KR102011927B1 - Catalyst composition and method for preparing polyolefin using the same - Google Patents
Catalyst composition and method for preparing polyolefin using the same Download PDFInfo
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- KR102011927B1 KR102011927B1 KR1020150018103A KR20150018103A KR102011927B1 KR 102011927 B1 KR102011927 B1 KR 102011927B1 KR 1020150018103 A KR1020150018103 A KR 1020150018103A KR 20150018103 A KR20150018103 A KR 20150018103A KR 102011927 B1 KR102011927 B1 KR 102011927B1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
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Abstract
The present invention relates to a catalyst composition comprising a binuclear metallocene compound having a high molecular weight and a wide molecular weight distribution and capable of polymerizing a high quality polyolefin having excellent productivity, and a method for producing a polyolefin using the same.
Description
The present invention relates to a catalyst composition and a method for producing a polyolefin using the same. More specifically, the present invention relates to a catalyst composition comprising a dinuclear metallocene compound having a novel structure capable of producing a polyolefin having a high molecular weight and a wide molecular weight distribution, and a method for producing a polyolefin using the same.
The Ziegler-Natta catalyst widely applied to the existing commercial processes is characterized by a wide molecular weight distribution of the produced polymer because it is a multi-site catalyst, and the composition of the comonomer is not uniform, thereby limiting the desired physical properties.
Metallocene catalysts, on the other hand, are single-site catalysts with one type of active site, which have a narrow molecular weight distribution of polymers and greatly control the molecular weight, stereoregularity, crystallinity, and especially the reactivity of comonomers, depending on the structure of the catalyst and ligand. There are advantages to it. However, the polyolefin polymerized with a metallocene catalyst has a narrow molecular weight distribution, so when applied to some products, there is a problem that it is difficult to apply in the field, such as productivity is significantly reduced due to the extruded load, etc. I've done a lot.
To this end, methods using mononuclear metallocene compounds and dinuclear metallocene compounds are known.
For example, for mononuclear metallocene compounds, US Pat. No. 5,032,562 describes a process for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. It is a method of producing a bimodal distribution polymer by supporting a titanium (Ti) -based Ziegler-Natta catalyst that generates a high molecular weight and a zirconium (Zr) -based metallocene catalyst that produces a low molecular weight on one support As a result, the supporting process is complicated, and the morphology of the polymer is degraded due to the promoter.
In addition, studies have been made to change the copolymer selectivity, activity, etc. of the catalyst when copolymerizing using a heteronuclear metallocene compound. Some metallocene catalysts have increased copolymer incorporation and activity. Reported.
For example, Korean Patent Application No. 2003-12308 discloses a method of controlling molecular weight distribution by supporting a dual nucleus metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. Is starting. However, this method is limited in realizing the characteristics of each catalyst at the same time, and also has the disadvantage of freeing the metallocene catalyst portion in the carrier component of the finished catalyst, causing fouling in the reactor.
In addition, a synthesis method of a Group 4 metal metallocene catalyst having a biphenylene bridge and polymerization of ethylene and styrene using the catalyst have been reported (Organometallics, 2005, 24, 3618). According to the method, the activity of the catalyst is higher than that of the mononuclear metallocene catalyst and the molecular weight of the obtained polymer is described. Another method has been reported that the bridge structure of the Group 4 heteronuclear metallocene catalyst can be changed to change the reactivity of the catalyst (Eur. Polym, J. 2007, 43, 1436).
However, using the above methods, in the case of the Group 4 metal metallocene catalyst having a biphenylene bridge previously reported, there is a problem in the addition of substituents and the change of the structure. Development is needed.
In order to solve the above problems, an object of the present invention is to provide a catalyst composition comprising a dinuclear metallocene compound of a novel structure.
In another aspect, the present invention is to provide a method for producing a polyolefin using the catalyst composition.
In order to solve the above problems, an aspect of the present invention provides a catalyst composition comprising a binuclear metallocene compound represented by the following formula (1).
