KR20160144208A - Supported metallocene catalyst and preparation of preparing polyolefin using the same - Google Patents
Supported metallocene catalyst and preparation of preparing polyolefin using the same Download PDFInfo
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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
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- 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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Abstract
The present invention relates to a high activity and low molecular weight supported metallocene catalyst and a process for preparing olefinic polymers using the same. More specifically, by introducing a tether group at the 4-position of indene and introducing an Si-bridged anthracene metallocene catalyst structure, an olefin polymer having high activity and low molecular weight can be produced in the production of the olefin polymer Supported metallocene catalyst and a process for producing an olefinic polymer using the same.
Description
The present invention relates to a supported metallocene catalyst capable of producing an olefin polymer having high activity and a low molecular weight, and a process for producing an olefin polymer using the same.
Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of olefinic polymers. The Ziegler-Natta catalysts have high activity, but because they are multi-site catalysts, the molecular weight distribution of produced polymers is wide The composition distribution of the comonomer 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 olefin polymer obtained by polymerization with the metallocene catalyst has a low melting point and a narrow molecular weight distribution, it is difficult to apply the olefin polymer in a field of application such as extrusion load, Of the molecular weight distribution.
Particularly, in order to solve the problems of the metallocene catalyst described above, many transition metal compounds in which a ligand compound containing a hetero atom is coordinated have been introduced. Specific examples of such a heteroatom-containing transition metal compound include azaferrocene compound having a cyclopentadienyl group containing a nitrogen atom, a structure in which a functional group such as a dialkylamine is linked with a cyclopentadienyl group as an additional chain A metallocene compound, or a titanium (lV) metallocene compound into which a cyclic alkylamine functional group such as piperidine is introduced.
However, among all these attempts, the metallocene catalysts actually applied to commercial plants are only a few, so that higher polymerization performance can be realized and olefin polymers of low molecular weight can be provided for improving processability There is still a need for research on metallocene compounds that can be used as polymerization catalysts.
On the other hand, in the metallocene catalyst system, a catalyst of the following general formula is known in the case of a low molecular weight olefin polymer catalyst group.
[General formula]
However, in the group of olefin polymer catalysts having a low molecular weight, there is no catalyst other than the above-mentioned structure, which is still commercialized. In particular, there is no silicon bridged ansa-metallocene catalyst group in the catalyst structure, which is not a non-bridge type. Therefore, there is a need for a new catalyst group capable of producing a low molecular weight olefin which can be used in various ways and has high activity.
In addition, although the catalyst represented by the above general formula is excellent in activity, it exhibits lower activity depending on the type of co-catalyst applied in the polymerization. Further, hydrogen polymerization is required to realize a lower molecular weight than the molecular weight region indicated by the catalyst, which causes a decrease in overall activity. Therefore, it is necessary to develop a highly active low-molecular-weight catalyst capable of realizing a lower molecular weight while increasing the activity by reducing the hydrogen input amount.
An object of the present invention is to provide a commercially available supported metallocene catalyst capable of producing an olefin polymer having a high activity and a low molecular weight.
Another object of the present invention is to provide a process for preparing an olefinic polymer using the supported metallocene catalyst.
The present invention provides a supported metallocene catalyst comprising a transition metal compound represented by the following general formula (1) supported on a support.
[Chemical Formula 1]
In Formula 1,
C 1 and C 2 are the same or different and at least one is a 4-substituted indenyl radical represented by the following formula a or b,
[Formula a] [Formula b]
Wherein R 1 , R 2 , R 4 , R 5 and R 6 are the same or different from each other and each independently represent hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, An arylalkyl having 7 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms, an alkylamido having 1 to 20 carbon atoms, an arylamido having 6 to 20 carbon atoms, or an alkylidene having 1 to 20 carbon atoms, R 3 are each independently - (CH 2 ) n'-OR, wherein R is a straight or branched alkyl group having 1 to 6 carbon atoms and n 'is an integer of 1 to 10,
When any of the above C 1 and C 2 is not a 4-substituted indenyl radical, the remainder is a cyclopentadienyl radical; Or a cyclopentadienyl radical substituted by hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl, aryl of 6 to 20 carbon atoms, or alkylaryl of 7 to 20 carbon atoms,
A is hydrocarbyl containing Si and having 1 to 30 carbon atoms;
n is 0 or 1,
M is a Group 4 transition metal,
X 1 and X 2 are the same or different and are each independently selected from the group consisting of halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms.
