KR101723494B1 - Transition metal compound for preparing catalyst for polymerizing olefin, precursor thereof and metallocene catalyst including the same - Google Patents
Transition metal compound for preparing catalyst for polymerizing olefin, precursor thereof and metallocene catalyst including the same Download PDFInfo
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- KR101723494B1 KR101723494B1 KR1020150173704A KR20150173704A KR101723494B1 KR 101723494 B1 KR101723494 B1 KR 101723494B1 KR 1020150173704 A KR1020150173704 A KR 1020150173704A KR 20150173704 A KR20150173704 A KR 20150173704A KR 101723494 B1 KR101723494 B1 KR 101723494B1
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Abstract
Description
The present application relates to metallocene compounds, their precursors and metallocene catalysts comprising them.
The metallocene compound is a compound in which a ligand such as a cyclopentadienyl group (Cp), an indenyl group, or a cycloheptadienyl group is coordinated to a transition metal or a transition metal halogen compound As a basic form of the sandwich structure.
The metallocene catalyst is a single-site catalyst composed of the metallocene compound and cocatalyst such as methylaluminoxane. The polymer polymerized with the metallocene catalyst has a molecular weight distribution The distribution of the comonomers is uniform, and the copolymerization activity is higher than that of the Ziegler-Natta catalyst.
Depending on the structure of the ligand, the metallocene catalyst may have a different stereoregularity even when the same monomer is used.
The embodiments are directed to a metallocene compound having a novel structure, a precursor thereof, and a metallocene catalyst containing the same.
The transition metal compound precursor for olefin polymerization catalyst comprises at least one of the compounds represented by the following formula (P1)
The transition metal compound for olefin polymerization comprises at least one of the compounds represented by the following formula (M1)
In Formula (P1) and Formula (M1), n, X 1 , X 2 , R 1 to R 12 are each as defined below, and R 11 and R 12 are connected to each other to form a substituted or unsubstituted C 5-20 ring is formed.
n is 1 to 4;
X 1 and X 2 are independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl, C 6-20 aryl, C 6, respectively -20 aryl C 1-20 alkyl, C 1-20 alkyl, amido, C6-20 aryl amino or is a C 1-20 alkylidene.
R 1 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl, C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3- 20 heteroaryl , Substituted or unsubstituted C 1-20 silyl.
The metallocene catalyst comprises a transition metal compound for the olefin polymerization catalyst, a compound represented by the following formula A-1 and at least one of the compounds represented by the following formula A-2, and a carrier:
(A-1)
(A-2)
In the above formulas A-1 and A-2, Ra is halogen, C 1-20 alkyl, C 3-6 cycloalkyl, C 6-14 aryl, unsubstituted or substituted with halogen, and n is an integer of 2 or more , D is aluminum or boron; Rb to Rd are the same or different from each other and each independently represents hydrogen, halogen, or C 1-20 alkyl, C 3-6 cycloalkyl, or C 6-14 aryl substituted or unsubstituted with halogen.
Embodiments can provide a metallocene compound having a novel structure of a ligand, a precursor thereof, and a metallocene catalyst containing the same.
1 shows the results of < 1 > H-NMR of [1- (1,2,3,4-tetrahydroquinolin-8-yl) -2-methyl-3,5,6,7-tetrahydro- Lt; / RTI >
FIG. 2 is a graph showing the results of measurement of the concentration of [1- (1,2,3,4-tetrahydroquinolin-8-yl) -2-methyl-4-phenyl-2,3,6,7-tetrahydro- ≪ 1 > H-NMR spectrum.
FIG. 3 is a 1 H-NMR spectrum of 8- (2-methyl-4-naphthyl-2,3,6,7-tetrahydro-s-indacenyl) -1,2,3,4-tetrahydroquinoline.
As used herein, the term " C AB "means" the number of carbon atoms is not less than A and not more than B ", and the terms "A to B""inthe" substituted "means" at least one hydrogen of the hydrocarbon compound or a hydrocarbon derivative halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1- 20 alkyl, C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkyl, amido, C 6-20 aryl or C 1-20 amido substituted with alkylidene "means, and" unsubstituted "means" hydrocarbon compounds or at least one hydrogen, halogen, C 1-20 alkyl hydrocarbon derivatives, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl, C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene ".
