.
< Example >
(1) Ligand precursor (indacene) synthesis
8-Bromo-6-methyl-1,2,3,5-tetrahydro-s-indacene (39.9 mmol , 9.9 g), (3,5-di-tert-butylphenyl) boronic acid ((3,5-di- tert- butylphenyl) boronic acid) (60 mmol, 14 g), sodium carbonate (99.8 mmol , 10.6 g), tetrakisphenylphenylphosphine palladium (2.0 mmol, 2.3 g) was added to a 250 mL round bottom flask and toluene (40 mL), EtOH (20 mL), H 2 O (20 mL) was added. It was. And the mixture was stirred for 24 hours in an oil bath preheated to 90 ° C. The reaction was confirmed by NMR, and if the reaction proceeded less, the reaction was further performed for 16 hours, or the reactants except for indacene and solvent were further prescribed according to the amount of indacene remaining, followed by reaction for 16 hours.
After the reaction, all of the ethanol was removed from the rotary evaporator, work up with water and hexane. The organic layer was collected, dried over MgSO 4 , and all solvent was removed. The crude mixture from which the solvent was removed was subjected to silica gel short column to remove black impurities. The solvent was again removed, and methanol was added to give a solid. The resulting solid was filtered and washed with methanol to afford 8- (3,5-di- tert -butylphenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene (8- ( 3,5-di- tert- butylphenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene) (11.8 g, yield 82%, white solid) was obtained.
1 H NMR (500 MHz, in CDCl 3 ): δ 7.44-7.31 (m, 4H), 7.12 (s, 1H), 6.47 (s, 1H), 3.19 (s, 2H), 2.97 (t, 2H), 2.8 (t, 2H), 2.09-2.02 (m, 5H), 1.38 (s, 9H)
(2) Synthesis of Ligand Compound
8- (3,5-di- tert -butylphenyl) -6-methyl-1,2,3,5-tetrahydro-s-indenecene (23.15 mmol, 8.3 g), CuCN (1.16 mmol, 0.1 g) Was put in a 100mL shrink flask to make an Ar state. When Ar state was formed, anhydrous toluene (64 mL) and anhydrous THF (6.4 mL) were added and cooled to -25 ° C. n- BuLi (2.5 M in Hexane, 24.31 mmol, 9.72 mL) was slowly injected. After the injection was completed, the temperature was raised to room temperature, followed by stirring at room temperature for 3 hours. Tether silane (13.89 mmol, 3.8 g) was injected into the flask as one shot at room temperature and stirred for 16 hours. Worked up with methyl tert-butyl ether (MTBE) and water, and the organic layers were collected to remove the solvent.
Purified by column, ligand compound ((6- ( tert- butoxy) hexyl) bis (4- (3,5-di- ( tert- butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro- s-indacen-1-yl) (methyl) silane) (10 g, yield 96%, light yellow solid) was obtained.
1 H NMR (500MHz, in CDCl 3 ): δ7.37 ~ 7.18 (m, 8H), 6.61 ~ 6.59 (m, 2H), 3.72 (d, 2H), 3.25 ~ 3.24 (m, 2H), 2.97 ~ 2.87 (m, 9H), 2.36-0.45 (m, 64H), -0.10--0.13 (m, 3H)
(3) catalyst synthesis
The ligand compound (1.67 mmol, 1.53 g) was placed in a 100 mL shrink flask to prepare an Ar state. When Ar state was formed, anhydrous diethyl ether (33.3 mL) was added thereto, and the mixture was cooled to -25 ° C. After slowly injecting n- BuLi (2.5 M in Hexane, 3.68 mmol, 1.47 mL), the mixture was heated to room temperature and stirred at room temperature for 3 hours. After stirring, the Ark Schrink flask containing this solution and HfCl 4 (11.07 mmol, 3.55 g) was cooled to −78 ° C. and the ligand solution was transferred to a flask containing hafnium at low temperature. After slowly warming to room temperature, the mixture was stirred at room temperature for 16 hours. After stirring, the produced solid was removed by filtration in Ar state, and the solvent was dried to obtain a crude mixture. It is dissolved in a minimum amount of anhydrous toluene and stored at low temperature (-25 ° C) to form a solid. The resulting solid was loosened by addition of pentane and collected by filtration. The obtained solid was dried to obtain a clean catalyst (0.25 mmol, 0.27 g, yield 15%, yellow solid).