The present invention also provides a process for producing an olefin-based polymer, which comprises polymerizing an olefin-based monomer under the supported metallocene catalyst.
The supported metallocene catalyst of the present invention has a structure in which a tether is introduced at the 4-position of indene, thereby exhibiting high activity in the production of the olefin-based polymer, thereby producing polyethylene having a low molecular weight. In addition, since the high activity catalyst of the present invention can be easily commercialized, when it is used for the polymerization of olefin monomers, olefin polymers having a low molecular weight of about 400,000 or less can be produced with improved processability.
The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises, " or" having ", and the like, are intended to specify the presence of stated features, integers, Components, or combinations thereof, as a matter of convenience, without departing from the spirit and scope of the invention.
In addition, the present invention can be variously modified and can take various forms, so that specific embodiments are exemplified and will be described in detail below. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Hereinafter, the present invention will be described in detail.
According to one embodiment of the present invention, there is provided a supported metallocene catalyst comprising a transition metal compound represented by the following general formula (1) supported on a support.
[Chemical Formula 1]
In Formula 1,
C 1 and C 2 are the same or different and at least one is a 4-substituted indenyl radical represented by the following formula a or b,
[Formula a] [Formula b]
Wherein R 1 , R 2 , R 4 , R 5 and R 6 are the same or different from each other and each independently represent hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, An arylalkyl having 7 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms, an alkylamido having 1 to 20 carbon atoms, an arylamido having 6 to 20 carbon atoms, or an alkylidene having 1 to 20 carbon atoms, R 3 are each independently - (CH 2 ) n'-OR, wherein R is a straight or branched alkyl group having 1 to 6 carbon atoms and n 'is an integer of 1 to 10,
When any of the above C 1 and C 2 is not a 4-substituted indenyl radical, the remainder is a cyclopentadienyl radical; Or a cyclopentadienyl radical substituted by hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl, aryl of 6 to 20 carbon atoms, or alkylaryl of 7 to 20 carbon atoms,
A is hydrocarbyl containing Si and having 1 to 30 carbon atoms;
n is 0 or 1,
M is a Group 4 transition metal,
X 1 and X 2 are the same or different and are each independently selected from the group consisting of halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms.
The present invention aims at developing a new catalyst group which is highly suitable for the preparation of olefinic polymers having a low molecular weight and which is easy to produce commercially. Thus, the present invention provides metallocene catalysts having high activity and low molecular weight at the metallocene level used in the preparation of conventional low molecular weight olefinic polymers.
For this purpose, in the present invention, a novel unit having a tetherp introduced at the 4-position of the indene structure as a metallocene catalyst is synthesized and introduced into a new Si bridged ansa-metallocene catalyst precursor, There is a characteristic that a high activity and a low molecular weight PE can be produced in the production of an olefinic polymer.
The metallocene catalyst having such properties has a structure as defined in the above formula (1).
In particular, among the substituents defined in Formula 1 above, at least one of C 1 and C 2 has a 4-substituted indenyl radical of formula a or b. That is, C 1 and C 2 in Formula 1 may be simultaneously or at least one of the 4-substituted indenyl radicals.
Thus, in the formula (1) inde all of C 1 and C 2 of the formula a or b of the 4-substituted carbonyl radical may be, inde one of C 1 and C 2 have the general formula a or b is a 4-substituted carbonyl radical remaining The substituent may be a cyclopentadienyl radical as described above; Or a cyclopentadienyl radical substituted with hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl, aryl of 6 to 20 carbon atoms, or alkylaryl of 7 to 20 carbon atoms.
