KR20170009594A - 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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- C—CHEMISTRY; METALLURGY
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- 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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- 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
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
The present invention relates to a metallocene compound having a novel structure capable of exhibiting high reactivity in the olefin polymerization reaction and easily controlling the properties such as the internal structure and mechanical properties of the synthesized olefin polymer, And to a process for preparing an olefin polymer using the catalyst composition.
Description
The present invention relates to a metallocene compound having a novel structure capable of controlling the microstructure of an olefin-based polymer while having high activity, a catalyst composition containing the metallocene compound, and a process for producing an olefin polymer using the metallocene compound.
Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Although the Ziegler-Natta catalysts have high activity, they have a wide molecular weight distribution of the produced polymers because of their high activity, The uniformity of the composition is not uniform and there is a limit in ensuring desired physical properties.
Recently, a metallocene catalyst in which a transition metal such as titanium, zirconium, or hafnium and a ligand containing a cyclopentadiene functional group are bonded has been developed and widely used. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. These metallocene catalysts are single active site catalysts having one kind of active site. The molecular weight distribution of the produced polymer is narrow and the molecular weight, stereoregularity, crystallinity, especially reactivity of the comonomer can be greatly controlled depending on the structure of the catalyst and the ligand There is an advantage. However, since the polyolefin polymerized with the metallocene catalyst has a low melting point and a narrow molecular weight distribution, it is difficult to apply the polyolefin in a field where the productivity is remarkably decreased due to the influence of the extrusion load, I have done a lot of effort to adjust.
In particular, in order to solve the problems of the above-mentioned metallocene catalysts, many metallocene compounds coordinated with a ligand compound containing a hetero atom have been introduced. Specific examples of such a metallocene compound containing a hetero atom include an azaferrocene compound having a cyclopentadienyl group containing a nitrogen atom, a functional group such as a dialkylamine is connected to a cyclopentadienyl group as an additional chain Or a titanium (lV) metallocene compound into which a cyclic alkylamine functional group is introduced such as piperidine, and the like.
However, among all of these attempts, the metallocene catalysts that are actually applied to commercial plants are only a few levels, and the anthra-metallocene compounds capable of controlling the microstructure of the olefinic polymer, Research is still needed.
The present invention is to provide a ligand compound and a metallocene compound having a novel structure capable of controlling the microstructure of an olefin-based polymer while having high activity.
The present invention also provides a catalyst composition comprising the metallocene compound.
The present invention also provides a process for producing an olefin polymer using the catalyst composition.
The present invention provides a ligand compound represented by the following general formula (1).
The present invention also provides a metallocene compound represented by the following general formula (2).
The present invention also provides a catalyst composition comprising the metallocene compound.
In addition, the present invention provides a process for preparing an olefin polymer using the catalyst composition.
Hereinafter, a ligand compound, a metallocene compound, a catalyst composition, and a method for producing an olefin polymer using the same according to a specific embodiment of the present invention will be described in detail.
According to one embodiment of the present invention, a ligand compound represented by the following formula (1) may be provided.
[Chemical Formula 1]
In Formula 1,
R 1 to R 11 each independently represent 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, 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 12 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms,
R 13 is hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,
A is silicon or carbon.
The present inventors have found that by virtue of the inherent chemical structure of the ligand compound of Formula 1, the electronic / stereoscopic environment around the transition metal that can be bonded thereto can be easily controlled, and the microstructure and mechanical properties of the synthesized polyolefin It is possible to provide a metallocene catalyst capable of easily controlling the characteristics of the catalyst.
The ligand compound of Formula 1 has a symmetrical cross-linking structure in which two indacene groups are connected by a silicon or carbon bridge. Particularly, a functional group such as an alkyl group or an alkoxy group is introduced at a specific position of the indacene group, The ligand compound can provide a catalyst capable of exhibiting high activity during olefin polymerization, and particularly capable of producing a polyolefin having a high melting point and a small amount of a fine powder.