[Formula 1]
In Chemical Formula 1,
R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X is a halogen atom;
n is an integer from 1 to 10;
m is an integer of 0 or 1.
The present invention also provides a method for producing a polyolefin comprising the step of polymerizing at least one or more olefin monomers in the presence of the catalyst composition.
By using the catalyst composition comprising a binuclear metallocene catalyst according to the present invention, it is possible to exhibit high activity while maintaining the advantages of other homogeneous catalysts when producing polyolefins.
In addition, the catalyst of the present invention can freely adjust the molecular weight and molecular weight distribution, thereby producing a high quality polyolefin having high molecular weight and wide molecular weight distribution and excellent productivity.
The dinuclear metallocene compound of the present invention is a dinuclear metallocene compound having a novel structure, and the catalyst composition including the dinuclear metallocene compound can produce a polyolefin having a desired physical property and a molecular weight distribution.
In addition, according to the polyolefin production method of the present invention, it is possible to polymerize a polyolefin having a high molecular weight and a wide molecular weight distribution by using the catalyst composition comprising the heteronuclear metallocene compound.
Hereinafter, the present invention will be described in detail.
According to one aspect of the invention, there is provided a catalyst composition comprising a binuclear metallocene compound of formula (1).
The catalyst composition according to one embodiment of the present invention may be a composition including a dinuclear metallocene compound represented by Chemical Formula 1 and a promoter.
Alternatively, the catalyst composition according to another embodiment of the present invention may be a composition including a mononuclear metallocene compound of Formula 2 and a linker compound represented by Formula 3 and a promoter.
[Formula 1]
In Chemical Formula 1,
R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X is a halogen atom;
n is an integer from 1 to 10;
m is an integer of 0 or 1.
[Formula 2]
[Formula 3]
In Chemical Formula 2,
R1 to R10, Q, X and m are as defined in Formula 1,
In Formula 3, Z is Cl or Br, n is 1 to 10.
In the present invention, "catalyst composition" means three components of the mononuclear metallocene compound of Formula 2, a linker compound and a promoter or alternatively, two components of the dinuclear metallocene compound of Formula 1 and the promoter of By the same time or in any order, in the presence or absence of any suitable solvent, in the presence or absence of monomers is meant a state which can be obtained as an active composition.
That is, the catalyst composition according to the present invention may include a mononuclear metallocene compound of Formula 2, a linker compound of Formula 3, and a cocatalyst, or may include a binuclear metallocene and a promoter of Formula 1 . Even when the catalyst composition comprises the mononuclear metallocene compound, the linker compound and the cocatalyst, the substantial olefin polymerization reaction may be performed by the binuclear metallocene compound produced by the reaction of the mononuclear metallocene compound with the linker compound. Can be.
The three components or two components of the catalyst composition may be used without being supported on a carrier, or may be supported and used on a carrier as necessary.
According to one embodiment of the present invention, the dinuclear metallocene compound of the present invention may be represented by the following Chemical Formula 1.
[Formula 1]
In Chemical Formula 1,
R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X is a halogen atom;
n is an integer from 1 to 10;
m is an integer of 0 or 1.
The dinuclear metallocene compound of Formula 1 includes Zr as two center metals in a structure, and a ligand linked to each center metal has two cyclopentadiene group skeletons bonded or bridged thereto It is a compound having no structure. In addition, the dinuclear metallocene compound of Chemical Formula 1 of the present invention may exhibit stable catalytic activity by providing a spacing with an alkyl chain between the center metals in order to reduce the interaction of the two center metals.
According to an embodiment of the present invention, in the dinuclear metallocene compound of Chemical Formula 1, R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. It may be an amine group, or two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings. In addition, R9 and R10 may be each independently hydrogen, alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, X is Cl, n may be an integer of 2 to 6.
Also, m may be an integer of 0 or 1, and when m is 0, it means that two cyclopentadiene group skeletons are not connected, and when m is 1, a structure connected by a -Q (R9R10)-bridge is represented. Indicates.