The 4-substituted indenyl radical of the above formula (a) or (b) may be derived from a radical compound of an indene structure into which a tetra is introduced at the 4-position.
Further, in the present invention, when having a non-bridged structure, at least one of C 1 and C 2 in formula (1) may be a 4-substituted indenyl radical of formula (a). That is, when n in the formula (1) of the present invention is 0, at least one of C 1 and C 2 or an indenyl radical represented by the above formula (a) may be simultaneously used.
In the present invention, in the case of Si bridged ansa-metallocene, at least one of C 1 and C 2 in formula (1) may be a 4-substituted indenyl radical of formula (b).
In particular, according to the present invention, a tether group is specifically included at the 4-position of indene. Therefore, in the above-mentioned formulas (a) and (b), the tether group substituted at the 4-position is the above-mentioned R 3 And a substituent.
Preferably, in the above formulas (a) and (b), R 3 is each independently - (CH 2 ) n'-OR wherein R is a straight or branched alkyl group having 2 to 4 carbon atoms and n ' .
And, as described above, R 3 The remaining substituents (i.e., R 1 , R 2 , R 4 , R 5, and R 6 ), except substituents, are the same or different from each other and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, Alkenyl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkyl having 1 to 20 carbon atoms It can be lead. Preferably, the substituents may each independently be hydrogen.
Further, in the present invention, when Si bridged ansa-metallocene is provided, A in formula (1) may be an alkyl group having 1 to 5 carbon atoms containing Si.
Each of X 1 and X 2 may independently be a halogen or an alkyl group having 1 to 20 carbon atoms.
On the other hand, the alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl 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 hydrocarbyl group means a monovalent hydrocarbon compound, and includes an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.
The halogen group means fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
As the transition metal of the fourth group defined as M, Ti (titanium), Zr (zirconium), hafnium (Hf) or the like can be used, but the present invention is not limited thereto.
In the transition metal compound according to a preferred embodiment of the present invention, the transition metal compound represented by Formula 1 may be any one of compounds represented by Chemical Formulas 1-1 and 1-2.
[Formula 1-1]
[Formula 1-2]
In the present invention, the method for preparing the transition metal compound represented by the formula (1) is not particularly limited, and may be prepared by using a substituted indene compound or a substituted or unsubstituted cyclopentadiene ligand compound. In addition, Formula 1 can be prepared in the presence of a base and a solvent. Preferably, the reaction may be carried out in the presence of a base in an organic solvent at a temperature of from -80 ° C to -20 ° C. In the present invention, as the reaction proceeds at a low temperature, the selectivity of the reaction can be increased. For example, the base may be n-BuLi or the like, but the present invention is not limited thereto.
In addition, the purification method used for obtaining the transition metal compound of the present invention may be a general method used in the organic synthesis method.
The method of producing the transition metal compound of the formula (1) of the present invention will be described in more detail in the following Examples.
Meanwhile, the metallocene catalyst of the present invention may be a catalyst in which the transition metal compound of Chemical Formula 1 is supported on a support. The carrier may be selected from the group consisting of silica, alumina and magnesia having a hydroxy group on the surface, but is not limited thereto.
In addition, the supported metallocene catalyst of the present invention may further contain a cocatalyst if necessary, and the kind thereof is not particularly limited.
Preferably, the catalyst of the present invention may further comprise at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (2) to (4).
(2)
- [Al (R 13) -O ] n -
In Formula 2,
R 13 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
(3)
J (R 13) 3
In Formula 3,
R 13 is as defined in Formula 3 above;
J is aluminum or boron;
[Chemical Formula 4]
[EH] + [ZA '4 ] - or [E] + [ZA' 4 ] -
In Formula 4,
E is a neutral or cationic Lewis acid;
H is a hydrogen atom;
Z is a Group 13 element;
A 'may be the same as or different from each other, and independently at least one hydrogen atom is replaced by halogen, an aryl group having 6 to 20 carbon atoms, to be.