In particular, the ligand compound of this embodiment has a bulky group of phenyl attached to a specific position of the indacene group, so that the electron donating effect is enhanced to improve the electron density around the metal And thus can exhibit high activity during olefin polymerization.
Further, the ligand compound may be a metallocene compound containing a ligand compound, wherein the ligand compound includes an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy of 1 to 20 carbon atoms in a bridge group connecting an indacene group The supported yield can be increased, and the activity of the catalyst can be increased.
Each of the substituents defined in Formula 1 will be described in detail 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 each include a straight chain or branched chain alkenyl group and an alkynyl group.
The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms. Specific examples thereof include phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, and anisole. However, the aryl group is not limited thereto.
The alkylaryl group means an aryl group having at least one straight or branched alkyl group having 1 to 20 carbon atoms, and the arylalkyl group means a straight or branched alkyl group having at least one aryl group having 6 to 20 carbon atoms introduced thereto.
The halogen group means fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
In the ligand compound of this embodiment, R 2 , R 3 and R 4 each independently may be hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen, methyl or tert-butyl.
The R 10 may be an alkyl group having 1 to 10 carbon atoms, preferably methyl.
R 12 is preferably tert-butoxy-hexyl, and A is preferably silicon.
Meanwhile, preferred examples of the ligand compound represented by the formula (1) include, but are not limited to, compounds represented by one of the following structural formulas:
The compound represented by the formula (1) can be synthesized by the following reaction scheme 1, but is not limited thereto. The method for preparing the compound represented by the formula (1) will be described in more detail in the following examples.
[Reaction Scheme 1]
In the above Reaction Scheme 1, the definitions of R 1 to R 13 and A are the same as those in Formula 1 above.
The compound represented by formula (I) prepared according to the above method may be a ligand compound capable of forming a chelate with a metal.
According to another embodiment of the present invention, a metallocene compound represented by the following general formula (2) may be provided.
(2)
In Formula 2,
R 1 to R 11 each independently represent 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, 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 12 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms,
R 13 is hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,
A is silicon or carbon,
Each X independently represents a halogen or an alkyl group having 1 to 20 carbon atoms.
The present inventors have found that the electronic / stereoscopic environment around the transition metal can be easily controlled owing to the chemical structure of the metallocene compound of Formula 2 wherein a ligand compound of a specific structure is bonded to the transition metal, Microstructure, mechanical properties, and the like can be easily controlled.
As described above, the metallocene compound of Formula 2 has a symmetrical cross-linking structure in which two indacene groups are connected by a silicon or carbon bridge. In particular, the metallocene compound of Formula 2 has an alkyl group, an alkoxy group And the like. The metallocene compound can exhibit high activity when polymerizing olefin, and can produce a polyolefin having a high melting point and a small amount of a fine powder.
As described above, in the metallocene compound of this embodiment, R 2 , R 3, and R 4 may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen, -Butyl.
The R 10 may be an alkyl group having 1 to 10 carbon atoms, preferably methyl.
R 12 is preferably tert-butoxy-hexyl, and A is preferably silicon.
Meanwhile, preferred examples of the metallocene compound represented by Formula 2 include, but are not limited to, compounds represented by one of the following structural formulas:
The metallocene compound represented by Formula 2 may be formed by reacting the ligand compound of Formula 1 with a metallocene compound. Specifically, the metallocene compound represented by Formula 2 may be synthesized by the following reaction scheme 2, but is not limited thereto. The method for preparing the compound represented by the above formula (2) will be described in more detail in the following examples.
[Reaction Scheme 2]
In the above Reaction Scheme 2, the definitions of R 1 to R 13 and A are the same as defined in the above formula (1), and X is a halogen or an alkyl group having 1 to 20 carbon atoms.
According to another embodiment of the present invention, there can be provided a catalyst composition for olefin polymerization comprising the metallocene compound represented by Formula 2 and the cocatalyst.
