Olefin polymerization catalyst and method for producing olefin polymer

Abstract

An object of the present invention is to provide a novel catalyst for olefin (co)polymer production, which has high activity without using a large amount of a cocatalyst and is aimed for obtaining a particulate olefin (co)polymer. The invention relates to an olefin polymerization catalyst which comprises: a solid carrier (1) that has been brought into contact with a specific compound; and a metal catalyst component (2) that contains a transition metal compound (C) containing a transition metal M belonging to Group 9, 10, or 11 of the periodic table and has a reactive group R.sup.a.

Claims

1. An olefin polymerization catalyst comprising a solid carrier (1) and a metal catalyst component (2) as follows: Solid carrier (1): a solid carrier that has been brought into contact with M.sup.1(OR.sup.b).sub.nR.sup.c.sub.3-n, ZnR.sup.b.sub.2, or LiR.sup.b, where: M.sup.2 represents aluminum or boron, R.sup.b and R.sup.c each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3; Metal catalyst component (2): a metal catalyst component that contains a compound represented by general formula (A) or (B) and a transition metal compound (C) containing a transition metal M belonging to Group 9, 10, or 11 of the periodic table and has a reactive group R.sup.a, ##STR00007## wherein: Z is hydrogen or a leaving group; m represents the valence of Z; E.sup.1 represents phosphorus, arsenic, or antimony; X.sup.1 represents oxygen or sulfur; R.sup.2 and R.sup.3 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, and may be combined with each other to form a ring; R.sup.4 to R.sup.6 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, a cyano group, or a nitro group; R.sup.7 represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom; and at least one of R.sup.2 to R.sup.7 is necessarily a substituent containing a reactive group represented by general formula (I):
-Q-R.sup.a(I) where Q represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, R.sup.a represents OR.sup.8, CO.sub.2R.sup.8, CO.sup.2M, C(O)N(R.sup.8).sub.2, C(O)R.sup.8, SR.sup.8, SO.sub.3R.sup.8, P(O)(OR.sup.8).sub.2-y(R.sup.9).sub.y, P(OR.sup.9).sub.3-x(R.sup.9).sub.x, P(R.sup.9).sub.2, NHR.sup.8, N(R.sup.8).sub.2, Si(OR.sup.8).sub.3-x(R.sup.8).sub.x, OSi(OR.sup.8).sub.3-x(R.sup.8).sub.x, SO.sub.3M, PO.sub.3M.sub.2, PO.sub.3M, P(O)(OR.sup.9).sub.2M, or an epoxy-containing group; R.sup.8 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R.sup.9 represents a hydrocarbon group having 1 to 10 carbon atoms, M represents an alkali metal, an ammonium, a quaternary ammonium, or a phosphonium, M represents an alkaline earth metal, x represents an integer of 0 to 3, and y represents an integer of 0 to 2.

2. The olefin polymerization catalyst according to claim 1, which is obtained by bringing the metal catalyst component (2) into contact with the solid carrier (1).

3. The olefin polymerization catalyst according to claim 1, which is obtained by bringing a mixture resulting from contact between the compound represented by the general formula (A) or (B) and the solid carrier (1) in contact with the transition metal compound (C).

4. The olefin polymerization catalyst according to claim 1, wherein the transition metal M is nickel, palladium, platinum, cobalt, or rhodium.

5. The olefin polymerization catalyst according to claim 1, wherein the solid carrier (1) is either an inorganic oxide or a polymer carrier.

6. The olefin polymerization catalyst according to claim 1, wherein R.sup.a is OR.sup.8, CO.sub.2R.sup.8, C(O)N(R.sup.8).sub.2, C(O)R.sup.8, SR.sup.8, P(R.sup.9).sub.2, NHR.sup.8, N(R.sup.8).sub.2, or Si(OR.sup.8).sub.3-x(R.sup.8).sub.x.

7. An olefin-prepolymerization catalyst wherein the olefin polymerization catalyst according to claim 1 is prepolymerized with an -olefin.

8. The olefin-prepolymerization catalyst according to claim 7, wherein the prepolymerization is carried out in the presence of a Lewis base.

9. The olefin-prepolymerization catalyst according to claim 7, wherein the -olefin is ethylene or propylene.

10. A method for producing an olefin polymer, which comprises homopolymerizing or copolymerizing an olefin having 2 or more carbon atoms in the presence of the olefin polymerization catalyst according to claim 1.

11. A method for producing an olefin/(meth)acrylate ester copolymer, which comprises copolymerizing an olefin having 2 or more carbon atoms and a (meth)acrylate ester in the presence of the olefin polymerization catalyst according to claim 1.

12. A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin having 2 or more carbon atoms in the presence of the olefin-prepolymerization catalyst according to claim 7.

13. A method for producing an olefin/(meth)acrylate ester copolymer, comprising copolymerizing an olefin having 2 or more carbon atoms and a (meth)acrylate ester in the presence of the olefin-prepolymerization catalyst according to claim 7.

