Ethylene/α-olefin copolymers and lubricating oils

Abstract

The invention has an object of providing ethylene/-olefin copolymers having high randomness and a small number of double bonds in the copolymers. The ethylene/-olefin copolymers of the invention are obtained by copolymerizing ethylene and an -olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst which includes a bridged metallocene compound (A) represented by the formula [I], and at least one compound (B) selected from organometallic compounds (B-1), organoaluminum oxy compounds (B-2) and compounds (B-3) capable of reacting with the bridged metallocene compound (A) to form an ion pair, and have a specific weight average molecular weight, a specific molecular weight distribution, a specific glass transition point and a specific value B. ##STR00001##

Claims

1. An ethylene/-olefin copolymer obtained by copolymerizing ethylene and an -olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising: a bridged metallocene compound (A) represented by the general formula [I] below, and at least one compound (B) selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2) and compounds (B-3) capable of reacting with the bridged metallocene compound (A) to form an ion pair, the ethylene/-olefin copolymer satisfying the following conditions (1) to (4): (1) the weight average molecular weight is in the range of 1,000 to 50,000; (2) the molecular weight distribution (Mw/Mn, Mw: weight average molecular weight, Mn: number average molecular weight) measured by gel permeation chromatography (GPC) is not more than 2.5; (3) the glass transition point (Tg) measured with a differential scanning calorimeter (DSC) is below 50 C.; and (4) the value B represented by the equation [1] below is not less than 1.2; $\begin{array}{cc}\left[\mathrm{Math}.1\right]& \\ B=\frac{P_{\mathrm{OE}}}{2P_O.Math.P_E}& \left[1\right]\end{array}$ (in the equation [1], PE is the molar fraction of ethylene components, PO is the molar fraction of -olefin components, and P.sub.OE is the molar fraction of ethylene -olefin sequences relative to all dyad sequences); ##STR00010## (in the formula [I], R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are all hydrogen atoms, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are each an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and may be the same as or different from one another, R.sup.13 and R.sup.14 are each an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and may be the same as or different from each other, any adjacent substituents among R.sup.1 to R.sup.14 may be bonded together to form a ring, Y is selected from Group XIV atoms, M is a titanium atom, a zirconium atom or a hafnium atom, Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of coordination through a lone pair of electrons, and may be the same or different when plural, n is 1, and j is an integer of 1 to 4).

2. The ethylene/-olefin copolymer according to claim 1, wherein one of R.sup.13 and R.sup.14 in the general formula [I] is an aryl group or a substituted aryl group.

3. The ethylene/-olefin copolymer according to claim 2, wherein one of R.sup.13 and R.sup.14 in the general formula [I] is an aryl group or a substituted aryl group and the other is an alkyl group having 1 to 20 carbon atoms.

4. The ethylene/-olefin copolymer according to claim 1, wherein M in the general formula [I] is a zirconium atom.

5. The ethylene/-olefin copolymer according to claim 1, wherein the compound (B-3) is used as the component (B).

6. The ethylene/-olefin copolymer according to claim 1, wherein the polymerization temperature in the copolymerization is not less than 130 C.

7. The ethylene/-olefin copolymer according to claim 1, wherein the copolymer contains ethylene-derived structural units in the range of 30 to 70 mol %.

8. A lubricating oil composition comprising the ethylene/-olefin copolymer described in claim 1.

9. An automobile lubricating oil comprising the lubricating oil composition described in claim 8.

10. The automobile lubricating oil according to claim 9, which is used as an automobile transmission oil and has a kinematic viscosity at 100 C. of not more than 7.5 mm.sup.2/s.

11. An industrial lubricating oil comprising the lubricating oil composition described in claim 8.

12. A lubricating oil composition comprising the ethylene/-olefin copolymer of claim 1.

13. An automobile lubricating oil comprising the lubricating oil composition described in claim 12.

14. The automobile lubricating oil according to claim 13, which is used as an automobile transmission oil and has a kinematic viscosity at 100 C. of not more than 7.5 mm.sup.2/s.

15. An industrial lubricating oil comprising the lubricating oil composition described in claim 12.

Description

EXAMPLES

(1) The present invention will be described in further detail based on examples hereinbelow without limiting the scope of the invention to such examples.

(2) [Evaluation Methods]

(3) In the following description such as Examples and Comparative Examples, properties and characteristics of ethylene/-olefin copolymers and lubricating oil compositions were measured by the following methods.

(4) Ethylene content (mol %)

(5) With Fourier transform infrared spectrophotometer FT/IR-610 or FT/IR-6100 manufactured by JASCO Corporation, the absorbance ratio (D1155 cm.sup.1/D721 cm.sup.1) of the absorption near 1155 cm.sup.1 based on the framework vibrations of propylene to the absorption near 721 cm.sup.1 based on the transverse vibrations of long-chain methylene groups was calculated. The ethylene content (wt %) was determined based on a calibration curve prepared beforehand (using standard samples in accordance with ASTM D3900). Subsequently, the propylene content (wt %) was obtained by subtracting the ethylene content (wt %) obtained above from 100 wt %. Next, the ethylene content (mol %) was determined using the following equation based on the ethylene content (wt %) and the propylene content (wt %).

(6) $\begin{array}{cc}\left[\mathrm{Math}.3\right]& \\ \mathrm{Ethylene}\mathrm{content}\left(\mathrm{mol}\%\right)=\frac{\left[\mathrm{Ethylene}\mathrm{content}\left(\mathrm{wt}\%\right)28\right]}{\begin{array}{c}\left[\mathrm{Ethylene}\mathrm{content}\left(\mathrm{wt}\%\right)28\right]+\\ \left[\mathrm{Propylene}\mathrm{content}\left(\mathrm{wt}\%\right)42\right]\end{array}}& \end{array}$
Value B

(7) A .sup.13C NMR spectrum was measured in o-dichlorobenzene/benzene-d.sub.5 (4/1 [vol/vol %]) as a measurement solvent at a measurement temperature of 120 C., a spectrum width of 250 ppm, a pulse repetition time of 5.5 sec and a pulse width of 4.7.Math.sec (45 pulse) (100 MHz, ECX400P manufactured by JEOL Ltd.) or at a measurement temperature of 120 C., a spectrum width of 250 ppm, a pulse repetition time of 5.5 sec and a pulse width of 5.0.Math.sec (45 pulse) (125 MHz, AVANCE III cryo-500 manufactured by Bruker BioSpin K.K.). The value B was calculated based on the equation [1] below.

(8) $\begin{array}{cc}\left[\mathrm{Math}.4\right]& \\ B=\frac{P_{\mathrm{OE}}}{2P_O.Math.P_E}& \left[1\right]\end{array}$

(9) In the equation [1], P.sub.E is the molar fraction of ethylene components, P.sub.O is the molar fraction of -olefin components, and P.sub.OE is the molar fraction of ethylene.-olefin sequences relative to all the dyad sequences.

(10) Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn) and Molecular Weight Distribution (Mw/Mn)

(11) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured as described below using GPC (HLC-8320GPC) manufactured by TOSOH CORPORATION. TSKgel SuperMultipore HZ-M (four columns) were used as separation columns. The column temperature was 40 C. Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a mobile phase. The developing speed was 0.35 ml/min. The sample concentration was 5.5 g/L. The sample injection amount was 20 l. A differential refractometer was used as a detector. Standard polystyrenes manufactured by TOSOH CORPORATION (PStQuick MP-M) were used. The average molecular weights were calculated relative to the molecular weights of the polystyrenes in accordance with general calibration procedures.

