JPH07173208A - New metallocene compound and olefin polymerization using the same - Google Patents

Abstract

PURPOSE:To provide a metallocene compd. which enables the production of a highly stereoregular olefin polymer at a high yield. CONSTITUTION:A metallocene compd. of the formula (wherein L is an indenyl or tetrahydroindenyl group optionally substd. by an alkyl or silicon-contg. hydrocarbon group; X is an optionally substd. 2,2'-substd. bipheny group; M is a tri- or tetravalent metal selected from Ti, Hf, and Zr; Y is halogen or 1-20C alkyl; and m is 1 or 2) is selected as a catalyst for olefin polymn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel metallocene compound and a method for polymerizing olefins using the same. Specifically, it relates to a metallocene compound having a specific structure and a method for polymerizing an olefin using the metallocene compound.

[0002]

2. Description of the Related Art A method for polymerizing an olefin by using an ordinary metallocene compound, particularly a method for stereoregularly polymerizing an α-olefin has been reported by Kaminsky et al. (Angew. Chem., Vol. 97, 507 (1985). )) Many improvements have been made. This catalyst system has a high activity but has a problem that the stereoregularity of the obtained polymer is not sufficient, and thus the catalyst obtained by the method of substituting some of the hydrogens of the cyclopentadienyl group with an alkyl group. It is common to try to improve stereoregularity (Yamazaki et al., Ch
emistry Letters, 1853 (1989), JP-A-4-268307
No.

[0003]

According to the above method, it is possible to produce a polyolefin having a considerably high activity and a high stereoregularity, but a catalyst which gives a novel polyolefin having a high activity and a high stereoregularity. Development of the system is desired.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on a novel metallocene compound which solves the above problems and provides a highly active and highly stereoregular polyolefin, and a polymerization method using the same, and completed the present invention. . That is, the present invention is a metallocene compound represented by the following general formula (1) [Chemical formula 2], and is characterized in that an olefin is polymerized using the metallocene compound represented by the following general formula (1). It is a method of polymerizing olefins.

[0005]

[Chemical 2] (In the formula, L represents an indenyl group or a tetrahydroindenyl group which may be substituted with an alkyl group or a silicon-containing hydrocarbon residue, and X is an optionally substituted 2,
2'-substituted biphenyl group, M is a trivalent or tetravalent metal selected from Ti, Hf and Zr, Y is a compound selected from a halogen atom or an alkyl group having 1 to 20 carbon atoms, m
Is 1 or 2. L in the general formula (1) is an alkyl group or an indenyl group or a tetrahydroindenyl group which may be substituted with a silicon-containing hydrocarbon residue. As the alkyl group, one having 1 to 20 carbon atoms is usually used. Examples of the silicon-containing hydrocarbon residue include a silyl group containing an alkylsilyl group having 1 to 20 carbon atoms such as trimethylsilyl group and an aryl group having 6 to 20 carbon atoms such as phenyldimethylsilyl group.

X is a 2,2'-substituted biphenyl group in which the remaining hydrogen may be replaced. Examples of the substituent include an alkyl group, an aryl group, a silyl group, and a halide group, which may be those in which a part of the residual hydrogen has been substituted or those in which all of the hydrogen has been substituted. As the central metal M,
Ti, Hf, and Zr are mentioned. Y is a halogen atom such as fluorine, chlorine, bromine or iodine or has 1 to 20 carbon atoms.
And the alkyl group m is 1 or 2.

Specific examples of the compound represented by the general formula (1) include the followings. 2,2'-Biphenyldiylbis (1-indenyl) zirconium dichloride, 2,2'-Biphenyldiylbis (2-methyl-1-indenyl) zirconium dichloride, 2,2'-
Biphenyldiylbis (2-ethyl-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (2-
Isopropyl-1-indenyl) zirconium dichloride, 2,2'-biphenyldylbis (2-tert-butyl-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (2-trimethylsilyl-1-indenyl) zirconium dichloride , 2,2'- Biphenyldiylbis (3
-Methyl-1-indenyl) zirconium dichloride, 2,
2'-biphenyldiylbis (3-ethyl-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis
(3-Isopropyl-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (3-tert-butyl-1-
Indenyl) zirconium dichloride,