Examples of the compound represented by the general formula (2) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.
Examples of the compound represented by the general formula (3) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
Examples of the compound represented by Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.
Preferably, the co-catalyst may be alumoxane, more preferably methylalumoxane (MAO), which is alkylalumoxane.
In the present invention, the molar ratio of the metallocene compound to the co-catalyst compound is not particularly limited, but may be 1:10 to 10: 1.
Also, in the copolymerization reaction, the catalyst composition including the metallocene catalyst may further include a reaction solvent, and examples of the reaction solvent include hydrocarbon solvents such as pentane, hexane, heptane and the like; Aromatic solvents such as benzene or toluene, but are not limited thereto.
According to another embodiment of the present invention, there is provided a process for producing an olefin-based polymer, which comprises polymerizing an olefin-based monomer under the above-described supported metallocene catalyst.
That is, the transition metal compound represented by Formula 1 may be used alone or in combination with a cocatalyst to prepare an olefin polymer as a catalyst composition.
Therefore, according to the present invention, since a transition metal compound having high activity is used as a catalyst, commercial production of an olefin polymer having a low molecular weight is possible. For example, a high activity and low molecular weight olefin polymer can be prepared by carrying out a polymerization process by bringing the supported metallocene catalyst containing the transition metal compound of formula (1) supported on the carrier and the olefin monomer into contact with each other.
In the process for producing an olefin polymer according to the present invention, the olefinic monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4- 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.
The olefin-based polymer of the present invention may be a polyethylene polymer, but is not limited thereto. That is, the olefin-based polymer may include an ethylene / alpha olefin copolymer obtained by polymerization of ethylene and an alpha olefin-based comonomer.
The alpha olefin-based comonomer may be an alpha olefin having 4 or more carbon atoms. Examples of the alpha olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, Tetradecene, 1-hexadecene, 1-octadecene, and the like, but are not limited thereto. Of these, alpha-olefins having 4 to 10 carbon atoms are preferable, and one or more alpha-olefins may be used as comonomers together.
Also, in the present invention, the polymerization reaction may be carried out by homopolymerization using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or solution reactor, as an olefin monomer, or copolymerization with two or more kinds of monomers.
The polymerization of the olefinic monomer can be carried out by reacting at a temperature of from about 25 to about 500 DEG C and from about 1 to about 100 kgf / cm < 2 > for about 1 to about 24 hours. In particular, the polymerization of the olefinic monomer may be carried out at a temperature of from about 25 ° C to about 500 ° C, preferably from about 25 ° C to about 200 ° C, more preferably from about 50 ° C to about 100 ° C. The reaction pressure can also be carried out at from about 1 to about 100 kgf / cm 2 , preferably from about 1 to about 50 kgf / cm 2 , and more preferably from about 5 to about 40 kgf / cm 2 .
The olefin-based polymer produced by the above method may exhibit a low molecular weight.
According to one embodiment of the present invention, the weight average molecular weight (Mw) of the olefinic polymer may be from about 10,000 to about 400,000 g / mol, or from about 10,000 to about 250,000 g / mol. The molecular weight distribution (Mw / Mn) of the olefinic polymer may be from about 1 to about 8, or from about 2 to about 4.
Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through a specific embodiment of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.