(12) The molecular weight distribution (Mw/Mn) was calculated by dividing the Mw measured by the above measurement method by the Mn measured by the above measurement method.

(13) Intrinsic Viscosity ([])

(14) The measurement was performed in decal in solvent at 135 C. Approximately 20 mg of the polymer was dissolved in 15 ml of decalin, and the specific viscosity .sub.sp was measured in an oil bath at 135 C. This decalin solution was diluted by the addition of 5 ml of decalin solvent, and the specific viscosity .sub.sp was measured in the similar manner. This dilution operation was repeated two more times, and the concentration (C) was extrapolated to zero. The .sub.sp/C value at the zero concentration was obtained as the intrinsic viscosity.
[]=lim(.sub.sp/C)(C.fwdarw.0)
Number of Double Bonds in Molecular Chains

(15) A .sup.1H NMR spectrum was measured in o-dichlorobenzene-d.sub.4 as a measurement solvent at a measurement temperature of 120 C., a spectrum width of 20 ppm, a pulse repetition time of 7.0 sec and a pulse width of 6.15 sec (45 pulse) (400 MHz, ECX400P manufactured by JEOL Ltd.). The number of double bonds was calculated based on the results.

(16) DSC Measurement

(17) X-DSC-7000 manufactured by Seiko Instruments Inc. was used. Approximately 8 mg of the ethylene/-olefin copolymer was placed into a readily closable aluminum sample pan, and the pan was arranged in the DSC cell. In a nitrogen atmosphere, the DSC cell was heated from room temperature to 150 C. at 10 C./min and was held at 150 C. for 5 minutes. Thereafter, the DSC cell was cooled to 100 C. at 10 C./min (cooling process). Next, the cell was held at 100 C. for 5 minutes and was heated at 10 C./min. With respect to the enthalpy curve recorded during this heating process, the intersection point of the tangent at the inflection point was obtained as the glass transition point (Tg). The determination of the glass transition point (Tg) was based on JIS K7121 9.3.

(18) Viscosity Characteristics

(19) The kinematic viscosity at 100 C., the kinematic viscosity at 40 C., and the viscosity index were measured and calculated by the methods described in JIS K2283.

(20) KRL Shear Stability

(21) The shear stability of the lubricating oil composition was evaluated with a KRL shear stability tester in accordance with the method described in DIN 52350-6. The blended oil was subjected to shear conditions (1450 rpm) at 60 C. for 20 hours and the decrease in kinematic viscosity at 100 C. between before and after the testing was determined.

(22) The durability is good when the decrease in kinematic viscosity after the application of shear stress by the above method is less than 10%. The durability is extremely excellent when the decrease in kinematic viscosity is less than 5%.

(23) Ultrasonic Shear Stability

(24) To evaluate the ultrasonic shear stability, the lubricating oil composition was ultrasonicated for 60 minutes in accordance with JASO M347 and the decrease in kinematic viscosity at 100 C. between before and after the testing was determined.

(25) The durability is good when the decrease in kinematic viscosity after the application of shear stress by the above method is less than 5%. The durability is extremely excellent when the decrease in kinematic viscosity is less than 1%.

(26) Low-Temperature Viscosity

(27) The low-temperature viscosity was measured at a prescribed temperature with a Brookfield viscometer in accordance with ASTM D2983.

(28) Synthesis of Metallocene Compounds

(29) The metallocene compounds used in Examples and Comparative Examples were synthesized by the following methods. The structures of the metallocene compounds synthesized and of the precursors of the compounds were identified by measuring data such as .sup.1H NMR spectra (270 MHz, GSH-270 manufactured by JEOL Ltd.) and FD-mass (hereinafter, written as FD-MS) spectra (SX-102A manufactured by JEOL Ltd.).

Synthetic Example 1

Synthesis of [methylphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-butylfluorenyl)]zirconium dichloride

(i) Synthesis of 6-methyl-6-phenylfulvene

(30) In a nitrogen atmosphere, a 200 mL three-necked flask was loaded with 7.3 g (101.6 mmol) of lithium cyclopentadiene and 100 mL of dehydrated tetrahydrofuran. The mixture was stirred. The resultant solution was cooled in an ice bath, and 15.0 g (111.8 mmol) of acetophenone was added dropwise. The mixture was stirred at room temperature for 20 hours. The resultant solution was quenched with an aqueous diluted hydrochloric acid solution. 100 mL of hexane was added, and soluble components were extracted. The organic phase was then washed with water and saturated brine and was dried with anhydrous magnesium sulfate. Thereafter, the solvent was distilled off, and the resultant viscous liquid was separated by column chromatography (hexane) to give the target product (a red viscous liquid) (amount 14.7 g, yield 78%). .sup.1H NMR spectroscopy identified the product to be 6-methyl-6-phenylfulvene. The measured values are given below.

(31) .sup.1H NMR spectrum (270 MHz, CDCl.sub.3): /ppm 7.39 (m, 5H), 6.64 (m, 1H), 6.57 (m, 1H), 6.48 (m, 1H), 6.18 (m, 1H), 2.54 (s, 3H).

(ii) Synthesis of methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane

(32) In a nitrogen atmosphere, a 100 mL three-necked flask was loaded with 2.01 g (7.20 mmol) of 2,7-di-t-butylfluorene and 50 mL of dehydrated t-butyl methyl ether. While performing cooling in an ice bath, 4.60 mL (7.59 mmol) of a (1.65 M) n-butyllithium/hexane solution was added gradually. The mixture was stirred at room temperature for 16 hours. Further, 1.66 g (9.85 mmol) of 6-methyl-6-phenylfulvene was added, and the mixture was stirred for 1 hour while performing heating under reflux. While performing cooling in an ice bath, 50 mL of water was added gradually. The resultant two-phase solution was transferred to a 200 mL separatory funnel. After 50 mL of diethyl ether had been added, the funnel was shaken several times and the aqueous phase was removed. The organic phase was washed with 50 mL of water three times and with 50 mL of saturated brine one time. The liquid was dried with anhydrous magnesium sulfate for 30 minutes and thereafter the solvent was distilled off under reduced pressure. A small amount of hexane was added, and the solution was ultrasonicated. The resultant solid precipitate was recovered, washed with a small amount of hexane, and dried under reduced pressure to afford 2.83 g (6.34 mmol, 88.1%) of methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane as a white solid. FD-MS spectroscopy identified the product to be methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane. The measured value is given below.

(33) FD-MS spectrum: M/z 446 (M.sup.+).

(iii) Synthesis of [methylphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-butylfluorenyl)]zirconium dichloride

(34) In a nitrogen atmosphere, a 100 mL Schlenk flask was loaded sequentially with 1.50 g (3.36 mmol) of methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane, 50 mL of dehydrated toluene and 570 L (7.03 mmol) of THF. While performing cooling in an ice bath, 4.20 mL (6.93 mmol) of a (1.65 M) n-butyllithium/hexane solution was added gradually. The mixture was stirred at 45 C. for 5 hours. The solvent was distilled off under reduced pressure, and 40 mL of dehydrated diethyl ether was added. The addition resulted in a red solution. While performing cooling in a methanol/dry ice bath, 728 mg (3.12 mmol) of zirconium tetrachloride was added. Stirring was performed for 16 hours while increasing the temperature gradually to room temperature, resulting in a red orange slurry. The solvent was distilled off under reduced pressure. In a glove box, the resultant solid was washed with hexane and was extracted with dichloromethane. The extract was concentrated by distilling off the solvent under reduced pressure. A small amount of hexane was added to the concentrate, and the mixture was allowed to stand at 20 C. The resultant red orange solid precipitate was washed with a small amount of hexane and was dried under reduced pressure. In this manner, 1.20 g (1.98 mmol, 63.3%) of [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-but ylfluorenyl)]zirconium dichloride was obtained as a red orange solid. .sup.1H NMR spectroscopy identified the product to be [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-but ylfluorenyl)]zirconium dichloride. The measured values are given below.