The transition metal compound precursor for olefin polymerization catalyst comprises at least one of the compounds represented by the following formula (P1)
In formula (P1), n, X 1 , X 2 , R 1 to R 12 are each as defined below, and R 11 and R 12 are connected to each other to form a substituted or unsubstituted C 5-20 To form a ring.
n is 1 to 4;
X 1 and X 2 are independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl, C 6-20 aryl, C 6, respectively -20 aryl C 1-20 alkyl, C 1-20 alkylamido, C 6-20 arylamido or C 1-20 alkylidene.
R 1 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted Substituted or unsubstituted C 1-6 alkyl, C 1-20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl , Substituted or unsubstituted C 1-20 silyl.
In the formula (P1), n may be 1, and the compounds represented by the formula (P1) may be at least one of the compounds represented by the following formula (P2).
In the formula (P2), each of R 13 to R 15 is independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, Substituted or unsubstituted C 1-20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 silyl.
In Formula P2, R 1 and R 2 may be hydrogen or methyl, each independently, R 3 is C 1-20 alkyl, C 6-20 aryl, C 1-20 alkyl, C 6-20 aryl, C 6- 20 aryl C 1-20 alkyl, C 1-20 alkyl, amido, C 6-20 aryl amido, C 1-20 heteroaryl C 3-20 alkyl, or may be a heteroaryl group, R 4 to R 14 may be hydrogen And R < 15 > may be hydrogen or C1-20 alkyl.
The compounds represented by the formula (P2) may be at least one of the compounds represented by the following formulas (1) to (56)
On the other hand, in the general formula P1 and
On the other hand, the transition metal compound for an olefin polymerization catalyst comprises at least one of the compounds represented by the following formula (M1)
In formula (M1), n, X 1 , X 2 , R 1 to R 12 are each as defined below, and R 11 and R 12 are connected to each other to form a substituted or unsubstituted C 5-20 To form a ring.
n is 1 to 4;
X 1 and X 2 are independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl, C 6-20 aryl, C 6, respectively -20 aryl C 1-20 alkyl, C 1-20 alkyl, amido, C6-20 aryl amino or is a C 1-20 alkylidene.
R 1 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkyl, C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3- 20 heteroaryl , Substituted or unsubstituted C 1-20 silyl.
In formula (M1), n may be 1, and the compounds represented by formula (M1) may be at least one of compounds represented by formula (M2)
In Formula M2, R 13 to R 15 each independently represent hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, Substituted or unsubstituted C 1-20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl group, a substituted or unsubstituted C 1-20 silyl.
In formula M2, R 1 and R 2 may be hydrogen or methyl, each independently, R 3 is C 1-20 alkyl, C 6-20 aryl, C 1-20 alkyl, C 6-20 aryl, C 6- 20 aryl C 1-20 alkyl, C 1-20 alkyl, amido, C 6-20 aryl amido, C 1-20 heteroaryl C 3-20 alkyl, or may be a heteroaryl group, R 4 to R 14 may be hydrogen And R < 15 > may be hydrogen or C1-20 alkyl.
The compounds represented by Formula M2 may be at least one of the compounds represented by the following Formulas 57 to 112:
In Formula M1, at least one of R 1 and R 2 , R 5 and R 6 , R 6 and R 7 , R 8 and R 9, and R 9 and R 10 is connected to form a substituted or unsubstituted C 5 -20 ring can be formed.
Hereinafter, production examples of transition metal precursor compounds for olefin polymerization catalysts represented by the general formulas (1), (17) and (37) will be described in detail.
Production Example 1 : 8- (2- methyl -3,5,6,7- Tetrahydro -s- Indasen -1 (2H) -yl) -1,2,3,4- Tetrahydroquinoline (Formula 1)
Aluminum chloride (AlCl 3) 14.1 g (106 mmol) is dichloromethane (dichloromethane) alpha was added 200 mL in a distributed-bromo feeders small butyryl bromide (α-Bromoisobutyryl bromide) 9.7 g (42 mmol) and indan (Indan ) Was added at 0 占 폚, and the mixture was stirred at room temperature for 12 hours or longer. After the stirring was completed, 50 mL of water was further added at 0 DEG C to terminate the reaction. Thereafter, the organic layer was extracted using a separatory funnel and the solvent was removed under vacuum to obtain 2-methyl-3,5,6,7-tetrahydro-s-indacene-1 (2H) ).
(M, 2H), 2.15 (m, 2H), 1.32 (m, 2H), 2.32 (d, 3H) ppm.