14. An olefin polymerization catalyst comprising a solid carrier (1) and a metal catalyst component (2) as follows: Solid carrier (1): a solid carrier that has been brought into contact with M.sup.1(OR.sup.b).sub.nR.sup.c.sub.3-n, ZnR.sup.b.sub.2, or LiR.sup.b, where: M.sup.2 represents aluminum or boron, R.sup.b and R.sup.c each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3; and Metal catalyst component (2): a metal catalyst component that contains a metal complex represented by general formula (D): ##STR00008## wherein: M is a transition metal belonging to Group 9, 10, or 11 of the periodic table; E.sup.1 represents phosphorus, arsenic, or antimony; X.sup.1 represents oxygen or sulfur; L.sup.1 represents a ligand coordinated to M, R.sup.1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom; L.sup.1 and R.sup.1 may be combined with each other to form a ring; R.sup.2 and R.sup.3 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom and may be combined with each other to form a ring; R.sup.4 to R.sup.6 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, a cyano group, or a nitro group; and R.sup.7 represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, provided that at least one of R.sup.2 to R.sup.7 is necessarily a substituent containing a reactive group represented by the general formula (I):
-Q-R.sup.a(I) wherein: Q represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, R.sup.a represents OR.sup.8, CO.sub.2R.sup.8, CO.sup.2M, C(O)N(R.sup.8).sub.2, C(O)R.sup.8, SR.sup.8, SO.sub.3R.sup.8, P(O)(OR.sup.8).sub.2-y(R.sup.9).sub.y, P(OR.sup.9).sub.3-x(R.sup.9).sub.x, P(R.sup.9).sub.2, NHR.sup.8, N(R.sup.8).sub.2, Si(OR.sup.8).sub.3-x(R.sup.8).sub.x, OSi(OR.sup.8).sub.3-x(R.sup.8).sub.x, SO.sub.3M, PO.sub.3M.sub.2, PO.sub.3M, P(O)(OR.sup.9).sub.2M, or an epoxy-containing group R.sup.8 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R.sup.9 represents a hydrocarbon group having 1 to 10 carbon atoms, M represents an alkali metal, an ammonium, a quaternary ammonium, or a phosphonium, M represents an alkaline earth metal, x represents an integer of 0 to 3, and y represents an integer of 0 to 2.

Description

EXAMPLES

(1) The present invention is described further in detail in the following Examples and Comparative Examples, but the present invention is not limited thereto.

(2) In the following Synthetic Examples, operations were conducted under a purified nitrogen atmosphere and, as solvents, anhydrous and deoxygenated ones were used unless otherwise noted.

(3) 1. Evaluation Method

(4) (1) Weight-Average Molecular Weight Mw, Number-Average Molecular Weight Mn, and Molecular Weight Distribution Mw/Mn:

(5) They were determined by the following GPC measurement.

(6) Firstly, a sample (about 20 mg) was collected in a vial for a pretreatment apparatus PL-SP 260VS for high temperature GPC manufactured by Polymer Laboratories Ltd., o-dichlorobenzene containing BHT as a stabilizer (concentration of BHT=0.5 g/L) was added thereto, and polymer concentration was adjusted so as to be 0.1% by weight. The polymer was dissolved by heating at 135 C. in the above-described pretreatment apparatus PL-SP 260VS for high temperature GPC, and filtered through a glass filter to prepare a sample. Incidentally, no polymer was trapped by the glass filter in the GPC measurement of the present invention.

(7) Next, GPC measurement was carried out using GPCV 2000 manufactured by Waters equipped with TSKgel GMH-HT (30 cm4 columns) manufactured by Tosoh Corporation as a column and an RI detector. The following measuring conditions were employed: injection amount of sample solution: about 520 L; column temperature: 135 C.; solvent: o-dichlorobenzene; and flow rate: 1.0 ml/minute. Calculation of molecular weight was carried out as follows. That is, commercially available monodisperse polystyrene was used as a standard sample, a calibration curve regarding to retention time versus molecular weight was prepared from viscosity formulas of the polystyrene standard sample and an ethylene-based polymer, and calculation of molecular weight was performed based on the calibration curve. Incidentally, as the viscosity formula, []=KM.sup. was used, and there were used K=1.38E.sup.4, =0.70 for polystyrene, and K=4.77E.sup.4, =0.70 for an ethylene-based polymer.