(35) .sup.1H NMR spectrum (270 MHz, CDCl.sub.3): /ppm 8.02 (d, J=8.9 Hz, 1H), 7.96 (d, J=9.1 Hz, 1H), 7.89-7.86 (br, 1H), 7.78 (br, 1H), 7.69-7.62 (m, 2H), 7.59-7.50 (m, 2H), 7.44-7.38 (m, 2H), 6.40-6.37 (m, 1H), 6.28-6.25 (m, 1H), 6.05 (br, 1H), 5.81-5.78 (m, 1H), 5.60-5.57 (m, 1H), 2.53 (s, 3H), 1.37 (s, 9H), 0.95 (s, 9H).

Synthetic Example 2

Synthesis of [diphenylmethylene[5-(2-methyl-4-i-propylcyclopentadienyl)](5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride

(i) Synthesis of 1-methyl-3-i-propyl-6,6-diphenylfulvene

(36) In a nitrogen atmosphere, a 200 mL three-necked flask was loaded with 2.13 g of 1-methyl-3-i-propylcyclopentadiene (GC purity: 88.5%) and 100 mL of dehydrated THF. While performing cooling in an ice bath, 10.7 mL (17.4 mmol) of a (1.63 M) n-butyllithium/hexane solution was added gradually. The mixture was stirred at room temperature for 4 hours. While performing cooling again in an ice bath, 2.37 g (20.7 mmol) of DMI was added gradually. The mixture was stirred at room temperature for 30 minutes. Thereafter, 3.49 g (19.2 mmol) of benzophenone was added, and the mixture was stirred for 20 hours while performing heating under reflux. While performing cooling in an ice bath, 50 mL of water was gradually added and further 50 mL of diethyl ether was added. The mixture was stirred at room temperature for 30 minutes. The resultant two-phase solution was transferred to a 500 mL separatory funnel. The organic phase was washed with 100 mL of water three times and with 100 mL of saturated brine one time. The liquid was dried with anhydrous magnesium sulfate for 30 minutes and thereafter the solvent was distilled off under reduced pressure. An orange brown solid was thus obtained. The product was separated by silica gel chromatography (300 g, hexane) to afford a red solution. The solvent was distilled off under reduced pressure. In this manner, 2.09 g (7.29 mmol) of 1-methyl-3-i-propyl-6,6-diphenylfulvene was obtained as a red oily product. .sup.1H NMR spectroscopy identified the product to be 1-methyl-3-i-propyl-6,6-diphenylfulvene. The measured values are given below.

(37) .sup.1H NMR spectrum (270 MHz, CDCl.sub.3): /ppm 7.36-7.22 (m, 10H), 6.25-6.23 (m, 1H), 5.74-5.73 (m, 1H), 2.68-2.52 (m, 1H), 1.48 (d, J=1.4 Hz, 3H), 1.12 (d, J=6.8 Hz, 6H).

(ii) Synthesis of (2-methyl-4-i-propylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)diphenylmethane

(38) In a nitrogen atmosphere, a 200 mL three-necked flask was loaded with 1.73 g (4.46 mmol) of octamethyloctahydrodibenzofluorene and 70 mL of dehydrated t-butyl methyl ether. While performing cooling in an ice bath, 2.90 mL (4.73 mmol) of a (1.63 M) n-butyllithium/hexane solution was added gradually. The mixture was stirred at room temperature for 7 hours. Further, 834 mg (2.91 mmol) of 1-methyl-3-i-propyl-6,6-diphenylfulvene was added, and the mixture was stirred for 17 hours while performing heating under reflux and was then cooled to room temperature. While performing cooling in an ice bath, 50 mL of water and subsequently 50 mL of diethyl ether were added gradually. The resultant two-phase solution was transferred to a 500 mL separatory funnel. The funnel was shaken several times and the aqueous phase was removed. The organic phase was washed with 100 mL of water three times and with 100 mL of saturated brine one time. The liquid was dried with anhydrous magnesium sulfate for 30 minutes and thereafter the solvent was distilled off under reduced pressure. The resultant solid was washed with methanol and was separated by silica gel chromatography (60 g, hexane) to afford a colorless solution. The solvent was distilled off under reduced pressure. In this manner, 1.03 g (1.53 mmol, 52.5%) of (2-methyl-4-i-propylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)diphenylmethane was obtained as awhile solid. FD-MS spectroscopy identified the product to be (2-methyl-4-i-propylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)diphenylmethane. The measured value is given below.

(39) FD-MS spectrum: M/z 673 (M.sup.+).

(iii) Synthesis of [diphenylmethylene[5-(2-methyl-4-i-propylcyclopentadienyl)](5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride

(40) In a nitrogen atmosphere, a 100 mL Schlenk flask was loaded sequentially with 926 mg (1.38 mmol) of (2-methyl-4-i-propylcyclopentadienyl)(octamethyloctahydrod ibenzofluorenyl)diphenylmethane, 30 mL of dehydrated toluene and 0.24 mL (3.0 mmol) of dehydrated THF. While performing cooling in an ice bath, 1.80 mL (2.93 mmol) of a (1.63 M) n-butyllithium/hexane solution was added gradually. The mixture was stirred at 45 C. for 4 hours to form a red solution. The solvent was distilled off under reduced pressure, and 30 mL of dehydrated diethyl ether was added to form again a red solution. While performing cooling in a methanol/dry ice bath, 280 mg (4.27 mmol) of zirconium tetrachloride was added. Stirring was performed for 17 hours while increasing the temperature gradually to room temperature, resulting in a red slurry. The solvent was distilled off under reduced pressure. In a glove box, the resultant solid was extracted with hexane. The extract was concentrated by distilling off the solvent under reduced pressure. Recrystallization was performed at 20 C. The solid precipitated was washed with a small amount of hexane and was dried under reduced pressure. In this manner, 345 mg (0.414 mmol, 34.5%) of [diphenylmethylene[.sup.5-(2-methyl-4-i-propylcyclopentadienyl)](.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride was obtained as a red solid. .sup.1H NMR spectroscopy and FD-MS spectroscopy identified the product to be [diphenylmethylene[.sup.5-(2-methyl-4-i-propylcyclopentadienyl)](.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride. The measured values are given below.

(41) .sup.1H NMR spectrum (270 MHz, CDCl.sub.3): /ppm 8.07-7.93 (m, 5H), 7.80-7.76 (m, 1H), 7.48-7.19 (m, 6H), 6.96 (s, 1H), 6.04 (s, 1H), 5.99 (d, J=3.0 Hz, 1H), 5.40 (d, J=3.0 Hz, 1H), 2.57 (sep, J=7.0 Hz, 1H), 1.85 (s, 3H), 1.7-1.6 (br m, 8H), 1.50 (s, 3H), 1.47 (s, 3H), 1.43 (s, 3H), 1.40 (s, 3H), 1.11 (d, J=7.0 Hz, 3H), 1.07 (s, 3H), 1.01 (d, J=7.0 Hz, 3H), 0.88 (s, 3H), 0.86 (s, 3H), 0.77 (s, 3H)

(42) FD-MS spectrum: M/z 832 (M.sup.+).

Synthesis of Other Metallocene Compounds

(43) [Ethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride was synthesized by a method described in Japanese Patent No. 4367687.