To a solution of 959 mg (7.2 mmol) of 1,2,3,4-tetrahydroquinoline in 10 mL of hexane was added 1.6 M of n-butyllithium (n-BuLi) (7.2 mmol) was slowly added at -30 ° C, and then the temperature was slowly raised to room temperature and then stirred for 12 hours or more. After completion of the stirring, the resultant solid was filtered and the solvent was removed, and then dissolved in 20 mL of diethyl ether, and carbon dioxide (CO 2 ) was added at -78 ° C. Then, the temperature was slowly raised to room temperature, and the mixture was stirred for 12 hours or more. Thereto, 570 mg (7.9 mmol) of tetrahydrofuran and 1.7 M (t-BuLi) And the mixture was stirred for 2 hours.
1.1 g (6.1 mmol) of 2-methyl-3,5,6,7-tetrahydro-s-indacene-1 (2H) -one and 518 mg (12.2 mmol) of lithium chloride Thereafter, the mixture was stirred at room temperature for 12 hours or longer. After completion of the stirring, 20 mL of water was added to terminate the reaction. The organic layer was extracted with diethyl ether, and the solvent was removed under vacuum. (2-methyl-3,5,6,7-tetrahydro-s-indacene-1 (2H) -yl) -1,2,3,4-tetrahydroquinoline was obtained through column chromatography Yield: 20%).
(M, 6H), 7.02 (d, 1H), 6.82 (t, 1H), 3.78 (brs, 1H), 3.18 , 8H), 1.90 (m, 5H), 1.62 (m, 2H).
Production Example 2 : 8- (2- methyl -4-phenyl-2,3,6,7- Tetrahydro -s- Indah Sen ) -1,2,3,4- Tetrahydroquinoline (Formula 17)
2-methyl -3,5,6,7- tetrahydro -s- indazol metallocene -1 (2H) - one 1.0 g (5.37 mmol) of aluminum chloride (AlCl 3) 1.65 g (12.4 mmol) in chloroform is dispersed (Chloroform) solution. After the addition was completed, stirring was carried out for 1 hour. After 1 hour, 858 mg (5.37 mmol) of bromine was slowly added to the solution at 0 ° C. After completion of the addition, the temperature was slowly raised to room temperature and stirred for 12 hours or more. After stirring, the reaction was terminated by adding 50 mL of water. The organic layer was extracted with dichloromethane and the solvent was removed under vacuum. 4-Bromo-2-methyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one was obtained (50%) by column chromatography.
(M, 2H), 1.32 (m, 2H), 2.32 (m, 2H) (d, 3H) ppm.
1.06 g (4.00 mmol) of 4-bromo-2-methyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one and 634 mg (5.20 mmol ) And 230 mg (5 mol%) of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) in 40 mL of tetrahydrofuran and 10 mL of methanol was added potassium carbonate (K 2 CO 3 ) aqueous solution of 2.0 M (3.3 M equivalent) was slowly added thereto. After the addition was completed, the temperature was raised to 80 ° C and the mixture was stirred for 12 hours or more. After stirring, 50 mL of water was added to terminate the reaction. The organic layer was extracted with ethyl acetate and the solvent was removed under vacuum. 2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one was obtained by column chromatography (yield: 77%).
1H NMR (CDCl3):? 7.60 (s, IH), 7.50-7.25 (m, 5H), 3.17 (m, IH), 3.00 , 2.51 (dd, 1H), 2.08 (m, 2H), 1.26 (d, 3H) ppm.
479 mg (3.60 mmol) of 1,2,3,4-tetrahydroquinoline was dissolved in hexane (10 mL) and n-butyllithium (n-BuLi) 1.6 M 3.78 mmol) was added slowly at -30 < 0 > C. After completion of the addition, the temperature was slowly raised to room temperature and stirred for 12 hours or more. After stirring, the resulting solid was filtered to remove the solvent, dissolved in 10 mL of diethyl ether, and carbon dioxide (CO 2 ) was added at -78 ° C. The temperature was slowly raised to room temperature and then stirred for 12 hours or more. 285 mg (3.95 mmol) of Tetrahydrofuran and 1.7 M (3.95 mmol) of t-butyllithium (t-BuLi) were continuously added at -20 캜 and stirred for 2 hours.
800 mg (3.05 mmol) of 2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one and 260 mg (6.11 mmol) of lithium chloride After the addition, the temperature was slowly raised to room temperature and stirred for 12 hours or more. After stirring, 20 mL of water was added to terminate the reaction. The organic layer was extracted with ethyl acetate and the solvent was removed under vacuum.