< Example >
The organic reagents and solvents used in the following examples were purchased from Aldrich 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 1 >
(One) Ligand Preparation of compounds
4-bromo-1-indanone (8.4 g, 40 mmol) was dissolved in MeOH (30 mL) in a dried 500 mL round bottom flask. The solution was cooled to 0 < 0 > C and NaBH4 (1.5 g, 40 mmol) was slowly added over 1 hour. After the completion of the reaction was confirmed by TLC, the solvent was removed under reduced pressure and then extracted with ether to obtain a brown viscous liquid. (> 99% yield)
1 H NMR (500MHz, CDCl 3 ): δ 1.92-1.99 (1H, m), 2.48-2.54 91H, m), 2.79-2.85 (1H, m), 3.04-3.10 (1H, m), 5.30 (1H, t), 7.12 (1H, t), 7.34 (1H, d), 7.42
The brown viscous intermediate (11 g, 50 mmol) from the previous reaction was dissolved in THF in a 500 mL round bottom flask, and HCl (240 mL, 5.8 M) was added and refluxed for 2 days. The product was isolated by column chromatography to give 4-bromo-1-indene (8.7 g, yield: 44 mmol, 88% yield) was obtained in the form of pale yellow liquid.
1 H NMR (500MHz, CDCl 3 ): δ 3.39 (2H, s), 6.62 (1H, d), 6.91 (1H, d), 7.16 (1H, t), 7.33 (1H, t)
4-Bromo-1-indene (8.7 g, 44 mmol) and NiCl 2 (dppe) (260 mg, 0.50 mmol) were dispersed in ether (80 mL) in a dried 250 mL schlenk flask. After cooling to 0 ° C, a solution of (6-tert-butoxy) hexyl magnesium chloride dispersed in THF was slowly added and stirred at room temperature overnight to obtain a greenish-yellow suspension. The reaction was quenched with aq. NH2Cl, extracted with ether and purified by column chromatography to give 4- (6- (tert-butoxy) hexyl) -1H-indene, a brown liquid product.
1 H NMR (500MHz, CDCl 3 ): δ 1.17 (9H, s), 1.27-1.67 (8H, m), 2.69 (2H, t), 3.31-3.33 (4H, m), 6.55 (1H, d), 6.88 (1H, d), 7.02 (1H, d), 7.21-7.26 (2H, m)
(2) Preparation of transition metal compounds
(2.72 g, 10 mmol) was dissolved in 100 ml of toluene, and 4.8 ml (4.0 eq.) Of MTBE was further added to the solution, to which was added 4- (6- (tert-butoxy) To the solution, an n- BuLi solution (2.5 M hexane solution, 4.8 ml, 12 mmol) was slowly added dropwise in a dry ice / acetone bath. After overnight reaction at room temperature, a yellowish slurry was obtained. ZrCl 4 (THF) 2 (1.89 g, 5.0 mmol) was prepared in a glove box to prepare a 50 ml solution of toluene, and the 4-T-Ind solution was dropwise fed in a dry ice / acetone bath. After the reaction at room temperature overnight, reddish slurry was identified. Thereafter, the reaction product was filtered to remove LiCl, and the toluene was vacuum dried to obtain red sticky oil (Formula 1-1) (2.78 g, 3.95 mmol, 79.2% yield).
1 H NMR (500 MHz, CDCl 3 ):? 0.89-0.92 (2H, m), 1.19 (18H, s), 1.28-1.70 (18H, m), 2.59-2.78 , < / RTI > m), 6.09-6.48 (4H, m), 7.07-7.55 (6H, m)
< Example 2 >
(1) Preparation of ligand compound
4-T-Ind (1.4 g, 5.0 mmol) was dissolved in a dry 250 mL schlenk flask in THF (30 mL) and then cooled to -78 ° C. n- BuLi solution (2.5 M hexane solution, 2.1 ml, 5.3 mmol) was slowly added dropwise and the mixture was stirred at room temperature overnight. A separate 250 mL Schlenk flask was charged with chloromethyl (2,3,4,5-tetramethylcyclopenta-2,4-dicarboxylate) dien-1-yl) silane (1.1 g, 5.0 mmol) was dissolved in THF, cooled to -78 ° C, and then subjected to lithiation reaction. This was stirred at room temperature overnight to obtain a red-brown solution. Quenching with water and extraction with ether followed by purification by column chromatography to obtain a yellow liquid type ligand (1.5 g, 3.4 mmol, 68% yield).