The cocatalyst is not particularly limited as it is customary in the art to which the present invention belongs, but alkyl aluminoxane may be preferably used, and silica, silica-alumina, organoaluminum compound and the like may be further included. When such a cocatalyst is used, X may be used as a catalyst in which X bonded to a metal element of the compound represented by Formula 2 is substituted with an alkyl group, for example, C 1-20 alkyl.
The catalyst composition may include a metallocene compound represented by Formula 2; And cocatalyst; In addition, a solvent may be further included.
As the solvent, any solvent known to be usable in the catalyst composition for olefin polymerization may be used without limitation, for example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene, xylene and benzene; Or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. The content of the solvent in the catalyst composition may be appropriately controlled depending on the characteristics of the catalyst composition used and the conditions of the production process of the olefin polymer to be used.
The catalyst for olefin polymerization may be a catalyst supported on a support. The carrier may be any of those generally used in the technical field to which the present invention belongs, so that it is not particularly limited, but preferably at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia may be used.
On the other hand, when supported on a support such as silica, since the silica carrier and the functional group of the compound represented by Chemical Formula 2 are chemically bonded and supported, there is almost no catalyst liberated from the surface in the olefin polymerization process, and thus polyolefin The fouling phenomenon of the wall surface of the reactor or the polymer particles tangling with each other may be small.
As such a carrier, silica, silica-alumina and the like, which are dried at a high temperature, may be preferably used. These carriers are usually oxides such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg (NO 3 ) 2 , A nitrate component may be included.
According to another embodiment of the present invention, there is also provided a process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition.
As described above, the metallocene compound of the above formula (2) can easily control the electronic / stereoscopic environment around the metal, so that the characteristics such as the internal structure and the mechanical properties of the synthesized polyolefin can be easily controlled.
The polymerization reaction of the olefin monomer can be used without limitation, such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization slurry polymerization process, or an emulsion polymerization process, which is known to be used for polymerization of olefin monomers.
Examples of olefin monomers that can be polymerized using the metallocene compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, etc., and diene olefin monomers or triene olefin monomers having two or more double bonds Can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized. When the polyolefin is a copolymer of ethylene and another comonomer, the monomer constituting the copolymer is selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl- Or more of the comonomer.
Here, the polymerization of the polyolefin can be carried out by reacting at a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm 2 for 1 to 24 hours. At this time, the polymerization reaction temperature is preferably 25 to 200 ° C, more preferably 50 to 100 ° C. The polymerization reaction pressure is preferably 1 to 70 kgf / cm 2, and more preferably 5 to 40 kgf / cm 2. The polymerization reaction time is preferably 1 to 5 hours.
The polymerization process can control the molecular weight range of the finally produced polymer product according to the hydrogenation or not added conditions. In particular, a polyolefin having a high molecular weight can be produced under a condition that hydrogen is not added, and a low molecular weight polyolefin can be produced even with a small amount of hydrogen addition by adding hydrogen. At this time, the hydrogen content added to the polymerization process is 0.07 L to 4 L under 1 atm of the reactor condition, or is supplied at a pressure of 1 bar to 40 bar or in a range of 168 ppm to 8,000 ppm in terms of the molar amount of hydrogen relative to the olefin monomer .
According to the present invention, a ligand compound, a metallocene compound, a catalyst composition containing the metallocene compound and the like, which can easily exhibit high reactivity in the olefin polymerization reaction and can easily control the properties such as the internal structure and mechanical properties of the produced olefin polymer A method for producing an olefin polymer using the catalyst composition may be provided.
The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
In the following Examples, Comparative Examples and Experimental Examples, organic reagents and solvents were purchased from Aldrich and Merck and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment.