(8) (2) IR Analysis:

(9) A comonomer content ([RA]) was determined by IR measurement of a sample transformed into a sheet by hot pressing. At that time, for an ethylene/acrylate ester copolymer, the content is a value obtained by converting an area ratio of 1,740 to 1,690 cm.sup.1/730 to 720 cm.sup.1 using the following equation.
[RA]=1.3503(area ratio)0.2208
(3) Measurement of Polymer Bulk Density (BD): It was Measured in Accordance with JIS K 7365 (1999).
2. Synthesis of Ligand

Synthetic Example 1: Synthesis of 2-bis(2,6-dimethoxyphenyl)phosphanyl-4-(3-butanon-1-yl)-6-pentafluorophenylphenol Ligand (B-195)

(1) Synthesis of 1,3-dimethoxy-2-iodobenzene (2)

(10) 1,3-Dimethoxybenzene (50 g, 0.36 mol) was dissolved in anhydrous tetrahydrofuran (500 mL). An n-hexane solution of n-butyllithium (166 mL, 2.5M, 0.42 mol) was slowly added thereto at 0 C. under a nitrogen atmosphere. To the resultant solution, a solution of iodine (96.5 g, 0.38 mol) dissolved in anhydrous tetrahydrofuran (200 mL) was added dropwise at 0 C. over a period of 40 minutes. The resultant solution was stirred at room temperature overnight. After completion thereof, methanol (80 mL) was added dropwise, the resultant mixture was concentrated under reduced pressure, and after adding water (200 mL), the mixture was extracted with ethyl acetate (250 mL) three times. After the extraction liquid was washed with sodium thiosulfate and a saturated sodium chloride solution, the liquid was dried over anhydrous sodium sulfate and concentrated to obtain 1,3-dimethoxy-2-iodobenzene (2) as a yellow solid (63 g, 66% yield).

(2) Synthesis of bis(2,6-dimethoxyphenyl)phosphine Chloride (3)

(11) The compound (2, 19.4 g, 73.5 mmol) was dissolved in anhydrous tetrahydrofuran (50 mL) and a tetrahydrofuran solution of isopropylmagnesium chloride (36.8 mL, 2.0M, 73.6 mmol) was gradually added thereto at 30 C., followed by stirring the resultant mixture at 15 C. for 1 hour. Then, the mixture was cooled to 78 C. and phosphorus trichloride (5.0 g, 36.4 mmol) was gradually added thereto. After the mixture was gradually warmed to 15 C. and stirred at 15 C. for 1 hour, the solvent was removed in vacuo. Anhydrous tetrahydrofuran (150 mL) was added to the resultant reaction intermediate containing bis(2,6-dimethoxyphenyl)phosphine chloride (3) and the resultant solution was used in the following reaction.

(3) Synthesis of 4-(3,5-dibromo-4-hydroxyphenyl)-2-butanone (B-195_5)

(12) Sodium bromide (231 g, 2.25 mol) and Oxone (registered trademark) (monopersulfate salt compound) (843 g, 1.37 mol) were added to an acetone (1 L)/water (1 L) mixed solution of 4-(4-hydroxyphenyl)-2-butanone (150 g, 0.91 mol) at 0 C. under an argon atmosphere and then the mixture was stirred for 14 hours. The reaction mixture was filtrated and the filtrate was washed with ethyl acetate (500 mL3). The filtrate and the washing liquid were concentrated under reduced pressure and the resultant concentrate was extracted with ethyl acetate (800 mL3). The extraction liquid was dehydrated over anhydrous sodium sulfate and then filtrated and the filtrate was concentrated to obtain the objective compound (B-195_5) (250 g, 0.78 mol, 86% yield).

(4) Synthesis of 2-methyl-2-(2-(3,5-dibromo-4-hydroxyphenyl)ethyl)-1,3-dioxolane (B-195_6)

(13) Trimethyl orthoformate (709 g, 6.68 mol) and p-toluenesulfonic acid (43 g, 0.20 mol) were added to a mixed solution of the compound (B-195_5), 430 g, 1.34 mol) and ethylene glycol (415 g, 6.69 mol) at 15 C. under an argon atmosphere and then the mixture was stirred for 14 hours. A saturated sodium hydrogen carbonate solution (500 mL) was added to the reaction mixture, followed by performing extraction with ethyl acetate (1 L3). After the extraction liquid was dehydrated over anhydrous sodium sulfate and filtrated, a crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10/1) to obtain the objective compound (B-195_6) (420 g, 1.15 mol, 86% yield) as a white solid.

(5) Synthesis of 2-methyl-2-(2-(3,5-dibromo-4-(methoxymethoxy)phenyl)ethyl)-1,3-dioxolane (B-195_7)

(14) The compound (B-195_6, 246 g, 0.67 mol) was added to an anhydrous tetrahydrofuran (500 mL) suspension of sodium hydride (54.4 g, 1.36 mol, mineral oil 40 wt % at 0 C. under an argon atmosphere and then the mixture was stirred for 1 hour. After chloromethyl methyl ether (112 g, 1.39 mol) was added thereto at 0 C. under an argon atmosphere, the mixture was stirred for 4 hours. Ice-water (500 mL) was added to the mixture, followed by extraction with ethyl acetate (500 mL3). The resultant extraction liquid was washed with a saturated sodium chloride solution, dehydrated over anhydrous sodium sulfate, and filtrated and then the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10/1) to obtain the objective compound (B-195_7) (250 g, 0.61 mol, 90% yield) as a colorless transparent liquid.