1 H NMR (500 MHz, CDCl 3 ):? -0.45 (3H, s), -0.17 (3H, s), 1.17 D), 6.71 (1H, s), 3.21 (1H, s), 3.29-3.34 (3H, , 6.99-7.10 (2 H, m), 7.39 (1 H, d)
(2) Preparation of transition metal compounds
To the dried 250 mL schlenk flask was dissolved the above prepared ligand (1.5 g, 3.4 mmol) in 30 mL of toluene and MTBE (10 mL), cooled to -78 ° C, and then an n- BuLi solution (2.5M hexane solution, 2.8 ml, 7.1 mmol) was added and stirred overnight to obtain a brown-orange solution. ZrCl 4 (THF) 2 (1.28 g, 3.4 mmol) was dispersed in toluene in a separately prepared 100 mL schlenk flask, cooled to -78 ° C, and the lithiated ligand solution was slowly injected. The mixture was stirred at room temperature overnight to obtain a yellow suspension. This was filtered to remove LiCl, and the filtrate from which the solvent had been removed was dispersed in pentane and filtered to obtain a solid portion (Formula 1-2) of yellow powder. (1.3 g, 2.1 mmol, 62% yield).
1 H NMR (500 MHz, CDCl 3 ):? 0.95 (3H, s), 1.15 (3H, s), 1.17 (9H, s), 1.39-1.82 (1H, s), 1.96 (6H, s), 2.82 (2H, t), 3.31 (2H, t), 5.96 1H, < / RTI > d), 7.33 (1H, d)
< Comparative Example 1 >
(3.81 g, 14 mmol) was dissolved in toluene (100 ml) and MTBE (3.4 ml, 28 mmol) was further introduced. To the solution was added n- BuLi solution (2.5 M hexane solution, 6.2 ml, 15.4 mmol) was added dropwise in a dry ice / acetone bath. After overnight reaction at room temperature, brown solution was obtained. ZrCl 4 (THF) 2 (2.64 g, 7 mmol) was prepared in a glove box and 50 ml of toluene solution was prepared. T-Ind-Li solution was dropwise fed in a dry ice / acetone bath. The red slurry was confirmed by stirring at room temperature overnight. Toluene was vacuum-dried to about 80%, and then recrystallized with hexane. The filter cake and the filtrate obtained by filtering the slurry were all recrystallized and were not obtained from the filter cake, and almost all the product was present in the filtrate. The solvent was removed by vacuum drying and red oil was obtained. (4.23 g, 87.5% yield).
1 H NMR (500MHz, CDCl 3 ): δ 0.84-1.63 (38H, m), 2.61-2.76 91H, m), 2.87-2.97 (1H, m), 3.24-3.33 (4H, m), 5.66 (0.5H , d), 5.80 (0.5H, d), 6.04 (0.5H, d), 6.28 (0.58H, d), 7.18-7.63
< Comparative Example 2 >
(One) Ligand Preparation of compounds
Chlorodimethyl ( TMCp ) Silane ( Chlorodimethyl ( TMCp ) silane , CDMTS ) Synthesis of
Tetramethylcyclopropane (TMCP) (6.0 mL, 40 mmol) was dissolved in a dry 250 mL schlenk flask in THF (60 mL) and then cooled to -78 ° C. n- BuLi solution (2.5 M hexane solution, 17 ml, 42 mmol) was slowly added dropwise and the mixture was stirred at room temperature overnight. Dichlorodimethylsilane (4.8 ml, 40 mmol) was dissolved in n-hexane in a separate 250 ml Schlenk flask and cooled to -78 deg. C, and the reacted TMCP-lithiated solution was slowly injected. It was stirred at room temperature overnight, and the solvent was removed under reduced pressure. The resulting product was dissolved in toluene and filtered to remove the remaining LiCl to give a yellow liquid (7.0 g, 33 mmol, 83% yield).