≪ Example: Synthesis of ligand compound and metallocene compound >
(1) Synthesis of 8- (4- ( tert- butyl) phenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene
8-Bromo-6-methyl- 1,2,3,5-tetrahydro-s-indacene (35mmol, 9.8g), (4- (tert -butyl) phenyl) boronic acid (70mmol, 12.5g), sodium carbonate ( 87.50 mmol, 9.3 g) and tetrakistriphenylphosphine palladium (1.80 mmol, 2 g) were placed in 250 mL RBF, and toluene (35 mL), ethanol (18 mL) and water (1 mL) were added. Then, the mixture was stirred in an oil bath preheated to 90 DEG C for 16 hours. The reaction was allowed to proceed for 16 hours if the reaction was less progressive, or the reaction was allowed to proceed for 16 hours after addition of indacene and solvent except for the solvent to the remaining indacene. When the reaction was complete, remove all of the ethanol from the rotary evaporator and work up with water and hexane. Combined organic layers were dried over MgSO 4 and remove all the solvent. The crude mixture, from which the solvent was removed, was subjected to silica gel short column to remove black impurities. Again, the solvent was removed and methanol was added to produce a solid. The resulting solid was filtered and washed with methanol to give 8.5 g (80%, white solid) of 8- (4- ( tert- butyl) phenyl) -6- ≪ / RTI >
1 H NMR (500MHz, in CDCl 3): 7.44 ~ 7.31 (m, 4H), 7.12 (s, 1H), 6.47 (s, 1H), 3.19 (s, 2H), 2.97 (t, 2H), 2.09 ~ 2.02 (m, 5 H), 1.38 (s, 9 H)
(2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Synthesis of (methyl) silane ligand
8- (4- (tert -butyl) phenyl ) -6-methyl-1,2,3,5-tetrahydro-s-indacene (16.40mmol, 5g), CuCN (0.82mmol, 0.07g) in a 100mL Schlenk flask And made an argon state. When the argon state was established, anhydrous toluene (45 mL) and anhydrous THF (5 mL) were added and cooled to -25 ° C. n- BuLi (2.5 M in Hexane, 18 mmol, 7.23 mL) was slowly poured into the flask, and after the injection was completed, the temperature was raised to room temperature and stirred for 3 hours. Tether silane (7.80 mmol, 2.1 g) was then poured into the flask at room temperature with one shot and stirred for 16 hours. Work up with MTBE and water and collect organic layers to remove solvent. The title compound was prepared in a manner similar to that described for the synthesis of (6- (tert-butoxy) hexyl) bis (4- (4- (tert- butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro-s- indacen- methyl) silane ligand (4 g, 64%, light yellow solid).
1 H NMR (500MHz, in CDCl 3): 7.45 ~ 7.34 (m, 8H), 7.26 (s, 1H), 7.19 (s, 1H), 3.70 ~ 3.65 (m, 2H), 3.26 ~ 3.24 (m, 2H ), 2.97-2.83 (m, 8H), 2.17-2.03 (m, 10H), 1.53-0.44 (m, 30H)
(3) (6- (tert-butoxy) hexyl) bis (4- (4- (tert- butyl) phenyl) -2-methyl- 1,5,6,7-tetrahydro- (methyl) silane Synthesis of Zirconium Metallocene Compound
(6- (tert-butoxy) hexyl) bis (4- (4- (tert-butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro- silane ligand (1.24 mmol, 1 g) was placed in a 50 mL Schlenk flask to form an argon state. When the argon state is established, anhydrous diethyl ether (25 mL) is added and cooled to -25 ° C. n- BuLi (2.5 M in Hexane, 2.73 mmol, 1.1 mL) was slowly injected. When the injection was completed, the temperature was raised to room temperature and stirred for 3 hours. After the stirring, the solution and a Schlenk flask containing argon (ZrCl 4 -2 (THF) (1.24 mmol, 0.47 g) in argon were cooled to -78 ° C. and the ligand solution was transferred at a low temperature into a flask containing zirconium . After slowly warming to room temperature, the mixture was stirred for 16 hours. After stirring, the resulting solid was filtered off with argon, and the solvent was evaporated to obtain a crude mixture. This was dissolved in a minimum amount of anhydrous toluene and stored at -25 ° C to -30 ° C to form a solid. The resulting solid was dissolved by adding excess amount of hexane at a low temperature and then filtered to collect. The obtained solid was dried to obtain a clean catalyst (6- (tert-butoxy) hexyl) bis (4- (tert- butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro- indacen-1-yl) (methyl) silane Zirconium (0.26 mmol, 0.25 g, 21%, yellow solid).