(6) Synthesis of 2-methyl-2-(2-(3-bromo-4-(methoxymethoxy)-5-bis(2,6-dimethoxyphenyl)-phosphanylphenyl)ethyl)-1,3-dioxolane (B-195_8)

(15) An n-hexane solution of n-butyllithium (29.4 mL, 2.5M, 73.5 mmol) was added to an anhydrous tetrahydrofuran (75 mL) solution of the compound (B-195_7, 30.2 g, 73.5 mmol) at 78 C. under an argon atmosphere and then the mixture was stirred for 1 hour. The solution of the compound (3, 73.5 mmol) obtained in (2) was added dropwise to the reaction mixture cooled to 78 C. and then the whole was gradually warmed to 15 C., followed by stirring for 14 hours. Ice-water (100 mL) was added to the reaction mixture, followed by extraction with methylene chloride (150 mL3). The extraction liquid was washed with a saturated sodium chloride solution (50 mL) and then dehydrated over anhydrous sodium sulfate. The dehydrated extraction liquid was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10/1) to obtain the objective compound (B-195_8) (15.0 g, 23.6 mmol, 32% yield) as a colorless transparent liquid.

(7) Synthesis of 2-methyl-2-(2-(3-(pentafluorophenyl)-4-(methoxymethoxy)-5-bis(2,6-dimethoxyphenyl)-phosphanylphenyl)ethyl)-1,3-dioxolane (B-195_9)

(16) An n-hexane solution of n-butyllithium (5.0 mL, 2.5M, 12.5 mmol) was added dropwise to an anhydrous tetrahydrofuran (40 mL) solution of the compound (B-195_8, 8.0 g, 12.6 mmol) at 78 C. under an argon atmosphere and then the mixture was stirred at 78 C. for 1 hour. Hexafluorobenzene (7.7 g, 41.4 mmol) was added dropwise to the reaction mixture at 78 C. and the whole was gradually warmed to 15 C., followed by stirring for 14 hours. Ice-water (50 mL) was added to the reaction mixture, followed by extraction with methylene chloride (75 mL3). The extraction liquid was washed with a saturated sodium chloride solution (50 mL) and then dehydrated over anhydrous sodium sulfate. The dehydrated extraction liquid was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10/1) to obtain the objective compound (B-195_9) (4.0 g, 5.5 mmol, 44% yield) as a colorless liquid.

(8) Synthesis of 2-bis(2,6-dimethoxyphenyl)phosphanyl-4-(3-butanon-1-yl)-6-pentafluorophenylphenol Ligand (B-195)

(17) An ethyl acetate solution of hydrogen chloride (4M, 40 mL) was added to an ethyl acetate (20 mL) solution of the compound (B-195_9, 4.0 g, 5.5 mmol) at 0 C. under an argon atmosphere. The mixture was gradually warmed to 25 C. and stirred for 1 hours. A saturated sodium hydrogen carbonate solution (50 mL) was added to the reaction mixture, followed by extraction with ethyl acetate (60 mL3). The extraction liquid was washed with a saturated sodium chloride solution (30 mL) and then dehydrated over anhydrous sodium sulfate. The dehydrated extraction liquid was concentrated under reduced pressure and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=5/1) to obtain the objective compound (B-195) (1.3 g, 2.1 mmol, 38% yield) as a white powder.

(18) .sup.1H-NMR (C.sub.6D.sub.6, , ppm): 7.72 (dd, J=14.0, 2.0 Hz, 1H), 7.73 (s, 6.99 (t, J=8.4 Hz, 2H), 6.89 (s, 1H), 6.20 (dd, J=8.4, 2.4 Hz, 4H), 3.17 (s, 12H), 2.73 (t, J=7.6 Hz, 2H), 2.16 (t, J=7.6 Hz, 2H), 1.55 (s, 3H); .sup.31P-NMR (C.sub.6D.sub.6, , ppm): 58.4 (s).

Synthetic Example 2: Synthesis of 2-bis(2,6-dimethoxy-4-(3-butanon-1-yl)phenyl)phosphanyl-6-pentafluorophenylphenol Ligand (B-200)

(1) Synthesis of 1-bromo-2-(methoxymethoxy)-3-bis(2,6-dimethoxy-4-((2-methyl-1,3-dioxolan-2-yl)ethyl)phenyl)phosphanylbenzene (B-200_5A)

(19) (1-1) Isopropylmagnesium chloride (25.0 mL, 2.0M, 50.0 mmol) was added dropwise to an anhydrous tetrahydrofuran (60 mL) solution of 1,3-dibromo-2-(methoxymethoxy)benzene (14.8 g, 50 mmol) at 30 C. under an argon atmosphere and the mixture was gradually warmed to 25 C., followed by stirring for 2 hours. Thereafter, the reaction mixture was cooled to 78 C. and stirred for 15 minutes and then phosphorus trichloride (20.5 g, 149 mmol) was added dropwise to the mixture cooled to 78 C. After the reaction mixture was gradually warmed to 25 C. and stirred for 1 hour, the solvent was removed by distillation in vacuo. The resultant residue was dissolved in anhydrous tetrahydrofuran (100 mL).