(44) [Diphenylmethylene(.sup.5-2-methyl-4-t-butylcyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride was synthesized by a method described in WO 2004/087775.

(45) [Dimethylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride was synthesized by a method described in JP-A-H04-69394.

(46) [Diphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride was synthesized by a method described in JP-A-H06-172433.

(47) [Diphenylsilylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride was synthesized by a method described in J. Organomet. Chem., 509, 63 (1996).

(48) [Bis(.sup.5-1,3-dimethylcyclopentadienyl)]zirconium dichloride was synthesized by a method described in JP-B-H06-62642.

(49) [Bis(.sup.5-1-methyl-3-n-butylcyclopentadienyl)]zirconium dichloride was synthesized by a method described in WO 95/04761.

(50) [Production of Ethylene/-Olefin Copolymers]

(51) Ethylene/-olefin copolymers were produced in Examples and Comparative Examples described below. The ethylene/-olefin copolymers obtained were hydrogenated by the method described below as required. Data such as the production conditions in Examples and Comparative Examples, and the properties of the ethylene/-olefin copolymers obtained are shown in Table 1 and Table 2.

(52) Hydrogenation Process

(53) A 1 L-volume stainless steel autoclave was loaded with 100 mL of a hexane solution of a 0.5 mass % Pd/alumina catalyst and 500 mL of a 30 mass % hexane solution of the ethylene/-olefin copolymer. After being tightly closed, the autoclave was purged with nitrogen. Next, the temperature was increased to 140 C. while performing stirring and the system was purged with hydrogen. The pressure was raised with hydrogen to 1.5 MPa and the hydrogenation reaction was performed for 15 minutes.

Example 1

Ethylene/Propylene Copolymerization with [ethylene(5-cyclopentadienyl)(5-2,7-di-t-butylfluorenyl)]zirconium dichloride (50 C.)

(54) A 1 L-volume glass polymerizer that had been thoroughly purged with nitrogen was loaded with 250 mL of heptane. After the temperature of the system had been increased to 50 C., 25 L/hr of ethylene, 75 L/hr of propylene and 100 L/hr of hydrogen were continuously supplied to the polymerizer. The mixture was stirred at a rotational speed of 600 rpm. Next, 0.2 mmol of triisobutylaluminum was added to the polymerizer. Subsequently, a mixture obtained beforehand by mixing 0.688 mmol of MMAO and 0.00230 mmol of [ethylene(.sup.5-cyclopentadienyl) (.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride for at least 15 minutes in toluene was fed to the polymerizer thereby to initiate the polymerization. The polymerization was performed at 50 C. for 15 minutes while continuously supplying ethylene, propylene and hydrogen. The polymerization was terminated by the addition of a small amount of isobutyl alcohol to the system. The unreacted monomers were purged. The polymer solution obtained was washed with 100 mL of 0.2 mol/L hydrochloric acid three times and with 100 mL of distilled water three times, and was dried with magnesium sulfate. The solvent was distilled off under reduced pressure. The polymer was dried at 80 C. under reduced pressure overnight. As a result, 1.43 g of the ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 48.4 mol %, Mw of 17430, Mw/Mn of 2.1, [] of 0.23 dl/g, Tg of 63 C. and a value B of 1.3. In the molecular chains, the number of vinyl double bonds was 0.05, that of vinylidene double bonds was 0.29, that of disubstituted olefin double bonds was <0.01, and that of trisubstituted olefin double bonds was 0.09 (per 1000 carbon atoms).

Example 2

Ethylene/Propylene Copolymerization with [diphenylmethylene(5-2-methyl-4-t-butylcyclopentadienyl)(5-2,7-di-t-butylfluorenyl)]zirconium dichloride (50 C.)

(55) The polymerization was performed in the same manner as in Example 1, except that 0.00230 mmol of [ethylene (.sup.5-cyclopentadienyl) (.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride was replaced by 0.00202 mmol of [diphenylmethylene(.sup.5-2-methyl-4-t-butylcyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride, 0.688 mmol of MMAO was replaced by 0.607 mmol of MMAO, the flow rate of ethylene was changed from 25 L/hr to 55 L/hr, and the flow rate of propylene was changed from 75 L/hr to 45 L/hr. As a result, 1.60 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 51.3 mol %, Mw of 18380, Mw/Mn of 1.8, [] of 0.24 dl/g, Tg of 62 C. and a value B of 1.1. In the molecular chains, the number of vinyl double bonds was 0.04, that of vinylidene double bonds was 0.12, that of disubstituted olefin double bonds was <0.01, and that of trisubstituted olefin double bonds was 0.06 (per 1000 carbon atoms).

Example 3

Ethylene/Propylene Copolymerization with [dimethylmethylene(5-cyclopentadienyl) (5-2,7-di-t-butylfluorenyl)]zirconium dichloride (50 C.)

(56) The polymerization was performed in the same manner as in Example 1, except that 0.00230 mmol of [ethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)] zirconium dichloride was replaced by 0.00215 mmol of [dimethylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride, 0.688 mmol of MMAO was replaced by 0.645 mmol of MMAO, the flow rate of ethylene was changed from 25 L/hr to 55 L/hr, and the flow rate of propylene was changed from 75 L/hr to 45 L/hr. As a result, 1.40 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 54.3 mol %, Mw of 28805, Mw/Mn of 1.9, [] of 0.34 dl/g, Tg of 60 C. and a value B of 1.3. In the molecular chains, the number of vinyl double bonds was 0.13, that of vinylidene double bonds was 1.10, that of disubstituted olefin double bonds was <0.01, and that of trisubstituted olefin double bonds was 0.29 (per 1000 carbon atoms).

Example 4

Ethylene/Propylene Copolymerization with [diphenylsilylene(5-cyclopentadienyl) (5-2,7-di-t-butylfluorenyl)]zirconium dichloride (50 C.)

(57) The polymerization was performed in the same manner as in Example 1, except that 0.00230 mmol of [ethylene (.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)] zirconium dichloride was replaced by 0.00288 mmol of [diphenylsilylene(.sup.5-cyclopentadienyl) (.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride, 0.688 mmol of MMAO was replaced by 0.868 mmol of MMAO, the flow rate of ethylene was changed from 25 L/hr to 35 L/hr, and the flow rate of propylene was changed from 75 L/hr to 65 L/hr. As a result, 2.31 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 50.6 mol %, Mw of 27184, Mw/Mn of 1.9, [] of 0.32 dl/g, Tg of 61 C. and a value B of 1.3. In the molecular chains, the number of vinyl double bonds was <0.01, that of vinylidene double bonds was 0.14, that of disubstituted olefin double bonds was <0.01, and that of trisubstituted olefin double bonds was <0.01 (per 1000 carbon atoms).

Example 5

Ethylene/propylene copolymerization with [methylphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-but ylfluorenyl)]zirconium dichloride (50 C.)

(58) The polymerization was performed in the same manner as in Example 1, except that 0.00230 mmol of [ethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)] zirconium dichloride was replaced by 0.00397 mmol of [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-but ylfluorenyl)]zirconium dichloride, 0.688 mmol of MMAO was replaced by 1.192 mmol of MMAO, the flow rate of ethylene was changed from 25 L/hr to 55 L/hr, and the flow rate of propylene was changed from 75 L/hr to 45 L/hr. As a result, 1.59 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 49.9 mol %, Mw of 34238, Mw/Mn of 1.9, [] of 0.40 dl/g, Tg of 60 C. and a value B of 1.3. In the molecular chains, the number of vinyl double bonds was 0.08, that of vinylidene double bonds was 0.90, that of disubstituted olefin double bonds was <0.01, and that of trisubstituted olefin double bonds was 0.22 (per 1000 carbon atoms).