(2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indacensile) -1,2,3,4-tetrahydroquinoline was obtained by column chromatography (Yield: 30 %).
1H NMR (CDCl3):? 7.50-7.11 (m, 5H), 7.00 (m, 2H), 6.95 2H), 2.96-2.83 (m, 4H), 2.79 (t, 2H), 2.03 (m, 2H), 1.98 (s, 3H) ppm.
Production Example 3 : 8- (2- methyl -4-phenyl-2,3,6,7- Tetrahydro -s- Indah Sen ) -1,2,3,4- Tetrahydroquinoline (37)
700 mg (2.64 mmol) of 4-bromo-2-methyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one and 1-naphthaleneboronic acid 590 mg (3.43 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) solution of the 150 mg (5 mol%) in tetrahydrofuran (tetrahydrofuran), 40 mL, methanol (methanol) 10 mL 2.0 M (3.3 M equivalent) of an aqueous solution of potassium carbonate (K 2 CO 3 ) was slowly added thereto. After the addition was completed, the temperature was raised to 80 ° C and the mixture was stirred for 12 hours or more. After stirring, 50 mL of water was added to terminate the reaction. The organic layer was extracted with ethyl acetate and the solvent was removed under vacuum.
2-Methyl-4-naphthyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one was obtained (96%) by column chromatography.
2H NMR (CDCl3):? 7.93 (t, 2H), 7.69 (s, 1H), 7.60-7.47 (m, 2H), 7.42-7.33 2H), 1.21 (t, 3H), 2.60 (m, 2H), 2.57-2.44 (m,
400 mg (2.98 mmol) of 1,2,3,4-tetrahydroquinoline was dissolved in hexane (10 mL) and n-butyllithium (n-BuLi) 1.6 M 3.13 mmol) was added slowly at -30 < 0 > C. After completion of the addition, the temperature was slowly raised to room temperature and stirred for 12 hours or more. After stirring, the resulting solid was filtered to remove the solvent, dissolved in 10 mL of diethyl ether, and carbon dioxide (CO 2 ) was added at -78 ° C. The temperature was slowly raised to room temperature and then stirred for 12 hours or more. 236 mg (3.27 mmol) of Tetrahydrofuran and 1.7 M (3.27 mmol) of t-butyllithium (t-BuLi) were continuously added at -20 캜 and stirred for 2 hours.
800 mg (2.53 mmol) of 2-methyl-4-naphthyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one and 214 mg (5.06 mmol) After the addition slowly, the temperature was slowly raised to room temperature and the mixture was stirred for 12 hours or more. After stirring, 20 mL of water was added to terminate the reaction. The organic layer was extracted with ethyl acetate and the solvent was removed under vacuum.
8- (2-methyl-4-naphthyl-2,3,6,7-tetrahydro-s-indacensyl) -1,2,3,4-tetrahydroquinoline was obtained by column chromatography (yield: 12%).
1H NMR (CDCl3):? 7.96-7.84 (m, 2H), 7.60-7.34 (m, 5H), 7.04-6.92 3.04-2.82 (m, 5H), 2.68-2.38 (m, 1H), 2.06-1.93 (m, 5H), 1.91 (s, 3H) ppm.
Hereinafter, production examples of the transition metal compound for an olefin polymerization catalyst represented by the general formulas (58) and (74) will be described in detail.
Manufacturing example 4: [1- (1,2,3,4- Tetrahydroquinoline -8-yl) -2- methyl -3,5,6,7- Tetrahydro -s-indacene] dimethyl Titanium (Formula 58) Produce
160 mg (0.53 mmol) of the ligand synthesized in Preparation Example 1 was dissolved in 10 mL of diethyl ether, and methyllithium (MeLi) 1.6 M (2.16 mmol) was slowly added at -78 ° C. After completion of the addition, slowly raise the temperature to room temperature. 100 mg (0.53 mmol) of titanium chloride (TiCl 4 ) was added thereto at room temperature, followed by stirring for 4 hours. When the reaction was completed, the solvent was removed under vacuum and extracted with hexane (Henxane).
The solvent was removed in vacuo to give [1- (1,2,3,4-tetrahydroquinolin-8-yl) -2-methyl-3,5,6,7-tetrahydro-s-indacen- (Yield: 24%).