1 H NMR (500 MHz, in CDCl 3 ): δ 7.47-7.16 (m, 8H), 6.60 (s, 2H), 3.39-3.36 (m, 2H), 3.19-2.85 (m, 8H), 2.30 (d , 6H), 2.09-0.87 (m, 59H)
(4) Preparation of Supported Catalyst
Silica gel (L203F, 3 g) was added to a 250 mL shrink flask under Ar, and MAO (23 mL, 30 mmol) was slowly injected at room temperature, followed by stirring at 95 ° C. for 18 hours. After completion of the reaction, the mixture was cooled to room temperature and left for 15 minutes to decant the solvent using a cannula. Toluene (25 mL) was added thereto, stirred for 1 minute, and left for 20 minutes to decant the solvent using a cannula. The catalyst (180 μmol) was dissolved in toluene (20 mL), then transferred to the upper flask with cannula and washed with toluene (5 mL). After stirring for 5 hours at 75 ℃, it was cooled to room temperature and left for 15 minutes to decant the solvent using a cannula. Toluene (25 mL) was added thereto, stirred for 1 minute, and left to stand for 10 minutes to decant the solvent using a cannula. Hexane (25 mL) was added in the same manner, stirred for 1 minute, left for 20 minutes to decant the solvent using a cannula, and dried under vacuum overnight. It was further dried in vacuo at 45 ° C. for 4 hours.
< Comparative example >
(1) Synthesis of Dimethylbis (2-methyl-4-phenyl-1H-inden-1-yl) silane
To a 77 mL 2-methyl-4-phenylindene toluene / THF = 10/1 solution (49.5 mmol), 21.8 mL of n-butyllithium solution (2.5 M, hexane solvent) were slowly added dropwise at 0 ° C., followed by 1 at 80 ° C. After stirring for an hour, the mixture was stirred at room temperature for one day. Thereafter, 2.98 mL of dichloromethylsilane was slowly added dropwise at 0 ° C. or lower, stirred for about 10 minutes, and heated to 80 ° C. for 1 hour. Then, water was added to separate the organic layer, and the silica column was purified and dried in vacuo to give a sticky yellow oil in a yield of 61% (racemic: meso = 1: 1).
1 H NMR (500 MHz, CDCl 3 ): δ 0.02 (6H, s), 2.37 (6H, s), 4.00 (2H, s), 6.87 (2H, t), 7.83 (2H, t), 7.45 (2H , t), 7.57 (4H, d), 7.65 (4H, t), 7.75 (4H, d)
(2) Synthesis of Dimethylbis (2-methyl-4-phenyl-1H-inden-1yl) silane Zirconium dichloride
To a 240 mL dimethylbis (2-methyl-4-phenylindenyl) silane ether / hexane = 1/1 solution (12.4 mmol), 10.9 mL of n-butyllithium solution (2.5M in hexane) was slowly added dropwise at -78 ° C. . Thereafter, the mixture was stirred at room temperature for one day, filtered and dried in vacuo to give a pale yellow solid. Ligand salt and bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconiumbis (tetrahydrofuran) synthesized in a glove box were used in a Schlenk flask. After weighing), ether was slowly added dropwise at -78 ° C and stirred for 1 day at room temperature. The red solution was separated by filtration, dried in vacuo and a toluene / ether = 1/2 solution was added to obtain a clean red solution. 1.5-2 equivalents of HCl ether solution (1M) was slowly added dropwise at -78 ° C, followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, an orange solid catalyst was obtained in a yield of 70% (racemic only).
1 H NMR (500 MHz, C6D6, 7.24 ppm): δ1.32 (6H, s), 2.24 (6H, s), 6.93 (2H, s), 7.10 (2H, t), 7.32 (2H, t), 7.36 (2H, d), 7.43 (4H, t), 7.60 (4H, d), 7.64 (2H, d)
(3) Preparation of Supported Catalysts
In the same manner as in Step 3 of Example, a silica-supported metallocene catalyst was prepared using the metallocene compound synthesized above (Dimethylbis (2-methyl-4-phenyl-1H-inden-1yl) silane Zirconium dichloride). .