2,2'-biphenyldiylbis (3-trimethylsilyl-1-indenyl) zirconium dichloride, 2,
2'-biphenyldiylbis (2,3-dimethyl-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (2,3-diethyl-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,
2'-biphenyldylbis (2-methyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2 '
-Biphenyldylbis (2-ethyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride,

2,2'-biphenyldiylbis (2-isopropyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (2-tert-
Butyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2'-biphenyldylbis (2-trimethylsilyl-4,5,6,7-tetrahydro-1-indenyl)
Zirconium dichloride, 2,2'-biphenyldiylbis (3-methyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (3
-Ethyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (3-
Isopropyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis
(3-tert-butyl-4,5,6,7-tetrahydro-1-indenyl)
Zirconium dichloride, 2,2'-biphenyldiylbis (3-trimethylsilyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2'-biphenyldiylbis (2,3-dimethyl-4, 5,6,7- Tetrahydro-1-
Indenyl) zirconium dichloride, 2,2'-biphenyldyl bis (2,3-diethyl-4,5,6,7-tetrahydro-
1-indenyl) zirconium dichloride, 2,2 '-(3,3'-
Dimethylbiphenyldiyl) bis (1-indenyl) zirconium dichloride,

2,2 '-(3,3'-dimethylbiphenyldiyl) bis (2-methyl-1-indenyl) zirconium dichloride, 2,2'-(3,3'-dimethylbiphenyldiyl) bis (3- Methyl-1-indenyl) zirconium dichloride, 2,2'-
(4,4 ', 6,6'-Tetramethylbiphenyldiyl) bis (1-indenyl) zirconium dichloride, 2,2'-(4,4 ', 6,6'
-Tetramethylbiphenyldiyl) bis (2-methyl-1-indenyl) zirconium dichloride, 2,2 '-(4,4', 6,6'-
Tetramethylbiphenyldiyl) bis (3-methyl-1-indenyl) zirconium dichloride, 2,2 '-(3,3'-dimethylbiphenyldiyl) bis (4,5,6,7-tetrahydro-1-indenyl) zirconium Dichloride, 2,2 '-(3,3'-dimethylbiphenyldiyl) bis (2-methyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, 2,2'
-(3,3'-Dimethylbiphenyldiyl) bis (3-methyl-4,5,
6,7- Tetrahydro-1-indenyl) zirconium dichloride, 2,2 '-(4,4', 6,6'-tetramethylbiphenyldiyl) bis (4,5,6,7-tetrahydro-1-indenyl) Zirconium dichloride, 2,2 '-(4,4', 6,6'-tetramethylbiphenyldiyl) bis (2-methyl-4,5,6,7-tetrahydro
-1-indenyl) zirconium dichloride, 2,2 '-(4,
4 ', 6,6'-Tetramethylbiphenyldiyl) bis (3-methyl
-4,5,6,7- Tetrahydro-1-indenyl) zirconium dichloride. Further, a complex in which a zirconium atom is replaced with a titanium atom or a hafnium atom, and a complex in which a chlorine atom is replaced with a bromine atom, a fluorine atom, an iodine atom or an alkyl group having 1 to 20 carbon atoms such as a methyl group can be given. .

In the present invention, ethylene and α-olefins having 3 to 20 carbon atoms can be exemplified as the olefin. Particularly, polymerization of α-olefin and copolymerization of α-olefins with each other, or α-olefin and a small amount of ethylene. Is preferably applied to the copolymerization of As the α-olefin, specifically, propylene, 1-butene, 1-
Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-
Examples include octadecene, 1-nonadecene, and 1-eicosane.

In the present invention, the olefin is a combination of the metallocene compound represented by the above-mentioned general formula (1), or a combination of the metallocene compound and an aluminoxane or an organometallic compound to produce a stable anionic species. Can be polymerized. The aluminoxane used in combination with the metallocene compound is represented by the following general formula (2)

[0013]

[Chemical 3] Alternatively, a compound represented by General Formula (3) [Chemical Formula 4] may be mentioned.