Example 6

Ethylene/Propylene Copolymerization with [methylphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-butylfluorenyl)]zirconium dichloride (130 C.)

(59) A 1 L-volume glass polymerizer that had been thoroughly purged with nitrogen was loaded with 250 mL of decane. After the temperature of the system had been increased to 130 C., 25 L/hr of ethylene, 75 L/hr of propylene and 100 L/hr of hydrogen were continuously supplied to the polymerizer. The mixture was stirred at a rotational speed of 600 rpm. Next, 0.2 mmol of triisobutylaluminum was added to the polymerizer. Subsequently, a mixture obtained beforehand by mixing 1.213 mmol of MMAO and 0.00402 mmol of [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride for at least 15 minutes in toluene was fed to the polymerizer thereby to initiate the polymerization. The polymerization was performed at 130 C. for 15 minutes while continuously supplying ethylene, propylene and hydrogen. The polymerization was terminated by the addition of a small amount of isobutyl alcohol to the system. The unreacted monomers were purged. The polymer solution obtained was washed with 100 mL of 0.2 mol/L hydrochloric acid three times and with 100 mL of distilled water three times, and was dried with magnesium sulfate. The solvent was distilled off under reduced pressure. The polymer was dried at 80 C. under reduced pressure overnight. As a result, 0.77 g of the ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 54.9 mol %, Mw of 4987, Mw/Mn of 1.8, [] of 0.08 dl/g, Tg of 71 C. and a value B of 1.2. In the molecular chains, the number of vinyl double bonds was 1.09, that of vinylidene double bonds was 1.74, that of disubstituted olefin double bonds was 0.11, and that of trisubstituted olefin double bonds was 0.28 (per 1000 carbon atoms).

Example 7

Ethylene/propylene copolymerization with [diphenylmethylene(5-2-methyl-4-i-propylcyclopentadienyl)(5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride

(60) A 2 L-volume stainless steel autoclave that had been thoroughly purged with nitrogen was loaded with 780 mL of heptane and 110 g of propylene. After the temperature of the system had been increased to 110 C., the total pressure was increased to 3 MPaG by supplying hydrogen at 1.35 MPa and ethylene at 0.44 MPa. Next, 0.4 mmol of triisobutylaluminum, 0.00025 mmol of [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride and 0.0010 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate were injected with nitrogen. The polymerization was initiated by stirring the mixture at a rotational speed of 400 rpm. The polymerization was performed at 110 C. for 8 minutes while keeping the total pressure at 3 MPaG by continuously supplying ethylene alone. The polymerization was terminated by the addition of a small amount of ethanol to the system. Unreacted ethylene, propylene and hydrogen were purged. The polymer solution obtained was washed with 1000 mL of 0.2 mol/L hydrochloric acid three times and with 1000 mL of distilled water three times, and was dried with magnesium sulfate. The solvent was distilled off under reduced pressure. The polymer was dried at 80 C. under reduced pressure overnight. As a result, 45.6 g of the ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 55.1 mol %, Mw of 12110, Mw/Mn of 1.8, [] of 0.17 dl/g, Tg of 64 C. and a value B of 1.1. In the molecular chains, the number of vinyl double bonds was 0.10, that of vinylidene double bonds was 0.14, that of disubstituted olefin double bonds was <0.01, and that of trisubstituted olefin double bonds was <0.01 (per 1000 carbon atoms). After the hydrogenation process, the total number of such double bonds in the molecular chains was less than 0.1 (per 1000 carbon atoms).

Example 8

Ethylene/Propylene Copolymerization with [diphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-butylfluorenyl)]zirconium dichloride

(61) The polymerization was performed in the same manner as in Example 7, except that the autoclave was loaded with 740 mL of heptane and 130 g of propylene, the system temperature was increased to 150 C., the total pressure was increased to 3 MPaG by supplying hydrogen at 0.65 MPa and ethylene at 0.26 MPa, 0.00025 mmol of [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride and 0.0010 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate were replaced by 0.000075 mmol of [diphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride and 0.00075 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, and the polymerization was performed at 150 C. for 5 minutes. As a result, 18.0 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 53.8 mol %, Mw of 10700, Mw/Mn of 1.8, [] of 0.16 dl/g, Tg of 65 C. and a value B of 1.2. In the molecular chains, the number of vinyl double bonds was 0.35, that of vinylidene double bonds was 0.96, that of disubstituted olefin double bonds was 0.05, and that of trisubstituted olefin double bonds was 0.07 (per 1000 carbon atoms). After the hydrogenation process, the total number of such double bonds in the molecular chains was 0.3 (per 1000 carbon atoms).

Example 9

Ethylene/Propylene Copolymerization with [methylphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-but ylfluorenyl)]zirconium dichloride

(62) The polymerization was performed in the same manner as in Example 7, except that the autoclave was loaded with 850 mL of heptane and 75 g of propylene, the system temperature was increased to 150 C., the total pressure was increased to 3 MPaG by supplying hydrogen at 1.56 MPa and ethylene at 0.11 MPa, 0.00025 mmol of [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride and 0.0010 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate were replaced by 0.00015 mmol of [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-but ylfluorenyl)]zirconium dichloride and 0.0015 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, and the polymerization was performed at 150 C. for 5 minutes. As a result, 25.1 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 48.8 mol %, Mw of 3570, Mw/Mn of 1.8, [] of 0.06 dl/g, Tg of 76 C. and a value B of 1.1. In the molecular chains, the number of vinyl double bonds was 0.70, that of vinylidene double bonds was 2.51, that of disubstituted olefin double bonds was 0.02, and that of trisubstituted olefin double bonds was 0.15 (per 1000 carbon atoms). After the hydrogenation process, the total number of such double bonds in the molecular chains was less than 0.1 (per 1000 carbon atoms).

Example 10

Ethylene/Propylene Copolymerization with [methylphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-but ylfluorenyl)]zirconium dichloride

(63) The polymerization was performed in the same manner as in Example 7, except that the autoclave was loaded with 710 mL of heptane and 145 g of propylene, the system temperature was increased to 150 C., the total pressure was increased to 3 MPaG by supplying hydrogen at 0.40 MPa and ethylene at 0.27 MPa, 0.00025 mmol of [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride and 0.0010 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate were replaced by 0.00010 mmol of [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-but ylfluorenyl)]zirconium dichloride and 0.001 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, and the polymerization was performed at 150 C. for 5 minutes. As a result, 52.2 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 53.1 mol %, Mw of 9660, Mw/Mn of 1.9, [] of 0.14 dl/g, Tg of 66 C. and a value B of 1.2. In the molecular chains, the number of vinyl double bonds was 0.59, that of vinylidene double bonds was 2.14, that of disubstituted olefin double bonds was 0.06, and that of trisubstituted olefin double bonds was 0.25 (per 1000 carbon atoms). After the hydrogenation process, the total number of such double bonds in the molecular chains was 0.2 (per 1000 carbon atoms).