More preferably, the dinuclear metallocene compound of Formula 1 may be represented by one of the structural formulas of Formulas 1a to 1e, but is not limited thereto.
[Formula 1a]
[Formula 1b]
[Formula 1c]
[Formula 1d]
[Formula 1e]
According to an embodiment of the present invention, the dinuclear metallocene compound of Chemical Formula 1 is a compound of Chemical Formula 2 by reacting a compound of Chemical Formula 2 with a linker compound of Chemical Formula 3 at a molar ratio of 2: 1. It can be prepared by the method of connecting the central metal (Zr) with an alkyl chain.
[Formula 2]
[Formula 3]
In Formula 2, R1 to R10, Q, X and m are as defined in Formula 1, Z in Formula 3 is Cl or Br, n is 1 to 10.
Since the reaction for the preparation of the binuclear metallocene compound of Chemical Formula 1 may use a conventional organic synthesis method well known in the art, the conditions are not particularly limited, and will be described in more detail in the following Examples.
In addition, since the reaction for the preparation of the mononuclear metallocene compound of Chemical Formula 2 may use a conventional organic synthesis method well known in the art, the conditions are not particularly limited, and the embodiment will be described in detail below. do.
The dinuclear metallocene compound represented by Chemical Formula 1 prepared in this manner has a novel structure, and the ligand structure included therein includes cyclopentadienyl or a derivative skeleton thereof.
In addition, an alkyl chain bonded between the center metals of the two metallocene compounds acts as a linker that connects the metal centers of the respective metallocene compounds, thereby reducing unnecessary interactions between the metals, thereby providing stable binuclear metals. It has the properties of rosene and easy to modify the ligand structure.
The cocatalyst which may be included in the catalyst composition of the present invention is not particularly limited as long as it is an organometallic compound including a Group 13 metal, and can be used when polymerizing an olefin under a general metallocene catalyst.
Preferably, the promoter may be used one or more selected from the group consisting of compounds represented by the formula (4) to (6).
[Formula 4]
-[Al (R 11 ) -O] c-
In Formula 4, R 11 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more. ,
[Formula 5]
D (R 12 ) 3
In Chemical Formula 5,
D is aluminum or boron, R 12 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[Formula 6]
[LH] + [ZA 4] - or [L] + [ZA 4] -
In Chemical Formula 6,
L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, A may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.
Examples of the compound represented by Formula 4 include methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like.
Examples of the alkyl metal compound represented by Formula 5 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum and diethyl. Chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p- Tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.
As the compound represented by the formula (6), for example, triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p -Tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium Tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethyl phosph Nium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium Umtetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl Aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetra Pentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetra Phenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, etc. have.
The catalyst composition according to the present invention comprises the steps of 1) contacting a metallocene compound represented by Formula 1 with a compound represented by Formula 4 or Formula 5 to obtain a mixture; And 2) it may be prepared by a method comprising the step of adding a compound represented by the formula (6) to the mixture.
In addition, the catalyst composition according to the present invention may be prepared by contacting the metallocene compound represented by Chemical Formula 1 with the compound represented by Chemical Formula 4 as a second method.
In the first method of preparing the catalyst composition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 or Chemical Formula 5 is preferably 1 / 5,000 to 1/2, More preferably, it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 4 or Chemical Formula 5 is more than 1/2, the amount of alkylating agent is so small that the alkylation of the metal compound does not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of Chemical Formula 6.
In addition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 6 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 /. 5 to 1. When the molar ratio of the metallocene compound represented by Chemical Formula 1 / compound represented by Chemical Formula 6 is greater than 1, the amount of the activator is relatively small, so that the activation of the metal compound may not be completed. If the activity is inferior, and if the molar ratio is less than 1/25, the activation of the metal compound is completely made, but the excess of the activator, the cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior .
In the second method of the method for preparing the catalyst composition, the molar ratio of the metallocene compound represented by Chemical Formula 1 / Compound 4 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000-1/100, most preferably 1 / 3,000-1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, resulting in a decrease in the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.
In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used. The metallocene compound and the cocatalyst compound can also be used in the form of silica or alumina.
The present invention also provides a method of polymerizing a polyolefin comprising the step of polymerizing an olefinic monomer in the presence of the catalyst composition.
In the method for producing a polyolefin according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, and these may be mixed and copolymerized.
The polyolefin is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.
In the case where the polyolefin is an ethylene / alpha olefin copolymer, the content of the alpha olefin which is the comonomer is not particularly limited and may be appropriately selected according to the use, purpose, and the like of the polyolefin. More specifically, it may be about 1 to about 99 mol%.
The polymerization reaction may be performed by homopolymerizing one olefin monomer or copolymerizing two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
According to one embodiment of the invention, the polymerization of the polyolefin may be carried out by reacting for about 10 minutes to about 2 hours at a temperature of about 20 to about 110 ℃ and a pressure of about 20 to about 100 bar. Preferably the reaction can be carried out at a temperature of about 80 to about 100 ° C and a pressure of about 30 to about 60 bar.
The polyolefin prepared by the production method of the present invention has a weight average molecular weight of about 5,000 to about 500,000, preferably about 10,000 to about 300,000. In addition, the molecular weight distribution (Mw / Mn) of the polyolefin may be about 2 to about 15, or about 3 to about 13, or about 5 to about 12.
Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.
< Example >
Nucleus Metallocene Synthesis of Compound
Produce Example One
1-1) Preparation of Ligand Compound
16 mL of 2.5 M n-BuLi (in hexane) was added to a THF solution of indene (6.7 g, 40 mmol) at −20 ° C. and stirred overnight at room temperature (RT). This solution was transferred to a 50 mL xylene dibromide (5.279 g, 20 mmol) THF solution under dry ice / acetone bath. After stirring overnight at room temperature (RT), water was added and the organic layer was extracted with ether. After separating the organic layer, water remaining in MgSO 4 was removed and the solvent was dried in vacuo to give a crude product of light yellow color. This was recrystallized with ether (hexane) / hexane (hexane) to obtain a high purity ligand compound (yield 67%).
1 H NMR (500 MHz, CDCl 3 ): 3.24 (4H, s), 3.89 (4H, s), 5.92 (2H, d), 7.18-7.44 (12H, m)
1-2) Preparation of Metallocene Compound
MTBE 11 mmol (2.2eq.) Was added to 50 mL of the toluene solution of 5 mmol of the ligand compound prepared in 1-1), 10 mmol of 2.5M n-BuLi, 4 mL were added at -20 ° C, and the mixture was stirred at room temperature overnight. The solution was transferred to a slurry of ZrCl 4 (THF) 2 5.3 mmol toluene under a dry ice / acetone bath, followed by stirring at room temperature overnight. This was filtered to give the titled yellow metallocene compound containing LiCl. (Yield 60%)
1 H NMR (500 MHz, CDCl 3 ): 4.24 (2H, d), 4.37 (2H, d), 5.72 (2H, s), 6.26 (2H, s), 7.15-7.61 (12H, m)
1-3) Preparation of Dinuclear Metallocene Compound
BrMg- (CH 2 ) 4 -MgBr 1.68g (6mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. 10mmol of the metallocene compound synthesized in the above 1-2) was added to another dried flask to form a slurry by injecting ether, and then, the BrMg- (CH 2 ) 4 -MgBr slurry was dried under a dry ice / acetone bath. The compound was transferred to the dissolved slurry. After stirring for one day, the filter was filtered off and all the solvent in the filtrate was removed. After recrystallization with hexane and then filtered once more to obtain a dinuclear metallocene compound.