[0014]

[Chemical 4] (In the general formula (2) or (3), R may be the same or different, is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or hydrogen, and p is 2 to 50, preferably It is an integer of 10 to 35) The ratio of aluminoxane to the above metallocene compound is generally 1 to 10000 mol times.
When using the above aluminoxane, the carbon number is 1
It is also possible to use an organometallic compound such as trialkylaluminum of about 12 in combination, and in this case, the amount of aluminoxane used can be relatively small, for example, 1 to 2000 mol times. The amount of the organometallic compound is usually 1 to 1000 mol times the metallocene compound.

In the present invention, a compound which forms a stable anion species upon contact with an organometallic compound can be used in combination with the metallocene compound. Preferred examples of the organometallic compound include alkyl metal compounds and aryl metal compounds of metals of Groups 1 to 3 of the periodic table, and particularly preferred are organometallic compounds of aluminum, magnesium, and zinc, for example, the metal is aluminum. Examples include triethylaluminum, diethylaluminum hydride and ethylaluminum sesquihydride, such as trialkylaluminum having 1 to 20 carbon atoms in the alkyl group, dialkylaluminum hydride and alkylaluminum sesquihydride, and those whose metal is magnesium include chlorides. Alkyl magnesium halides such as methyl magnesium and dialkyl magnesiums such as dimethyl magnesium, and those whose metal is zinc are dialkyl zincs such as diethyl zinc and Such diaryl zinc, such as phenyl zinc can be exemplified.
In addition, various compounds can be exemplified as the compound which forms a stable anion upon contact with these organometallic compounds, and an ion pair of a stable cation and a stable anion can be preferably exemplified, and specifically, magnesium chloride. Metal halides such as triphenylmethane cation,
Cation such as diphenylamino cation and polyvalent borane, carborane, metallacarborane, ion pair such as polyoxoanion can be preferably exemplified, for example, many of which are exemplified in JP-A-1-501950, 1-502036 and the like. Compounds. . In particular, an ion pair of tetrakispentafluorophenylborane anion and tetrakispentafluorophenylaluminum can be preferably used.

In the present invention, the polymerization can be carried out by a bulk polymerization method or a gas phase polymerization method in addition to the usual solution polymerization method. The polymerization temperature is usually -100 to 200 ° C, preferably room temperature to 100. ℃. The polymerization pressure is not particularly limited and is from normal pressure to 50 kgf / cm ² .

[0017]

EXAMPLES The present invention will be further described with reference to the following examples.

Example 1 (Synthesis of 2,2'-biphenyldiylbis (3-methyl-4,5,6,7-tetrahydro-1-indenyl) titanium dichloride) 2,2'-biphenyldilithium under nitrogen 3-Methyl-4,5,6,7-tetrahydro-1-indanone was added dropwise to the THF solution,
It was hydrolyzed by reacting at room temperature for 3 hours. The obtained 2,2'-bis (3-methyl-4,5,6,7-tetrahydro-1-hydroxyindanyl) biphenyl was dehydrated by heating in decalin and reacted with potassium hydride. To the THF solution of 1.17 g of the obtained 2,2'-bis (3-methyl-4,5,6,7-tetrahydroindenyl) biphenyldipotassium salt, 1.34 g of titanium trichloride 3THF complex was added and refluxed for 3 hours, Further, the mixture was stirred at room temperature for 24 hours. The resulting reddish brown solution was oxidized with hydrochloric acid, extracted with ether, dried and the solution was removed to obtain 1.24 g of a purple solid. This solid was recrystallized from diethyl ether to obtain 0.3 g of deep purple crystals. The analytical values of this compound are shown below. ¹ H-NMR (90 MHz, CDCl ₃ solution, TMS standard) δ: 7.69-7.14 (m, 8
H (+ 8H)), 6.44 (s, 2H), 5.46 (s, 2H), 3.52-1.10 (m, 16H (+16
H)), 2.12 (s.6H), 1.65 (s, 6H), elemental analysis calculated C: 7
1.79%, H: 6.02%, analytical value C: 71.61%, H: 6.13%