Example 11

Ethylene/Propylene Copolymerization with [methylphenylmethylene(5-cyclopentadienyl)(5-2,7-di-t-but ylfluorenyl)]zirconium dichloride

(64) The polymerization was performed in the same manner as in Example 7, except that the autoclave was loaded with 910 mL of heptane and 45 g of propylene, the system temperature was increased to 130 C., the total pressure was increased to 3 MPaG by supplying hydrogen at 2.24 MPa and ethylene at 0.09 MPa, 0.00025 mmol of [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride and 0.0010 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate were replaced by 0.00060 mmol of [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-but ylfluorenyl)]zirconium dichloride and 0.006 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, and the polymerization was performed at 130 C. for 5 minutes. As a result, 22.9 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 51.9 mol %, Mw of 2680, Mw/Mn of 1.6, [] of 0.05 dl/g, Tg of 77 C. and a value B of 1.1. In the molecular chains, the number of vinyl double bonds was 0.24, that of vinylidene double bonds was 1.39, that of disubstituted olefin double bonds was 0.17, and that of trisubstituted olefin double bonds was 0.05 (per 1000 carbon atoms). After the hydrogenation process, the total number of such double bonds in the molecular chains was less than 0.1 (per 1000 carbon atoms).

Comparative Example 1

Ethylene/Propylene Copolymerization with [bis(5-1,3-dimethylcyclopentadienyl)]zirconium dichloride

(65) The polymerization was performed in the same manner as in Example 7, except that the autoclave was loaded with 210 mL of heptane and 395 g of propylene, the system temperature was increased to 80 C., the total pressure was increased to 3 MPaG by supplying hydrogen in 300 mL and ethylene at 0.32 MPa, 0.00025 mmol of [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride and 0.0010 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate were replaced by 0.00030 mmol of [bis(.sup.5-1,3-dimethylcyclopentadienyl)]zirconium dichloride and 0.003 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, and the polymerization was performed at 80 C. for 5 minutes. As a result, 23.3 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 52.2 mol %, Mw of 4420, Mw/Mn of 2.2, [] of 0.08 dl/g, Tg of 74 C. and a value B of 1.0. In the molecular chains, the number of vinyl double bonds was 0.08, that of vinylidene double bonds was 9.11, that of disubstituted olefin double bonds was 0.08, and that of trisubstituted olefin double bonds was 0.20 (per 1000 carbon atoms). After the hydrogenation process, the total number of such double bonds remaining in the molecular chains was above 1 (per 1000 carbon atoms).

Comparative Example 2

Ethylene/Propylene Copolymerization with [bis(5-1-methyl-3-n-butylcyclopentadienyl)]zirconium dichloride

(66) The polymerization was performed in the same manner as in Example 7, except that the autoclave was loaded with 210 mL of heptane and 395 g of propylene, the system temperature was increased to 80 C., the total pressure was increased to 3 MPaG by supplying hydrogen in 300 mL and ethylene at 0.32 MPa, 0.00025 mmol of [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride and 0.0010 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate were replaced by 0.00030 mmol of [bis(.sup.5-1-methyl-3-n-butylcyclopentadienyl)]zirconium dichloride and 0.003 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, and the polymerization was performed at 80 C. for 5 minutes. As a result, 45.6 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 51.6 mol %, Mw of 4530, Mw/Mn of 2.1, [] of 0.08 dl/g, Tg of 75 C. and a value B of 1.0. In the molecular chains, the number of vinyl double bonds was 0.07, that of vinylidene double bonds was 8.98, that of disubstituted olefin double bonds was 0.11, and that of trisubstituted olefin double bonds was 0.13 (per 1000 carbon atoms). After the hydrogenation process, the total number of such double bonds remaining in the molecular chains was above 1 (per 1000 carbon atoms).

Comparative Example 3

Ethylene/Propylene Copolymerization with [bis(5-1,3-dimethylcyclopentadienyl)]zirconium dichloride (50 C.)

(67) The polymerization was performed in the same manner as in Example 1, except that 0.00230 mmol of [ethylene (.sup.5-cyclopentadienyl) (.sup.5-2,7-di-t-butylfluorenyl)] zirconium dichloride was replaced by 0.00622 mmol of [bis(.sup.5-1,3-dimethylcyclopentadienyl)]zirconium dichloride, 0.688 mmol of MMAO was replaced by 1.871 mmol of MMAO, the flow rate of ethylene was changed from 25 L/hr to 5 L/hr, the flow rate of propylene was changed from 75 L/hr to 95 L/hr, and the flow rate of hydrogen was changed from 100 L/hr to 0 L/hr. As a result, 0.72 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 52.5 mol %, Mw of 4620, Mw/Mn of 2.0, [] of 0.08 dl/g, Tg of 73 C. and a value B of 1.2. In the molecular chains, the number of vinyl double bonds was 0.07, that of vinylidene double bonds was 10.68, that of disubstituted olefin double bonds was 0.08, and that of trisubstituted olefin double bonds was 0.13 (per 1000 carbon atoms).

Comparative Example 4

Ethylene/Propylene Copolymerization with [bis(5-1-methyl-3-n-butylcyclopentadienyl)]zirconium dichloride (50 C.)

(68) The polymerization was performed in the same manner as in Example 1, except that 0.00230 mmol of [ethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)] zirconium dichloride was replaced by 0.00720 mmol of [bis(.sup.5-1-methyl-3-n-butylcyclopentadienyl)]zirconium dichloride, 0.688 mmol of MMAO was replaced by 2.160 mmol of MMAO, the flow rate of ethylene was changed from 25 L/hr to 10 L/hr, the flow rate of propylene was changed from 75 L/hr to 90 L/hr, and the flow rate of hydrogen was changed from 100 L/hr to 0 L/hr. As a result, 1.19 g of an ethylene-propylene copolymer was obtained. The polymer had an ethylene content of 46.9 mol %, Mw of 3627, Mw/Mn of 2.0, [] of 0.06 dl/g, Tg of 76 C. and a value B of 1.2. In the molecular chains, the number of vinyl double bonds was 0.05, that of vinylidene double bonds was 12.35, that of disubstituted olefin double bonds was 0.06, and that of trisubstituted olefin double bonds was 0.11 (per 1000 carbon atoms).

(69) TABLE-US-00001 TABLE 1 Components (B) Ethylene Propylene Hydrogen Polymerization Polymerization Polymer Components (A) (B-1) (B-2) flow rate flow rate flow rate temperature time yield Mileage Type mmol Type mmol Type mmol L/hr L/hr L/hr C. min g kg/mmol-Zr Ex. 1 i 0.00230 a 0.2 b 0.688 25 75 100 50 15 1.43 0.62 Ex. 2 ii 0.00202 a 0.2 b 0.607 55 45 100 50 15 1.60 0.79 Ex. 3 iii 0.00215 a 0.2 b 0.645 55 45 100 50 15 1.40 0.65 Ex. 4 iv 0.00288 a 0.2 b 0.868 35 65 100 50 15 2.31 0.80 Ex. 5 v 0.00397 a 0.2 b 1.192 55 45 100 50 15 1.59 0.40 Ex. 6 v 0.00402 a 0.2 b 1.213 25 75 100 130 15 0.77 0.19 Comp. viii 0.00622 a 0.2 b 1.871 5 95 0 50 15 0.72 0.12 Ex. 3 Comp. ix 0.00720 a 0.2 b 2.160 10 90 0 50 15 1.19 0.17 Ex. 4 Ethylene/ Numbers of double bonds in molecular chains propylene Vinyl Vinylidene Disubstituted Trisubstituted Total contents [] Tg Value Bonds/ Bonds/ Bonds/ Bonds/ Bonds/ mol %/mol % Mw Mn Mw/Mn dl/g C. B 1000 C 1000 C 1000 C 1000 C 1000 C Ex. 1 48.4/51.6 17430 8490 2.1 0.23 63 1.3 0.05 0.29 <0.01 0.09 0.43 Ex. 2 51.3/48.7 18380 10330 1.8 0.24 62 1.1 0.04 0.12 <0.01 0.06 0.22 Ex. 3 54.3/45.7 28805 15363 1.9 0.34 60 1.3 0.13 1.10 <0.01 0.29 1.51 Ex. 4 50.6/49.4 27184 14132 1.9 0.32 61 1.3 <0.01 0.14 <0.01 <0.01 0.14 Ex. 5 49.9/50.1 34238 17888 1.9 0.40 60 1.3 0.08 0.90 <0.01 0.22 1.19 Ex. 6 54.9/45.1 4987 2806 1.8 0.08 71 1.2 1.09 1.74 0.11 0.28 3.22 Comp. 52.5/47.5 4620 2260 2.0 0.08 73 1.2 0.07 10.68 0.08 0.13 10.96 Ex. 3 Comp. 46.9/53.1 3627 1837 2.0 0.06 76 1.2 0.05 12.35 0.06 0.11 12.57 Ex. 4

(70) The types of the components (A), the component (B-1) and the component (B-2) in Table 1 are as follows.