(20) (1-2) An n-hexane solution of n-butyllithium (40.0 mL, 2.5M, 100 mmol) was added dropwise to an anhydrous tetrahydrofuran (100 mL) of 1,3-dimethoxy-5-(2-methyl-1,3-dioxolan-2-yl)-2-ethyl)benzene (25.2 g, 99.9 mmol) at 0 C. under an argon atmosphere and then the whole was gradually warmed to 25 C. and stirred for 2 hours. The reaction mixture was added dropwise to the mixture synthesized in (1-1) at 78 C. and then the whole was gradually warmed to 25 C., followed by stirring for 16 hours. Ice-water (300 mL) was added to the reaction mixture and then the organic solvent was removed under reduced pressure. After it was extracted with ethyl acetate (150 mL3), the extraction liquid was washed with a saturated sodium chloride solution (300 mL) and then dehydrated over anhydrous sodium sulfate. The resultant extraction liquid was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=5/1) to obtain the objective compound (B-200_5A) (13.8 g, 18.4 mmol, 37% yield) as a white solid.

(2) Synthesis of 1-(pentafluorophenyl)-2-(methoxymethoxy)-3-bis(2,6-dimethoxy-4-((2-methyl-1,3-dioxolan-2-yl)ethyl)phenyl)phosphanylbenzene (B-200_6)

(21) An n-hexane solution of n-butyllithium (7.3 mL, 2.5M, 18.3 mmol) was added dropwise to an anhydrous tetrahydrofuran (20 mL) solution of the compound (B-200_5A, 13.8 g, 18.4 mmol) at 78 C. under an argon atmosphere and then the mixture was stirred at 78 C. for 1 hour. Hexafluorobenzene (11.3 g, 60.7 mmol) was added dropwise thereto and the whole was gradually warmed to 25 C., followed by stirring for 16 hours. After ice-water (100 mL) was added to the reaction mixture, the organic solvent was removed under reduced pressure. It was extracted with ethyl acetate (50 mL3). The extraction liquid was washed with a saturated sodium chloride solution (100 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=5/1) to obtain the objective compound (B-200_6) (5.80 g, 6.9 mmol, 38% yield) as a white solid.

(3) Synthesis of 2-bis(2,6-dimethoxy-4-(3-butanon-1-yl)phenyl)phosphanyl-6-pentafluorophenylphenol Ligand (B-200)

(22) An ethyl acetate solution of hydrogen chloride (4M, 10.0 mL) was added dropwise to an ethyl acetate (6.0 mL) solution of the compound (B-200_6, 0.200 g, 0.239 mmol) at 0 C. under an argon atmosphere. The mixture was gradually warmed to 15 C. and stirred for 1.0 hours and then the organic solvent was removed under reduced pressure. A saturated sodium hydrogen carbonate solution (30 mL) was added thereto, followed by extraction with ethyl acetate (30 mL3). The extraction liquid was washed with a saturated sodium chloride solution (30 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated under reduced pressure and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=5/1) to obtain the objective compound (B-200) (0.100 g, 0.142 mmol, 59% yield) as a white solid.

(23) .sup.1H-NMR (C.sub.6D.sub.6, , ppm): 7.72 (ddd, J=13.2, 7.6, 1.2 Hz, 1H), 7.83 (br(s), 1H), 7.03 (d, J=7.2 Hz, 1H), 6.84 (t, J=7.6 Hz, 1H), 6.15 (d, J=2.8 Hz, 4H), 3.24 (s, 12H), 2.72 (t, J=7.6 Hz, 4H), 2.18 (t, J=7.6 Hz, 4H), 1.62 (s, 6H); .sup.31P-NMR (C.sub.6D.sub.6, , ppm): 59.7 (s).

Synthetic Example 3: Synthesis of 2-(2,6-dimethoxyphenyl)(2,6-diphenoxyphenyl)phosphanyl-4-(3-butanon-1-yl)-6-pentafluorophenyl Phenol Ligand (B-203)

(1) Synthesis of 2-methyl-2-(3-bromo-4-(methoxymethoxy)-5-(2,6-dimethoxyphenyl)(2,6-diphenoxyphenyl)phosphanylphenyl)ethyl)-1,3-dioxolane (B-203_11A)

(24) (1-1) 1,3-Dimethoxy-2-iodobenzene (2, 1.3.2 g, 50.0 mmol) was dissolved in anhydrous tetrahydrofuran (60 mL) and a tetrahydrofuran solution of isopropylmagnesium chloride (25.0 mL, 2.0M, 50.0 mmol) was gradually added thereto at 30 C., followed by stirring the resultant mixture at 15 C. for 1 hour. Then, the mixture was cooled to 78 C. and phosphorus trichloride (8.40 g, 61.2 mmol) was added thereto, followed by stirring for another 1 hour. Thereafter, the solvent and excessive phosphorus trichloride were removed in vacuo and then anhydrous tetrahydrofuran (80 mL) was added to the residue. The resultant one was used in the next reaction.