1 H NMR (500 MHz, CDCl3): 1.82 (4H, m), 2.03 (4H, m), 3.41 (4H, dd), 3.72 (4H, dd), 5.4 (4H, m), 6.4 (4H, m) , 7.0 to 7.9 (24H, m)
Produce Example 2
2-1) Preparation of Metallocene Compound
J. AM. CHEM. SOC. VOL. 126, No. 46, 2004 pp. Metallocene compounds (1, 2-ethylene bis (indenyl) ZrCl 2 ) were synthesized as disclosed in 15231-15244.
1 H NMR (500MHz, C6D6): 2.96 (4H, m), 5.75 (2H, d), 6.45 (2H, q), 6.90-7.28 (8H, m)
2-2) Preparation of Dinuclear Metallocene Compound
BrMg- (CH 2 ) 4 -MgBr 1.68g (6mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. In another dried flask, 4.18 g (10 mmol) of the metallocene compound of 2-1) was added to form a slurry by injecting ether, and then a BrMg- (CH 2 ) 4 -MgBr slurry was metallized under a dry ice / acetone bath. Transferred to the thick compound slurry. After stirring for one day, the mixture was filtered, recrystallized with hexane, and then filtered once more to obtain a dinuclear metallocene compound. (Yield 34%)
1 H NMR (500MHz, C6D6): 1.52 (4H, m), 1.85 (4H, m), 2.56 (4H, d), 2.74 (4H, d), 5.54 (4H, d), 6.75 (4H, d) , 6.84 (4H, t), 6.91 (4H, d), 7.09 (4H, t), 7.56 (4H, d)
Produce Example 3
3-1) Preparation of Metallocene Compound
The dried flask was prepared to prepare 8 g (20 mmol) of the metallocene catalyst of Preparation Example 2-1). After replacing the inside of the flask with argon, 800 mL of dry dichloromethane was injected to make a slurry. In a glove box, 580 mg of PtO 2 was weighed into a flask, and then 300 mL of dichloromethane was added to make a slurry, which was transferred to a metallocene catalyst slurry and stirred for about 5 minutes.
After one day, the autoclave pressure vessel was pre-washed, dried in an oven, prepared, and then replaced with argon in the pressure vessel, and then a slurry of the metallocene catalyst and PtO 2 was mixed into the pressure vessel using a cannula. Moved. After venting all the argon in the pressure vessel, 30 atm of H 2 was substituted and reacted for 20 hours while stirring at 300 rpm. The title metallocene compound was obtained by filtering this mixture in a filter system that was not in contact with outside air and then removing the solvent in the filtrate.
1 H NMR (500MHz, C6D6): 1.34 (4H, m), 1.83 (2H, m), 1.85 (2H, m), 2.16 (4H, m), 2.42 (6H, m), 3.14 (2H, m) , 5.25 (2H, d), 6.34 (2H, d)
3-2) Preparation of Dinuclear Metallocene Compound
0.4 g (1.4 mmol, purity 95 wt%) of BrMg- (CH 2 ) 4 -MgBr was added to the dried flask, and ether was injected to make a slurry. 1-1 (2.3 mmol) of the metallocene compound of 3-1) was added to another dried flask, and ether was injected to make a slurry, and then a BrMg- (CH 2 ) 4 -MgBr slurry was metallized under a dry ice / acetone bath. Transferred to the thick compound slurry. The mixture was stirred for one day and then filtered to obtain a dinuclear metallocene compound. (Yield 45%)
1 H NMR (500MHz, C6D6): 1.32 (8H, m), 1.84 (8H, m), 1.94 (8H, m), 2.4 (16H, m), 3.32 (8H, m), 5.24 (4H, d) , 6.56 (4H, d)
Produce Example 4
4-1) Preparation of Metallocene Compound
N-BuCp was prepared from n-butylchloride and NaCp according to a known method, and ZrCl 4 ( THF) 2 was reacted thereto to prepare a metallocene compound.