(71) Components (A)

(72) i: [ethylene (.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)] zirconium dichloride ii: [diphenylmethylene(.sup.5-2-methyl-4-t-butylcyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride iii: [dimethylmethylene(.sup.5-cyclopentadienyl) (.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride iv: [diphenylsilylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride v: [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-but ylfluorenyl)]zirconium dichloride viii: [bis(.sup.5-1,3-dimethylcyclopentadienyl)]zirconium dichloride ix: [bis(.sup.5-1-methyl-3-n-butylcyclopentadienyl)]zirconium dichloride
<Component (B-1)> a: triisobutylaluminum
<Component (B-2)> b: MMAO

(73) TABLE-US-00002 TABLE 2 Hydrogen Ethylene Polymer- partial partial Total ization Polymer- Mileage Components (B) Hep- Pro- pres- pres- pres- temper- ization Polymer kg/ Components (A) (B-1) (B-3) tane pylene sure sure sure ature time yield mmol- Type mmol Type mmol Type mmol mL g MPa MPa MPa C. min g Zr Ex. 7 vi 0.00025 a 0.4 c 0.0010 780 110 1.35 0.44 3 110 8 45.6 182 Ex. 8 vii 0.000075 a 0.4 c 0.00075 740 130 0.65 0.26 3 150 5 18.0 240 Ex. 9 v 0.00015 a 0.4 c 0.0015 850 75 1.56 0.11 3 150 5 25.1 167 Ex. 10 v 0.00010 a 0.4 c 0.001 710 145 0.40 0.27 3 150 5 52.2 522 Ex. 11 v 0.00060 a 0.4 c 0.006 910 45 2.24 0.09 3 130 5 22.9 38 Comp. viii 0.00030 a 0.4 c 0.003 210 395 300 mL 0.32 3 80 5 23.3 78 Ex. 1 Comp. ix 0.00030 a 0.4 c 0.003 210 395 300 mL 0.32 3 80 5 45.6 152 Ex. 2 Ethylene/ Numbers of double bonds in molecular chains propylene Vinyl Vinylidene Disubstituted Trisubstituted Total contents [] Tg Value Bonds/ Bonds/ Bonds/ Bonds/ Bonds/ mol %/mol % Mw Mn Mw/Mn dl/g C. B 1000 C 1000 C 1000 C 1000 C 1000 C Ex. 7 55.1/44.9 12110 6760 1.8 0.17 64 1.1 0.10 0.14 <0.01 <0.01 0.24 Ex. 8 53.8/46.2 10700 5810 1.8 0.16 65 1.2 0.35 0.96 0.05 0.07 1.42 Ex. 9 48.8/51.2 3570 2000 1.8 0.06 76 1.1 0.70 2.51 0.02 0.15 3.38 Ex. 10 53.1/46.9 9660 5200 1.9 0.14 66 1.2 0.59 2.14 0.06 0.25 3.04 Ex. 11 51.9/48.1 2680 1640 1.6 0.05 77 1.1 0.24 1.39 0.17 0.05 1.85 Comp. 52.2/47.8 4420 2030 2.2 0.08 74 1.0 0.08 9.11 0.08 0.20 9.46 Ex. 1 Comp. 51.6/48.4 4530 2190 2.1 0.08 75 1.0 0.07 8.98 0.11 0.13 9.28 Ex. 2

(74) The types of the components (A), the component (B-1) and the component (B-3) in Table 2 are as follows.

(75) Components (A)

(76) vi: [diphenylmethylene(.sup.5-2-methyl-4-i-propylcyclopentadienyl)(.sup.5-octamethyloctahydrodibenzofluorenyl)]zirconium dichloride vii: [diphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride v: [methylphenylmethylene(.sup.5-cyclopentadienyl)(.sup.5-2,7-di-t-butylfluorenyl)]zirconium dichloride viii: [bis(.sup.5-1,3-dimethylcyclopentadienyl)]zirconium dichloride ix: [bis(.sup.5-1-methyl-3-n-butylcyclopentadienyl)]zirconium dichloride
<Component (B-1)> a: triisobutylaluminum
<Component (B-3)> c: N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate
[Preparation of Lubricating Oil Compositions]

(77) In the preparation of lubricating oil compositions described below, the following components were used in addition to the ethylene/-olefin copolymers.

(78) Low-viscosity base oils: Synthetic hydrocarbon oil PAO (NEXBASE 2006 manufactured by NESTE, PAO-6) having a kinematic viscosity at 100 C. of 5.8 mm.sup.2/s, API (American Petroleum Institute) Group II mineral oil (YUBASE-L3 (mineral oil A) manufactured by SK LUBRICANTS) having a kinematic viscosity at 100 C. of 3.0 mm.sup.2/s, and API Group III mineral oils (YUBASE-4 (mineral oil B) and YUBASE-6 (mineral oil C) manufactured by SK LUBRICANTS) having kinematic viscosities at 100 C. of 4.2 mm.sup.2/s and 6.5 mm.sup.2/s, respectively.

(79) Polymethacrylates: VISCOPLEX 0-220 (number average molecular weight 23,000, PMA-A) and VISCOPLEX 0-110 (number average molecular weight 9,100, PMA-B) manufactured by EVONIK

(80) Polybutenes: Nisseki Polybutenes HV-1900 (PB-A) and HV-300 (PB-B) manufactured by JX Nippon Oil & Energy Corporation

(81) Fatty acid ester: SYNATIVE ES TSTC manufactured by BASF

(82) Extreme pressure additive package: HITEC-3339 manufactured by AFTON CHEMICAL

(83) Automatic transmission oil DI package: HITEC-2426 manufactured by AFTON CHEMICAL

(84) Pour-point depressant: IRGAFLO 720P manufactured by BASF

(85) Automobile Gear Oils

(86) In Formulation Examples 1 to 3, the formulations were controlled so that the kinematic viscosity at 100 C. would be about 14.0 mm.sup.2/s to meet SAE (Society of Automobile Engineers) Gear Oil Viscosity Grade 90. Table 3 sets forth the lubricating oil characteristics of the lubricating oil compositions obtained in Formulation Examples and Comparative Formulation Examples described below.

Formulation Example 1

(87) The hydrogenated copolymer obtained in Example 9, the fatty acid ester and the extreme pressure additive package were blended so that their proportions would be 40.5 mass %, 15.0 mass % and 3.9 mass %, respectively. PAO-6 was added to the blend in such an amount that the total mass would be 100 mass %.

Formulation Example 2

(88) The hydrogenated copolymer obtained in Example 10, the fatty acid ester and the extreme pressure additive package were blended so that their proportions would be 14.0 mass %, 15.0 mass % and 3.9 mass %, respectively. PAO-6 was added to the blend in such an amount that the total mass would be 100 mass %.