1 H NMR (500MHz, CDCl 3 ): δ 0.24 (6H, s), 1.82 (6H, s), 1.98 (6H, s), 3.08 (1H, s)
Ligand synthesis
T-Ind (2.72 g, 10 mmol) was dissolved in 50 ml of THF in a dried 250 ml schlenk flask, and then an n- BuLi solution (2.5 M hexane solution, 4.8 ml, 12 mmol) was added dropwise in a dry ice / acetone bath. After overnight reaction at room temperature, a red solution was obtained. The CDMTS (2.15 g, 10.0 mmol) synthesized above was dissolved in a separate 250 mL schlenk flask in THF, and the T-Ind-Li solution was dropwise fed in a dry ice / acetone bath. The mixture was stirred overnight at room temperature to identify a dark brown slurry. Quenching with water and extraction with ether gave the ligand (H413L) (4.18 g, 9.27 mmol, 92.7% yield).
1 H NMR (500MHz, CDCl 3 ): δ -0.43 (3H, s), -0.15 (3H, s), 1.21 (9H, s), 1.42-2.08 (22H, m), 2.61 (1H, s), M), 3.52 (1H, s), 6.21 (1H, s), 7.17-7.43 (4H, m)
(2) Preparation of transition metal compounds
Ligand (H413L) (4.18g, 9.27mmol) is dissolved in a toluene 100ml, n -BuLi solution (2.5M hexane solution, 8.2ml, 20.4mmol) in a solution injected into a added MTBE (4.4 ml, 4.0 eq. ) Of Was added dropwise in a dry ice / acetone bath. After overnight reaction at room temperature, brown solution was obtained. ZrCl 4 (THF) 2 (3.50 g, 9.27 mmol) was prepared in a glove box, and 50 ml of toluene solution was prepared. The ligand-Li solution was dropwise fed in a dry ice / acetone bath. The reddish slurry was confirmed by stirring at room temperature overnight. The slurry was filtered to remove LiCl, toluene was vacuum-dried at about 90%, and recrystallized with hexane. The slurry was filtered to obtain a yellow filter cake. (2.5 g, 4.1 mmol, 44.1% yield).
1 H NMR (500MHz, CDCl 3 ): δ 0.93 (3H, s), 1.17 (12H, s), 1.37-1.63 (8H, m), 2.81-2.87 (1H, m), 2.93-2.97 (1H, m ), 3.29-3.31 (2H, t), 5.55 (1H, s), 7.02-7.57 (4H, m)
< Comparative Example 3 >
A compound represented by the following formula was prepared by a conventional method and used in Comparative Example 3.
≪ Olefin polymerization Example >
Copolymer production
The catalyst (20 μmol) was placed in a flask under argon, 20 mL of toluene was added and stirred to make a 1 mM catalyst solution. At this time, the catalysts used were the metallocene compounds of Examples 1 to 2 and Comparative Examples 1 to 3, respectively, and a 1 mM catalyst solution in toluene was used.
Then, a 100 mL capacity Andrew bottle was prepared and assembled with the impeller part, and then the inside was replaced with argon in the glove box. After the glove box treatment, 70 mL of toluene was added to 10 mL of MAO (10 wt% toluene) solution in Andrew Bartlet, where a small amount of TMA was prescribed. 5 mL (5 μmol) of a 1 mM catalyst solution (toluene) was injected into the Andrew Bottle. Thereafter, the Andrew bottle was immersed in an oil bath heated to 90 ° C, the upper part of the bottle was fixed to a mechanical stirrer, and the mixture was stirred until the reaction solution reached 90 ° C. Then, the interior of the bottle was purged with ethylene gas three times, the ethylene valve was opened, and a mechanical stirrer was operated to react at 500 rpm for 30 minutes.