(25) (1-2) An n-hexane solution of n-butyllithium (20.0 mL, 2.50M, 50.0 mmol) was added dropwise to an anhydrous tetrahydrofuran (40 mL) solution of 1,3-diphenoxybenzene (13.1 g, 49.9 mmol) at 0 C. under an argon atmosphere and then the whole was gradually warmed to 15 C. and stirred for 2 hours. The mixed solution was added dropwise to the tetrahydrofuran solution obtained in (1-1) at 78 C. and the whole was gradually warmed to 15 C., followed by stirring for 1 hour.

(26) (1-3) An n-hexane solution of n-butyllithium (20.0 mL, 2.50M, 50.0 mmol) was added dropwise to an anhydrous tetrahydrofuran (50 mL) solution of 2-methyl-2-(2-(3,5-dibromo-4-(methoxymethoxy)phenyl)ethyl)-1,3-dioxolane (B-195_7, 20.5 g, 50.0 mmol) at 78 C. under an argon atmosphere, followed by stirring for another 1 hour. The mixture was added to the mixture obtained in (1-2) at 78 C. and the whole was gradually warmed to 15 C., followed by stirring for 16 hours. Ice-water (300 mL) was added to the reaction mixture and then the organic solvent was removed under reduced pressure, followed by extraction with ethyl acetate (150 mL3). The extraction liquid was washed with a saturated sodium chloride solution (300 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. Thereafter, the filtrate was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=20/1) to obtain the objective compound (B-203_11A) (13.8 g, 18.2 mmol, 36% yield) as a white solid.

(2) Synthesis of 2-methyl-2-(2-(3-(pentafluorophenyl)-4-(methoxymethoxy)-5-(2,6-dimethoxyphenyl)(2,6-diphenoxyphenyl)phosphanylphenyl)ethyl)-1,3-dioxolane (B-203_12A)

(27) An n-hexane solution of n-butyllithium (7.3 mL, 2.5M, 18.3 mmol) was added dropwise to an anhydrous tetrahydrofuran (50 mL) solution of the compound (B-203_11A, 13.8 g, 18.2 mmol) at 78 C. under an argon atmosphere and then the mixture was stirred at 78 C. for 1 hour. Hexafluorobenzene (12.5 g, 67.2 mmol) was added dropwise thereto and the whole was gradually warmed to 15 C., followed by stirring for 16 hours. After ice-water (100 mL) was added to the reaction mixture, the organic solvent was removed under reduced pressure. The residue was extracted with ethyl acetate (150 mL3). The extraction liquid was washed with a saturated sodium chloride solution (150 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=20/1) to obtain the objective compound (B-203_12A) (9.50 g, 11.2 mmol, 62% yield) as a white solid.

(3) Synthesis of 2-(2,6-dimethoxyphenyl)(2,6-diphenoxyphenyl)phosphanyl-4-(3-butanon-1-yl)-6-pentafluorophenylphenol Ligand (B-203)

(28) An ethyl acetate solution of hydrogen chloride (4M, 15 mL) was added dropwise to an ethyl acetate (8 mL) solution of the compound (B-203_12A, 0.403 g, 0.486 mmol) at 0 C. under an argon atmosphere. The mixture was gradually warmed to 25 C. and stirred for 1 hours and then the organic solvent was removed under reduced pressure. A saturated sodium hydrogen carbonate solution (30 mL) was added to the resultant residue, followed by extraction with ethyl acetate (30 mL2). The extraction liquid was washed with a saturated sodium chloride solution (30 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated under reduced pressure to obtain the objective compound (B-203) (0.36 g, 0.474 mmol, 98% yield) as a white powder.

(29) .sup.1H-NMR (C.sub.6D.sub.6, , ppm): 7.68 (s, 1H), 7.64 (dd, J=13.2, 2.0 Hz, 1H), 6.99-6.94 (m, 4H), 6.90 (t, J=8.4 Hz, 1H), 6.80-6.71 (m, 8H), 6.50 (dd, J=8.0, 2.8 Hz, 2H), 6.09 (dd, J=8.0, 2.8 Hz, 2H), 3.17 (s, 6H), 2.53 (t, J=7.6 Hz, 2H), 1.98 (t, J=7.6 Hz, 2H), 1.53 (s, 3H); .sup.31P-NMR (C.sub.6D.sub.6, , ppm): 59.2 (s).