(Polymerization) 500 ml of dry heptane was charged into a 1.5 l autoclave which had been sufficiently replaced with nitrogen, and propylene was added to the mixture.
Charged at 0 kgf / cm ² and then synthesized above, 2,2′-biphenyldyl bis (3-methyl-4,5,6,7-tetrahydro-1-
Indenyl) Titanium dichloride 20 mg and Tosoh Akzo Co., Ltd. methylaluminoxane (MAO, concentration 7.80 mol)
/ l) of toluene solution (4.7 ml) was added and the mixture was polymerized at 40 ° C for 1 hour. After the polymerization, a small amount of methanol was added to stop the polymerization, unreacted propylene was purged, the obtained powder was filtered, washed with methanol / hydrochloric acid and further washed with methanol, dried at 80 ° C. and weighed to 1.5. g of polymer was obtained. The intrinsic viscosity of this polymer measured with a 135 ° C. tetralin solution was 2.99 dl / g, and the differential scanning calorimetry (DS
C) is a crystalline polymer with a melting point of 162 ° C and a crystallization temperature of 112 ° C measured at a temperature rising rate of 10 ° C / min and a temperature lowering rate of 10 ° C / min. It was polypropylene.

Example 2 (Synthesis of 2,2'-biphenyldiylbis (3-methyl-4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride) 2,2'-synthesized in Example 1 Bis (3-methyl-4,5,6,7-tetrahydro-1-indenyl) biphenyldipotassium salt 1.5
1.21 g of zirconium tetrachloride 2TH in 9 g of THF solution
The F complex was added and the mixture was refluxed for 4 hours and further stirred at room temperature for one day. The solvent was evaporated from the obtained yellow solution, and the obtained solid was extracted with hot hexane for 3 days to obtain 0.3 g of a yellow solid. Further recrystallized from THF / ethyl ether to 0.
1 g of pale yellow plate crystals were obtained. The analytical values of this compound are shown below. ¹ H-NMR (90 MHz, CDCl ₃ solution, TMS standard) δ: 7.72-7.09 (m, 8
H (+ 8H)), 6.07 (d, 2H), 5.49 (d, 2H), 2.96-0.89 (m, 16H (+16
H)), 2.15 (s, 6H), 1.75 (s.6H), Elemental analysis value Calculated value C: 6
6.41%, H: 5.57%, analytical value C: 66.12%, H: 5.65%

(Polymerization) 2,2'-biphenyldiylbis (3-
Methyl-4,5,6,7-tetrahydro-1-indenyl) Titanium dichloride Change to 20 mg 2,2'-biphenyldylbis (3-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride 10 mg And 2.2 ml of a toluene solution of methylaluminoxane (MAO, concentration 7.80 mol / l) manufactured by Tosoh Akzo Co., Ltd. was used.
16 g of polymer was obtained. The intrinsic viscosity of this polymer measured with a 135 ° C tetralin solution was 0.65 dl / g, and the melting point measured with DSC at a temperature rising rate of 10 ° C / min and a temperature lowering rate of 10 ° C / min.
It was a crystalline polymer at 148 ° C and a crystallization temperature of 106 ° C, and was an isotactic polypropylene according to the infrared absorption spectrum.

[0022]

Industrial Applicability By carrying out the method of the present invention, it is possible to produce a highly stereoregular polymer of an olefin with a high yield, which is extremely valuable industrially.

Claims (4)

[Claims] 1. A novel metallocene compound represented by the following general formula (1) [Chemical formula 1]. [Chemical 1] (In the formula, L represents an indenyl group or a tetrahydroindenyl group which may be substituted with an alkyl group or a silicon-containing hydrocarbon residue, and X is an optionally substituted 2,
2′-substituted biphenyl group, M is a trivalent or tetravalent metal selected from Ti, Hf and Zr, Y is a halogen atom or an alkyl group having 1 to 20 carbon atoms, and m is 1 or 2. ) 2. A method for polymerizing an olefin, which comprises polymerizing an olefin using a metallocene compound represented by the general formula (1). 3. The method according to claim 2, wherein the metallocene compound represented by the general formula (1) and an aluminoxane are used in combination. 4. The method according to claim 2, wherein the metallocene compound represented by the general formula (1) is used in combination with a compound which produces a stable anion species by contacting with the organometallic compound.