1 H NMR (500MHz, in CDCl 3): 7.49 ~ 7.33 (m, 10H), 6.70 (s, 2H), 3.39 ~ 3.36 (m, 2H), 3.04 ~ 2.80 (m, 8H), 2.21 (d, 6H ), 2.03-1.14 (m, 34H), 0.90-0.87 (m, 3H)
(4) Preparation of supported catalyst
Silica gel (3 g) was placed in a 250 mL Schlenk flask under argon and methylaluminoxane (MAO; 23 mL, 30 mmol) was slowly added at room temperature and stirred at 95 ° C for 18 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (25 mL) was added, stirred for 1 minute, left to stand for 20 minutes, and the solvent was decanted with a cannula. Then, the metallocene compound (180 μmol) prepared in the above (3) was dissolved in toluene (20 mL), and the flask was transferred using a cannula and washed with toluene (5 mL). After stirring at 75 ° C for 5 hours, the mixture was cooled to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (25 mL) was added, stirred for 1 minute, left for 10 minutes, and the solvent was decanted with a cannula twice. In the same manner, hexane (25 mL) was added, stirred for 1 minute, left to stand for 20 minutes, the solvent was decanted with a cannula and dried under vacuum overnight. Lt; RTI ID = 0.0 > 45 C < / RTI > for 4 hours.
<Comparative Example>
(1) Synthesis of Dimethylbis (2-methyl-4-phenyl-1H-inden-1-yl) silane
21.8 mL of a n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 2-methyl-4-phenylindene toluene / THF = 10/1 solution (49.5 mmol) at 0 ° C, And the mixture was stirred at room temperature for one day. Thereafter, 2.98 mL of dichloromethylsilane was slowly added dropwise at 0 DEG C or lower, stirred for about 10 minutes, then heated to 80 DEG C and stirred for 1 hour. The organic layer was separated by adding water, and the silica column was purified and vacuum dried to obtain a sticky yellow oil in a yield of 61%.
1 H NMR (500MHz, CDCl 3 , 7.24ppm): 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
(2) Synthesis of Dimethylbis (2-methyl-4-phenyl-1H-inden-1yl) silane Zirconium dichloride
10.9 mL of a n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 240 mL of a dimethyl bis (2-methyl-4-phenylindenyl) silane ether / hexane = 1/1 solution (12.4 mmol) . Thereafter, the mixture was stirred at room temperature for one day, filtered and vacuum dried to obtain a pale yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichloro zirconium bis (tetrahydrofuran) were dissolved in a Schlenk flask ), Ether was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for one day. The red solution was separated by filtration, dried in vacuo, and a toluene / ether = 1/2 solution was added to obtain a clear red solution. 1.5-2 equivalent of HCl ether solution (1M) was slowly added dropwise at -78 deg. C, followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, the catalyst of orange solid component was obtained in a yield of 70% (racemic only).
1 H NMR (500MHz, C6D6, 7.24ppm): 1.32 (6H, s), 2.24 (6H, s), 6.93 (2H, s), 7.10 (2H, t), 7.32 (2H, t), 7.36 (2H , 7.43 (4H, t), 7.60 (4H, d), 7.64 (2H, d)
<Experimental Example>
(1) homopolymerization of propylene
The reaction was carried out under argon conditions using a 2 L autoclave reactor. The polymerization reactor was heated to 80 DEG C, dried under vacuum for 30 minutes, and then placed under argon conditions for 1 hour until 30 DEG C was reached. At this time, the pressure inside the reactor was maintained at 5 bar. The pressure inside the reactor was removed, TEAL (3 mL) was injected, and H 2 was injected at 100 cc / min if necessary. C 3 (770 g) and stirred for 10 minutes. Then, the metallocene catalysts prepared in Examples and Comparative Examples were injected into the reactor with Hex (15 mL) and washed with Hex (5 mL). The internal temperature of the polymerization reactor was raised to 67 캜, and when the temperature reached 70 캜, the polymerization was carried out for 1 hour. After the completion of the reaction, unreacted propylene was bubbled.