Synthetic Example 4: Synthesis of 2-bis(2,6-dimethoxy-4-(3-butanon-1-yl)phenyl)phosphanyl-6-trimethylsilylphenol Ligand (B-302)

(1) Synthesis of 1-(trimethylsilyl)-2-(methoxymethoxy)-3-bis(2,6-dimethoxy-4-((2-methyl-1,3-dioxolan-2-yl)ethyl)phenyl)phosphanylbenzene (B-302_10)

(30) An n-hexane solution of n-butyllithium (6.70 mL, 2.5M, 16.8 mmol) was added dropwise to an anhydrous tetrahydrofuran (60 mL) solution of 1-bromo-2-(methoxymethoxy)-3-bis(2,6-dimethoxy-4-((2-methyl-1,3-dioxolan-2-yl)ethyl)phenyl)phosphanylbenzene (B-200_5A, 12.5 g, 16.7 mmol) at 78 C. under an argon atmosphere and then the mixture was stirred at 78 C. for 1 hour. Trimethylsilyl chloride (2.20 g, 20.3 mmol) was added dropwise thereto and then the mixture was gradually warmed to 15 C., followed by stirring for 14 hours. Ice-water (100 mL) was added to the reaction mixture, followed by extraction with ethyl acetate (100 mL3). The extraction liquid was washed with a saturated sodium chloride solution (150 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=5/1) to obtain the objective compound (B-302_10) (7.50 g, 10.1 mmol, 60% yield) as a white solid.

(2) Synthesis of 2-bis(2,6-dimethoxy-4-(3-butanon-1-yl)phenyl)phosphanyl-6-trimethylsilylphenol Ligand (B-302)

(31) An ethyl acetate solution of hydrogen chloride (4M, 20.0 mL) was added dropwise to an ethyl acetate (60 mL) solution of the compound (B-302_10, 3.00 g, 4.04 mmol) at 0 C. under an argon atmosphere, followed by stirring for another 1 hour. A saturated sodium hydrogen carbonate solution (60 mL) was added to the reaction mixture, followed by extraction with ethyl acetate (60 ml3). The extraction liquid was washed with a saturated sodium chloride solution (60 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated under reduced pressure and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=1/1) to obtain the objective compound (B-302) (1.50 g, 2.46 mmol, 61% yield) as a white solid.

(32) .sup.1H-NMR (C.sub.6D.sub.6, , ppm): 7.72 (ddd, J=12.8, 7.2, 1.6 Hz, 1H), 7.55 (d, J=4.8 Hz, 1H), 7.39 (d, J=7.2, 1.6 Hz, 1H), 6.89 (t, J=7.2 Hz, 1H), 6.15 (d, J=2.8 Hz, 4H), 3.24 (s, 12H), 2.73 (t, J=7.6 Hz, 4H), 2.19 (t, J=7.6 Hz, 4H), 1.63 (s, 6H), 0.40 (s, 9H); .sup.31P-NMR (C.sub.6D.sub.6, , ppm): 61.9 (s).

Synthetic Example 5: Synthesis of 2-bis(2,6-dimethoxyphenyl)phosphanyl-4-(2-hydroxyethoxy)methyl)-6-pentafluorophenylphenol Ligand (B-304)

(1) Synthesis of 3,5-dibromo-4-(methoxymethoxy)benzaldehyde (B-304_6)

(33) Diisopropylethylamine (84.1 g, 0.651 mol) and chloromethyl methyl ether (52.4 g, 0.651 mol) were added to an anhydrous methylene chloride (500 mL) solution of 1,3-dibromo-4-hydroxybenzaldehyde (90.8 g, 0.324 mol), followed by stirring for another 14 hours. A saturated sodium hydrogen carbonate solution (30 mL) was added to the reaction mixture, followed by extraction with methylene chloride (300 mL3). The extraction liquid was washed with a saturated sodium chloride solution (300 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated under reduced pressure to obtain the objective compound (B-304_6) (97.0 g, 0.299 mol, 92% yield) as a white solid.

(2) Synthesis of 3,5-dibromo-4-(methoxymethoxy)benzenemethanol (B-304_7)

(34) Sodium borohydride (84.1 g, 2.22 mol) was added to a solution of anhydrous tetrahydrofuran (200 mL) and anhydrous methanol (200 mL) of the compound (B-304_6, 97.0 g, 0.324 mol) at 0 C. under an argon atmosphere, followed by stirring for another 1 hour. A saturated ammonium chloride solution (300 mL) was added to the reaction mixture, followed by extraction with methylene chloride (300 mL3). The extraction liquid was washed with a saturated sodium chloride solution (300 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. The filtrate was concentrated under reduced pressure to obtain the objective compound (B-304_7) (82.4 g, 0.253 mol, 78% yield) as a white solid.