1 H NMR (500MHz, C6D6): 0.82 (6H, t), 1.20 (4H, m), 1.42 (4H, m), 2.63 (4H, t), 5.72 (3H, t), 5.90 (3H, t)
4-2) Preparation of Dinuclear Metallocene Compound
BrMg- (CH 2 ) 4 -MgBr 2.75g (5mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. In another dried flask, 4.04 g (10 mmol) of the metallocene compound of 4-1) was added to form a slurry by injecting ether, and then a BrMg- (CH 2 ) 4 -MgBr slurry was metallized under a dry ice / acetone bath. Transferred to the Rosene compound slurry. The mixture was stirred for one day and then filtered to obtain a dinuclear metallocene compound. (Yield 85%)
1 H NMR (500MHz, C6D6): 0.89 (12H, m), 1.23 (4H, m), 1.28 (8H, m), 1.42 (4H, m), 1.48 (8H, m), 2.62 (8H, m) , 5.37 ~ 6.20 (12H, m)
Produce Example 5
5-1) Preparation of Metallocene Compound
After dissolving 1.16 g (10 mmol) of indene in THF soltion, 4.8 ml (12 mmol) of 2.5M n-BuLi in hexane was added at -78 ° C, and the mixture was stirred overnight at room temperature. The solution was transferred to 50 ml of THF solution of 1.57 g (5 mmol) of 2,3-bis (bromomethyl) naphthalene under a dryice / acetone bath. After stirring at room temperature overnight (overnight), water was added and the organic layer was extracted with ether. The organic layer was separated, residual water was removed with MgSO 4, and the solvent was dried in vacuo to obtain a crude product of light yellow. The crude product was recrystallized from ether / hexane to give a high purity ligand compound (yield 100%).
3.8 g (10 mmol) of the ligand compound synthesized above was dissolved in a dry 250 mL schlenk flask, and dissolved in 100 mL of toluene. Then, 2 mL (10 mmol) of MTBE was added thereto, followed by 8 mL (20 mmol) of 2.5 M. nBuLi hexane solution was added and lithiation was performed. After one day, 3.7 g (10 mmol) of ZrCl 4 (THF) 2 was taken in a glove box and placed in a 250 mL schlenk flask to prepare a suspension with toluene. After cooling the above two flasks to -78 ℃, lithiated ligand compound was slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature. After the reaction was carried out for one day, the mixture was filtered in a filter system that did not come into contact with outside air to remove LiCl, blow out all the solvent, and then re-crystallized by pouring hexane to filter the filter cake. ) To obtain a metallocene compound (yield 100%).
1 H NMR (500 MHz, CDCl 3): 4.4 (2H, d), 4.54 (2H, d), 5.71 (4H, br s), 7.15-7.99 (14H, m)
5-2) Preparation of Binary Metallocene Compounds
BrMg- (CH 2 ) 4 -MgBr 1.68g (6mmol, purity 95wt%) was added to the dried flask, and ether was injected to make a slurry. In another dried flask, 5.4 g (10 mmol) of the metallocene compound synthesized in the above 5-1) was added to form a slurry by injecting ether, followed by BrMg- (CH 2 ) 4 -MgBr slurry under a dry ice / acetone bath. Was transferred to the slurry in which the metallocene compound was dissolved. After stirring for one day, the filter was filtered off and all the solvent in the filtrate was removed. After recrystallization with hexane and then filtered once more to obtain a dinuclear metallocene compound.
1 H NMR (500 MHz, CDCl 3): 1.25 (4H, m), 1.31 (4H, m), 4.2 (2H, d), 4.28 (2H, d), 4.4 (2H, d), 4.45 (2H, d), 6.1 (8H, m), 6.8-8.0 (28H, m)
Polyolefin polymerization Example
Example 1-1
A 300 mL Andrew bottle was prepared, assembled with an impeller part, and then replaced with argon in a glove box. 180 mL of toluene prescribed with a small amount of trimethylaluminum (TMA) was added to the finished Andrew bottle in a glove box, and 5 mL of MAO (10 wt% toluene) solution was added thereto. In a 100 mL flask prepared separately, 10 μmol of the heteronuclear metallocene compound of Preparation Example 1 was dissolved in 20 mL of MAO to prepare a catalyst solution. 5 mL of catalyst solution was taken and injected into the Andrew bottle, and the top of the bottle was fixed to the mechanical stirrer while soaking in an oil bath heated to 90 ° C. After purging the inside of the bottle three times with ethylene gas, the ethylene valve was opened and a mechanical stirrer was operated to proceed the reaction at 500 rpm for 30 minutes.