(M, 2H), 6.43 (s, IH), 4.52 (m, IH) 2H), 2.46 (m, 4H), 1.86 (s, 3H), 1.63-1.76 (m, 4H), 0.84 3H).
Manufacturing example 5: [1- (1,2,3,4- Tetrahydroquinoline -8-yl) -2- methyl -4-phenyl-2,3,6,7-tetrahydro-s-indacensile] dimethyl titanium (74)
303 mg (0.80 mmol) of the ligand synthesized in Preparation Example 2 was dissolved in 10 mL of diethyl ether, and methyllithium (MeLi) 1.6 M (3.21 mmol) was added slowly at -78 ° C. After completion of the injection, slowly raise the temperature to room temperature. 152 mg (0.80 mmol) of titanium chloride (TiCl 4 ) was added slowly at room temperature and then stirred for 4 hours. After the reaction was completed, the solvent was removed under vacuum and extracted with hexane (Hexane).
The solvent was removed in vacuo to give [1- (1,2,3,4-tetrahydroquinolin-8-yl) -2-methyl-4-phenyl-2,3,6,7-tetrahydro-s- ] Dimethyl titanium. (Yield: 55%).
1H NMR (C6D6):? 7.82 (d, 2H), 7.50 (t, IH), 7.37 (t, 2H), 7.15 3H), 1.82 (m, 4H), 0.93 (s, 3H), 0.28 (s, 3H) .
The metallocene catalyst may include a transition metal compound for the olefin polymerization catalyst, a cocatalyst compound, and a carrier capable of supporting them.
The co-catalyst compound is not particularly limited as long as it is widely used in the metallocene catalyst field, and includes, for example, a first co-catalyst compound of at least one compound represented by the following formula A-1, And at least one of a mixture of the first co-catalyst compound and the second co-catalyst compound.
(A-1)
(A-2)
In the above formulas A-1 and A-2, Ra is halogen, C 1-20 alkyl substituted with halogen, C 3-6 cycloalkyl, C 6-14 aryl; n is an integer of 2 or more; D is aluminum or boron; Rb to Rd are the same or different from each other and each independently represents hydrogen, halogen, or C 1-20 alkyl, C 3-6 cycloalkyl, or C 6-14 aryl substituted or unsubstituted with halogen.
The support is not particularly limited as long as it can support the transition metal compound for the olefin polymerization catalyst and the promoter compound, and can be, for example, carbon, silica, alumina, zeolite, magnesium chloride and the like.
As the method of supporting the transition metal compound for olefin polymerization catalyst and the above promoter compound on the carrier, known physical adsorption method or known chemical adsorption method may be used.
The physical adsorption method includes, for example, a method in which a solution in which the transition metal compound for an olefin polymerization catalyst is dissolved is contacted with the carrier and then dried, or a method in which the transition metal compound for the olefin polymerization catalyst and the catalyst compound Contacting the solution with the carrier and drying the solution, or a method in which a solution in which the transition metal compound for an olefin polymerization catalyst is dissolved is contacted with the carrier and then dried to prepare a carrier carrying the transition metal compound for the olefin polymerization catalyst, Alternatively, a solution in which the co-catalyst compound is dissolved may be contacted with the support, followed by drying to prepare a support carrying the promoter compound, and then mixing them.
The chemical adsorption method includes, for example, a method in which the promoter compound is first supported on the surface of the support, and then the transition metal compound for olefin polymerization catalyst is supported on the promoter compound, (For example, in the case of silica, the hydroxyl group (-OH) on the silica surface) with the metallocene compound.
The total amount of the transition metal compound for the olefin polymerization catalyst may be 0.001 mmol to 1 mmol based on 1 g of the support. The supported amount of the promoter compound may be 2 mmol to 15 mmol have.
Hereinafter, a method for producing an olefin polymer using the metallocene catalyst as a polymerization catalyst will be described.
The olefin polymer can be prepared by polymerizing the olefin monomers in the presence of the metallocene catalyst. The olefin monomers can be selected from the group consisting of, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-dodecene, 1-tetradecene, 1-hexadecene, and the like, and the olefin polymer may be a homopolymer or a copolymer.
The olefin polymer can be produced, for example, by gas phase polymerization, solution polymerization, slurry polymerization or the like. When the olefin polymer is prepared by the solution polymerization method or the slurry polymerization method, examples of the solvent to be used include C 5-12 aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; And mixtures thereof. However, the present invention is not limited to these.