(2) Random polymerization of propylene
The reaction was carried out under argon conditions using a 2 L autoclave reactor. The polymerization reactor was heated to 80 DEG C, dried under vacuum for 30 minutes, and then purged with argon for 1 hour until the temperature reached 30 DEG C. [ At this time, the pressure inside the reactor was maintained at 5 bar. The pressure inside the reactor was removed, TEAL (3 mL) was injected, and H 2 was injected at 100 cc / min if necessary. C 3 (770 g) and stirred for 10 minutes. Then, the metallocene catalysts prepared in Examples and Comparative Examples were injected into the reactor with Hex (15 mL) and washed with Hex (5 mL). The internal temperature of the polymerization reactor was set at 67 DEG C and C2 was injected at 200 cc / min for 1 hour. When the internal temperature of the reactor reached 70 DEG C, the polymerization was carried out for 1 hour. After the completion of the reaction, unreacted propylene was bubbled.
(3) Method of measuring physical properties of polymer
1) Catalytic activity: Calculated as the ratio of the weight of polymer produced (kg PP) per unit time (h) to the catalyst content (mmol and g of catalyst) used.
2) Melting point (Tm) of polymer: The melting point of the polymer was measured using a differential scanning calorimeter (DSC, DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 ° C., and then the temperature was maintained for 5 minutes. After the temperature was further cooled to 20 ° C., the temperature was increased again. The temperature rising rate and the falling rate were adjusted to 10 ° C./min Respectively.
3) Particle size distribution (PSD)
After injecting the sample into a hopper with a light diffraction particle size analyzer (Symatec HELOS), the APS (Acerage Particle Size), the span value, and the content of 75 μm or less (fine powder) were confirmed by setting the method in the range of 50 to 3500 μm.
(4) Measurement results of physical properties of polymer
The homo and random polymerization process conditions and physical properties of polypropylene produced using the metallocene supported catalysts prepared in Examples and Comparative Examples were measured and the results are shown in Table 1 (homopolymerization) and Table 2 ).
As shown in Tables 1 and 2, the metallocene compound having a specific substituent group in the indascene group and the bridge group as the supported catalyst according to this embodiment exhibited substantially higher activity in the production of the polyolefin , And it was confirmed that the homopolypropylene prepared in Examples 1 to 3 had a melting point higher than 153 ° C.
Further, referring to the result of the particle size distribution (PSD) measurement, in the case of the metallocene compound produced in the examples, the chain structure bonded to the silicon enables the catalyst to be effectively bonded to the carrier, It can be confirmed that the generation of fine particles is remarkably reduced and the polymerization process can be stably performed.
Claims (11)
[Chemical Formula 1]
In Formula 1,
R 1 to R 11 each independently represent 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, 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 12 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms,
R 13 is hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,
A is silicon or carbon.
R 2 , R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
Wherein R 10 is a ligand compound, characterized in that the alkyl group having 1 to 10 carbon atoms.
Wherein A is silicon.
Wherein R 3 is tert-butyl, R 12 is tert-butoxy-hexyl, and R 10 is methyl.
The compound represented by Formula 1 is a ligand compound having one of the following formulas:
(2)
In Formula 2,
R 1 to R 11 each independently represent 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, 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 12 is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms,
R 13 is hydrogen, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,
A is silicon or carbon,
Each X independently represents a halogen or an alkyl group having 1 to 20 carbon atoms.
Wherein R 2 , R 3 and R 4 are each independently hydrogen, methyl or tert-butyl, R 12 is tert-butoxy-hexyl and R 10 is methyl.
The compound represented by Formula 2 is a metallocene compound having one of the following formulas:
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