During the reaction, the vortex line inside the vessel was checked from time to time, and when the line became flat, the reaction was terminated prematurely. After the reaction, the temperature was lowered to room temperature, and the gas inside the container was vented. Then, the contents were poured into about 400 mL of ethanol, stirred for about 1 hour, filtered, and the resulting polymer was dried in a vacuum oven set at 60 DEG C for 20 hours.
The mass of the obtained polymer was calculated, and the activity of the catalyst was calculated. From the 10 mg sample, GPC analysis was performed to confirm the molecular weight and the degree of distribution. The results are shown in Table 1 below.
kg / gCat · hr
NOTE In Table 1, a. C2 9 bar, TiBAL 0.5 g, Al / Zr: 100, 80 ° C / 1 hr
Referring to Table 1, in Example 1, the catalytic activity was increased and the molecular weight of the polymer was increased as compared with Comparative Example 1 having a tether group at the 3-position of indene. Also, in Example 2, which had a tether group at the 4-position of indene and a Si-bridged ansamethallocene with cyclopentadienyl group, the molecular weight of the active and polymer was increased as compared with Comparative Example 2 having the tether group at the 3-position. In addition, in Comparative Example 3, since the substituent was not bonded to the indene group in the metallocene structure, it showed a certain molecular weight, but the activity was very low.
Claims (10)
[Chemical Formula 1]
In Formula 1,
C 1 and C 2 are the same or different and at least one is a 4-substituted indenyl radical represented by the following formula a or b,
[Formula a] [Formula b]
Wherein R 1 , R 2 , R 4 , R 5 and R 6 are the same or different from each other and each independently represent hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, An arylalkyl having 7 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms, an alkylamido having 1 to 20 carbon atoms, an arylamido having 6 to 20 carbon atoms, or an alkylidene having 1 to 20 carbon atoms, R 3 are each independently - (CH 2 ) n'-OR, wherein R is a straight or branched alkyl group having 1 to 6 carbon atoms and n 'is an integer of 1 to 10,
When any of the above C 1 and C 2 is not a 4-substituted indenyl radical, the remainder is a cyclopentadienyl radical; Or a cyclopentadienyl radical substituted by hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl, aryl of 6 to 20 carbon atoms, or alkylaryl of 7 to 20 carbon atoms,
A is hydrocarbyl containing Si and having 1 to 30 carbon atoms;
n is 0 or 1,
M is a Group 4 transition metal,
X 1 and X 2 are the same or different and are each independently selected from the group consisting of halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms.
and when n is 0, at least one of C 1 and C 2 or simultaneously an indenyl radical represented by the above-mentioned formula (a).
In the above formulas (a) and (b), R 1 is each independently - (CH 2 ) n'-OR wherein R is a straight or branched alkyl group having 2 to 4 carbon atoms and n 'is an integer of 4 to 8. Supported metallocene catalyst.
And A is an alkyl group having 1 to 5 carbon atoms containing Si.
Wherein the transition metal compound represented by the formula (1) is any one of compounds represented by the following formulas (1-1) and (1-2).
[Formula 1-1]
[Formula 1-2]
And at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (2) to (4).
(2)
- [Al (R 13) -O ] n -
In Formula 2,
R 13 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
(3)
J (R 13) 3
In Formula 3,
R 13 is as defined in Formula 2 above;
J is aluminum or boron;
[Chemical Formula 4]
[EH] + [ZA '4 ] - or [E] + [ZA' 4 ] -
In Formula 4,
E is a neutral or cationic Lewis acid;
H is a hydrogen atom;
Z is a Group 13 element;
A 'may be the same as or different from each other, and independently at least one hydrogen atom is replaced by halogen, an aryl group having 6 to 20 carbon atoms, to be.
The support is a supported metallocene catalyst selected from the group consisting of silica, alumina, and magnesia, the surface of which comprises a hydroxy group.
And polymerizing the olefin-based monomer.
The olefin-based monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, and 1-eicosene.
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