Formulation Example 3

(89) The hydrogenated copolymer obtained in Example 8, the fatty acid ester and the extreme pressure additive package were blended so that their proportions would be 12.5 mass %, 15.0 mass % and 6.5 mass %, respectively. PAO-6 was added to the blend in such an amount that the total mass would be 100 mass %.

Comparative Formulation Example 1

(90) PMA-A, the fatty acid ester and the extreme pressure additive package were blended so that their proportions would be 18.4 mass %, 15.0 mass % and 3.9 mass %, respectively. PAO-6 was added to the blend in such an amount that the total mass would be 100 mass %.

Comparative Formulation Example 2

(91) PMA-B, the ester and the extreme pressure additive package were blended so that their proportions would be 31.4 mass %, 15.0 mass % and 3.9 mass %, respectively. PAO-6 was added to the blend in such an amount that the total mass would be 100 mass %.

(92) TABLE-US-00003 TABLE 3 Comp. Comp. Form. Form. Form. Form. Form. Ex. 1 Ex. 2 Ex. 3 Ex. 1 Ex. 2 Copolymer of Ex. 9 mass % 40.5 Copolymer of Ex. 10 mass % 14.0 Copolymer of Ex. 8 mass % 12.5 PMA-A mass % 18.4 PMA-B mass % 31.4 PAO-6 mass % 40.6 67.1 70.5 62.7 49.7 Fatty acid ester mass % 15 15 15 15 15 Extreme pressure additive package mass % 3.9 3.9 3.9 3.9 3.9 Kinematic viscosity at 100 C. mm.sup.2/s 13.9 13.8 13.9 14.0 14.0 Kinematic viscosity at 40 C. mm.sup.2/s 92.8 84.5 85.1 73.5 85.2 Viscosity index 153 166 168 198 168 Low-temperature viscosity (40 C.) mPa .Math. s 49,000 32,000 30,000 21,000 41,000 KRL shear stability % <1.0 1.2 4.2 29.8 4.5

(93) The above viscosity of gear oils is suited for applications such as automobile differential gear oils and manual transmission oils. The lubricating oil compositions which contained the copolymers obtained in accordance with the present invention achieved much higher shear stability than the composition of Comparative Formulation Example 1 which involved PMA-A generally used in automobile gear oils. As compared to the composition of Comparative Formulation Example 2 which exhibited higher shear stability than in Comparative Formulation Example 1, the inventive compositions compared equally in shear stability but compared favorably in low-temperature viscosity.

(94) Automobile Automatic Transmission Oils

(95) In Formulation Examples 4 and 5, the formulations involved the automatic transmission oil DI package and were controlled so that the kinematic viscosity at 100 C. would be less than 5.5 mm.sup.2/s to allow a comparison with a commercial automatic transmission oil (AUTO FLUID WS manufactured by TOYOTA MOTOR CORPORATION). Table 4 describes the lubricating oil characteristics of lubricating oil compositions obtained.

Formulation Example 4

(96) The hydrogenated copolymer obtained in Example 10, the DI package and the pour-point depressant were blended so that their proportions would be 2.8 mass %, 8.0 mass % and 0.5 mass %, respectively. A low-viscosity base oil containing the mineral oil A and the mineral oil B in a mass ratio of 2:3 was added to the blend in such an amount that the total mass would be 100 mass %.

Formulation Example 5

(97) The hydrogenated copolymer obtained in Example 8, the DI package and the pour-point depressant were blended so that their proportions would be 2.5 mass %, 8.0 mass % and 0.5 mass %, respectively. A low-viscosity base oil containing the mineral oil A and the mineral oil B in a mass ratio of 2:3 was added to the blend in such an amount that the total mass would be 100 mass %.

(98) TABLE-US-00004 TABLE 4 Commercial Form. Form. automatic Ex. 4 Ex. 5 transmission oil Copolymer of Ex. 10 mass % 2.8 Copolymer of Ex. 8 mass % 2.5 PB-A mass % PB-B mass % Mineral oil A mass % 35.5 35.6 Mineral oil B mass % 53.2 53.4 Pour-point depressant mass % 0.5 0.5 DI package mass % 8.0 8.0 Kinematic viscosity mm.sup.2/s 5.47 5.45 5.46 at 100 C. Kinematic viscosity mm.sup.2/s 25.9 25.3 23.4 at 40 C. Viscosity index 152 156 182 Low-temperature mPa .Math. s 8,100 7,900 10,200 viscosity (40 C.) Ultrasonic shear % <1.0 <1.0 2.3 stability

(99) The use of the inventive copolymers in automatic transmission oils has been shown to provide extremely excellent shear stability in addition to a viscosity index and a low-temperature viscosity comparable to those of commercial oils. That is, the use of the copolymers obtained in accordance with the invention makes it possible to reduce the initial viscosity as produced to a greater extent than heretofore possible.

(100) By changing the DI package, similar formulations provide similar effects also in variable transmission oils. The oils may be suitably used as manual transmission oils by replacing the DI package with an extreme pressure additive package.

(101) Industrial Lubricating Oils

(102) In Formulation Examples 6 and 7, the formulations were controlled so that the kinematic viscosity at 40 C. would be about 288 to 352 mm.sup.2/s to meet ISO (International Organization for Standardization) viscosity grade 320 (ISO VG320). Table 5 describes the lubricating oil characteristics of lubricating oil compositions obtained in Formulation Examples and Comparative Formulation Examples below.

Formulation Example 6

(103) The hydrogenated copolymer obtained in Example 10, the pour-point depressant and the extreme pressure additive package were blended so that their proportions would be 32.2 mass %, 0.5 mass % and 1.2 mass %, respectively. The mineral oil C was added to the blend in such an amount that the total mass would be 100 mass %.

Formulation Example 7

(104) The hydrogenated copolymer obtained in Example 8, the pour-point depressant and the extreme pressure additive package were blended so that their proportions would be 28.1 mass %, 0.5 mass % and 1.2 mass %, respectively. The mineral oil C was added to the blend in such an amount that the total mass would be 100 mass %.

Comparative Formulation Example 3

(105) PB-A, the pour-point depressant and the extreme pressure additive package were blended so that their proportions would be 28.6 mass %, 0.5 mass % and 1.2 mass %, respectively. The mineral oil C was added to the blend in such an amount that the total mass would be 100 mass %.

Comparative Formulation Example 4

(106) PB-B, the pour-point depressant and the extreme pressure additive package were blended so that their proportions would be 41.4 mass %, 0.5 mass % and 1.2 mass %, respectively. The mineral oil C was added to the blend in such an amount that the total mass would be 100 mass %.

(107) TABLE-US-00005 TABLE 5 Comp. Comp. Form. Form. Form. Form. Ex. 6 Ex. 7 Ex. 3 Ex. 4 Copolymer of mass % 32.2 Ex. 10 Copolymer of mass % 28.1 Ex. 8 PB-A mass % 28.6 PB-B mass % 41.4 Mineral oil C mass % 66.1 70.2 69.7 56.9 Pour-point mass % 0.5 0.5 0.5 0.5 depressant Extreme mass % 1.2 1.2 1.2 1.2 pressure additive package Kinematic mm.sup.2/s 331 337 308 301 viscosity at 40 C. Low- mPa .Math. s 135,000 128,000 163,000 242,000 temperature viscosity (30 C.)

(108) The lubricating oil compositions which contained the inventive copolymers attained a marked enhancement in low-temperature viscosity as compared to Comparative Formulation Examples which involved the polybutenes.