After the reaction was completed, the temperature was lowered to room temperature, and the gas in the vessel was vented. After pouring about 500 mL of ethanol and stirring for about 1 hour, the obtained polymer through a filter (dry) was dried for 20 hours in a 60 ℃ oven. The mass of the obtained polymer was calculated to calculate the activity of the catalyst therefrom, and a polymer sample was taken to perform GPC analysis to confirm molecular weight and molecular weight distribution (PDI).
Example 1-2
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 5 ml of 1-hexene was added to the comonomer to proceed with the reaction.
Example 2-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 2 was used.
Example 2-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 2 was used.
Example 3-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 3 was used.
Example 3-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 3 was used.
Example 4-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 4 was used.
Example 4-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 4 was used.
Example 5-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 5 was used.
Example 5-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 10 μmol of the heteronuclear metallocene compound of Preparation Example 5 was used.
Comparative example 1-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 1-2) of Preparation Example 1 was used.
Comparative example 1-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 1-2) of Preparation Example 1 was used.
Comparative example 2-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 2-1) of Preparation Example 2 was used.
Comparative example 2-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 2-1) of Preparation Example 2 was used.
Comparative example 3-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 3-1) of Preparation Example 3 was used.
Comparative example 3-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 3-1) of Preparation Example 3 was used.
Comparative example 4-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 4-1) of Preparation Example 4 was used.
Comparative example 4-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 4-1) of Preparation Example 4 was used.
Comparative example 5-1
In Example 1-1, polyolefin polymerization was carried out in the same manner as in Example 1-1, except that 20 μmol of the mononuclear metallocene compound obtained in 5-1) of Preparation Example 5 was used.
Comparative example 5-2
In Example 1-2, polyolefin polymerization was carried out in the same manner as in Example 1-2, except that 20 μmol of the mononuclear metallocene compound obtained in 5-1) of Preparation Example 5 was used.
The catalytic activity and physical properties of the olefin polymer in the above Examples and Comparative Examples are shown in Table 1 below.
(Unit: ton / mol hr)
Molecular Weight (Mw)
(Unit: g / mol)
Referring to Table 1, when comparing the Examples and Comparative Examples, the olefin polymer having a high molecular weight and a broad molecular weight distribution when using the heteronuclear metallocene catalyst of the present invention rather than a mononuclear metallocene catalyst It can be seen that can be obtained. This effect was also the same when 1-hexene was used as comonomer.
Claims (9)
Catalyst composition comprising a promoter:
[Formula 1]
In Chemical Formula 1,
R1 to R8 may be the same or different from each other, and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 carbon atoms An arylalkyl group of 20 to 20, or an amine group having 1 to 20 carbon atoms, and two adjacent groups of R1 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings, provided that R1 to R8 Except when are all hydrogen;
R9 and R10 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 10 carbon atoms An aryloxy group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms;
Q is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 7 to 40 carbon atoms, or an arylalkylene group having 7 to 40 carbon atoms;
X is a halogen atom;
n is an integer from 1 to 10;
m is an integer of 1.
[Formula 1a]
[Formula 1b]
[Formula 1c]
[Formula 1d]
[Formula 4]
-[Al (R 11 ) -O] c-
In Formula 4, R 11 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and c is an integer of 2 or more. ,
[Formula 5]
D (R 12 ) 3
In Chemical Formula 5,
D is aluminum or boron, R 12 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[Formula 6]
[LH] + [ZA 4] - or [L] + [ZA 4] -
In Chemical Formula 6,
L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, A may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.
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