< Experimental Example >
1) Homopolymerization of propylene
The reaction was done under argon conditions using a 2L autoclave reactor. The polymerization reactor was heated to 80 ° C. and dried under vacuum for 30 minutes and then placed under argon conditions for 1 hour until it reached 30 ° C. At this time, the pressure inside the reactor was maintained at 5 bar. Triethylaluminum (TEAL) (3 mL) was injected without the reactor internal pressure and H 2 was injected at 100 cc / min if necessary. After injecting propylene (C 3 ) (770 g) and stirring for 10 minutes, each of the metallocene catalysts prepared in Examples and Comparative Examples was injected into the reactor with hexane (15 mL) and washed with hexane (5 mL). . The temperature inside the polymerization reactor was raised to 67 ° C. and the polymerization was carried out for 1 hour when it reached 70 ° C. After the reaction was completed, unreacted propylene was vented. At this time, according to the hydrogen injection amount, it was classified into Comparative Examples 1-2 and Examples 1-3.
2) Random Polymerization of Propylene
The reaction was done under argon conditions using a 2L autoclave reactor. The polymerization reactor was heated to 80 ° C., dried under vacuum for 30 minutes, and then purged with argon for 1 hour until it reached 30 ° C. At this time, the pressure inside the reactor was maintained at 5 bar. Triethylaluminum (TEAL) (3 mL) was injected without the reactor internal pressure and H 2 was injected at 100 cc / min if necessary. After injecting propylene (C 3 ) (770 g) and stirring for 10 minutes, the metallocene catalyst prepared in Example was injected into the reactor with hexane (15 mL) and washed with hexane (5 mL). The temperature inside the polymerization reactor was set at 67 ° C. and ethylene (C 2) was injected at 200 cc / min for 1 hour. The polymerization was carried out for 1 hour when the temperature inside the reactor reached 70 ℃. After the reaction was completed, unreacted propylene was vented. At this time, according to the hydrogen injection amount, it classified into Examples 4-6.
3) Measurement method of the physical properties of the polymer
a. Catalyst activity: calculated as the ratio of the weight of polymer produced (kg PP) per catalyst content (mmol and g of catalyst) used, based on unit time (h).
b. Melting point (Tm) of the polymer: The melting point of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 ° C. and then maintained at that temperature for 5 minutes, cooled to 20 ° C. again, and then increased in temperature, wherein the rate of rise and fall of the temperature were adjusted to 10 / min, respectively. .
c. Particle size distribution (PSD): After injecting the sample into the hopper of the optical diffraction particle size analyzer (HELOS), set the method in the range of 50 ~ 3500㎛, APS (Acerage Particle Size), Span value and 75㎛ or less ) Was checked.
d. Melt Flow Rate (MFR): Based on ASTM D-1238, measured under conditions of a load of 190 ° C. and 2.16 kg.
4) Measurement results of the physical properties of the polymer
The results of measuring the properties of the homo and random polymerization processes and the resulting polypropylene prepared using the respective metallocene supported catalysts prepared in Examples and Comparative Examples are shown in Tables 1 (homo polymerization) and Table 2 (random polymerization). ).
In Table 1, Examples 1 to 3, compared to Comparative Examples 1 and 2, can produce a polymer of high molecular weight and high Tm.
In Table 1, it can be seen that in Examples 4 to 6, polymers having high molecular weight, high Tm, and high C2 content (high polymerizability) can be prepared.
In addition, referring to the particle size distribution (PSD) measurement results, in the case of the metallocene compound prepared in Example, the chain structure bonded to silicon enables the catalyst to be effectively bonded to the carrier, compared to the catalyst without this chain structure. It can be seen that the generation of fine powder is significantly reduced, so that the polymerization process can be stably performed.
The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (10)
[Formula 1]
(In Formula 1,
R 1 to R 9 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms,
R 10 is an alkyl group having 1 to 20 carbon atoms substituted with tert-butoxy,
R 11 is an alkyl group having 1 to 20 carbon atoms,
A is silicon or carbon,
Each X is independently halogen or an alkyl group having 1 to 20 carbon atoms)
Wherein R 10 is tert-butoxy-hexyl and R 11 is methyl.
A is silicon metallocene compound.
[Formula 1a]
(In Formula 1a,
A is an element of group 14,
R 10 is an alkyl group having 1 to 20 carbon atoms substituted with tert-butoxy,
R 11 is an alkyl group having 1 to 20 carbon atoms,
Each X is independently halogen)
[Formula 1b]
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