Hereinafter, embodiments belonging to the spirit of the invention will be described with reference to the above-described chemical structures, production examples, and the like. However, the spirit of the invention is not limited to the exemplary chemical structures and the production examples, and the ideas of the invention can be variously modified based on the exemplified chemical structures and the manufacturing examples. It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or scope of the inventive concept. . It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (11)
In the above formula (P2)
R 1 and R 3 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted Substituted or unsubstituted C 1-6 alkyl, C 1-20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl , Or substituted or unsubstituted C 1-20 silyl,
R 2 , R 4 to R 10 and R 13 to R 15 are each hydrogen.
Wherein R 1 is hydrogen or methyl and R 3 is selected from the group consisting of hydrogen, C 1-20 alkyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 Alkyl, C 1-20 alkylamido, C 6-20 arylamido, C 1-20 heteroalkyl or C 3-20 heteroaryl.
Wherein the compound represented by the general formula (P2) is at least one of compounds represented by Chemical Formulas 1, 5, 9, 13, 17, 21, 25, 29, 33 and 37: :
In Formula (M2), X 1 and X 2 are each independently halogen or C 1-20 alkyl,
R 1 and R 3 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted Substituted or unsubstituted C 1-6 alkyl, C 1-20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl , Or substituted or unsubstituted C 1-20 silyl,
R 2 , R 4 to R 10 and R 13 to R 15 are each hydrogen,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf).
Wherein R 1 is hydrogen or methyl and R 3 is selected from the group consisting of hydrogen, C 1-20 alkyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 Alkyl, C 1-20 alkylamido, C 6-20 arylamido, C 1-20 heteroalkyl or C 3-20 heteroaryl.
The compounds represented by Formula M2 are represented by the following Formulas 57, 58, 61, 62, 65, 66, 69, 70, 73, 74, 77, 78, 81, 82, 85, 86, 89, 90, A transition metal compound for an olefin polymerization catalyst characterized by being at least one of the compounds represented by the formula:
At least one of the compounds represented by the following formula (A-1) and the compounds represented by the following formula (A-2), and
carrier;
≪ RTI ID = 0.0 > metallocene < / RTI &
(A-1)
(A-2)
In the above formulas A-1 and A-2, Ra is halogen, C 1-20 alkyl, C 3-6 cycloalkyl, C 6-14 aryl, unsubstituted or substituted with halogen, and n is an integer of 2 or more , D is aluminum or boron; Rb to Rd are the same or different from each other and each independently represents hydrogen, halogen, or C 1-20 alkyl, C 3-6 cycloalkyl, or C 6-14 aryl substituted or unsubstituted with halogen.
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WO2019182968A1 (en) * | 2018-03-19 | 2019-09-26 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content pedm using tetrahydroindacenyl catalyst systems |
US10894841B2 (en) | 2018-03-19 | 2021-01-19 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content PEDM having low glass transition temperatures using tetrahydroindacenyl catalyst systems |
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KR20060123293A (en) * | 2003-12-10 | 2006-12-01 | 바젤 폴리올레핀 게엠베하 | Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins |
KR20080065868A (en) * | 2007-01-10 | 2008-07-15 | 주식회사 엘지화학 | Method for preparing transition metal complexes, transition metal complexes prepared using the mathod, catalysts composition containing the complexes |
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KR20060123293A (en) * | 2003-12-10 | 2006-12-01 | 바젤 폴리올레핀 게엠베하 | Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins |
KR20080065868A (en) * | 2007-01-10 | 2008-07-15 | 주식회사 엘지화학 | Method for preparing transition metal complexes, transition metal complexes prepared using the mathod, catalysts composition containing the complexes |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2019182968A1 (en) * | 2018-03-19 | 2019-09-26 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content pedm using tetrahydroindacenyl catalyst systems |
US10894841B2 (en) | 2018-03-19 | 2021-01-19 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content PEDM having low glass transition temperatures using tetrahydroindacenyl catalyst systems |
US10899853B2 (en) | 2018-03-19 | 2021-01-26 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content PEDM using tetrahydroindacenyl catalyst systems |
US11466102B2 (en) | 2018-03-19 | 2022-10-11 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content PEDM having low glass transition temperatures using tetrahydroindacenyl catalyst systems |
US11597782B2 (en) | 2018-03-19 | 2023-03-07 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content PEDM using tetrahydroindacenyl catalyst systems |
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