(3) Synthesis of 3,5-dibromo-4-(methoxymethoxy)benzyl Bromide (B-304_8)

(35) Triphenylphosphine (21.9 g, 83.5 mmol) and N-bromosuccinimide (14.9 g, 83.7 mmol) were added to an anhydrous methylene chloride (100 mL) solution of the compound (B-304_7, 18.0 g, 55.2 mmol) at 0 C. under an argon atmosphere, followed by stirring for another 1 hour. Ice-water (100 mL) was added to the reaction mixture, followed by extraction with methylene chloride (100 mL3). The extraction liquid was washed with a saturated sodium chloride solution (100 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. A crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10/1) to obtain the objective compound (B-304_8) (14.0 g, 36.0 mmol, 65% yield) as a white solid.

(4) Synthesis of 1-(methoxymethoxy)-2,6-dibromo-4-(2-(1-tetrahydro-2H-pyran-2-yl)ethoxymethyl)benzene (B-304_10)

(36) Sodium hydride (1.10 g, 27.5 mmol, mineral oil 40 wt %) was added to an anhydrous tetrahydrofuran (60 mL) of 2-(1-tetrahydro-2H-pyran-2-yl)oxy)ethanol (3.80 g, 26.0 mmol) at 0 C. under an argon atmosphere and then the mixture was stirred for another 15 minutes. After an anhydrous tetrahydrofuran (20 mL) solution of the compound (B-304_8, 10.0 g, 25.7 mmol) was added dropwise thereto at 0 C. under an argon atmosphere, the mixture was gradually warmed to 15 C. and stirred for 24 hours. Ice-water (100 mL) was added to the reaction mixture, followed by extraction with methylene chloride (100 mL3). The extraction liquid was washed with a saturated sodium chloride solution (100 mL), dehydrated over anhydrous sodium sulfate, and filtrated. A crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10/1) to obtain the objective compound (B-304_10) (7.94 g, 17.5 mmol, 68% yield) as a white solid.

(5) Synthesis of 1-(methoxymethoxy)-2-bromo-4-(2-(1-tetrahydro-2H-pyran-2-yl)ethoxymethyl)-6-(bis(2,6-dimethoxyphenyl)phosphanyl)benzene (B-304_11)

(37) (5-1) 2,6-Dimethoxyiodobenzene (2, 11.0 g, 41.7 mmol) was dissolved in anhydrous tetrahydrofuran (40 mL) and a tetrahydrofuran solution of isopropylmagnesium chloride (21.0 mL, 2.0M, 42.0 mmol) was gradually added thereto at 30 C. and then the whole was warmed to 15 C. and stirred for 1 hour. Then, the mixture was cooled to 78 C. and phosphorus trichloride (2.90 g, 21.1 mmol) was gradually added thereto, and then the mixture was gradually warmed to 15 C. and stirred for 1 hour. After the solvent was removed from the reaction mixture in vacuo, anhydrous tetrahydrofuran (50 mL) was added to the residue.

(38) (5-2) An n-hexane solution of n-butyllithium (8.4 mL, 2.5M, 21.0 mmol) was added dropwise to an anhydrous tetrahydrofuran (60 mL) solution of the compound (B-304_10, 9.50 g, 20.9 mmol) at 78 C. under an argon atmosphere and then the mixture was stirred for 1 hour. The reaction solution obtained in (5-1) was added dropwise thereto at 78 C. and the whole was gradually warmed to 15 C. and stirred for 14 hours. Ice-water (100 mL) was added to the reaction mixture, followed by extraction with methylene chloride (150 mL3). The extraction liquid was washed with a saturated sodium chloride solution (50 mL) and then dehydrated over anhydrous sodium sulfate. The dehydrated extraction liquid was concentrated and the resultant crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate=2/1) to obtain the objective compound (B-304_11) (13.0 g, 19.1 mmol, 91% yield) as a colorless transparent liquid.

(6) Synthesis of 1-(methoxymethoxy)-2-(bis(2,6-dimethoxyphenyl)phosphanyl)-4-(2-(1-tetrahydro-2H-pyran-2-yl)ethoxymethyl)-6-pentafluorophenylbenzene (B-304_12)

(39) An n-hexane solution of n-butyllithium (7.80 mL, 2.5M, 19.5 mmol) was added dropwise to an anhydrous tetrahydrofuran (100 mL) solution of the compound (B-304_11, 13.0 g, 19.1 mmol) at 78 C. under an argon atmosphere and then the mixture was stirred at 78 C. for 1 hour. Hexafluorobenzene (9.60 g, 51.6 mmol) was added dropwise thereto and then the whole was gradually warmed to 15 C. and stirred for 14 hours. Ice-water (100 mL) was added to the reaction mixture, followed by extraction with ethyl acetate (100 mL3). The extraction liquid was washed with a saturated sodium chloride solution (150 mL) and then dehydrated over anhydrous sodium sulfate, followed by filtration. A crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (petroleum ether/ethyl acetate=1/1) to obtain the objective compound (B-304_12) (5.00 g, 6.52 mmol, 34% yield) as a white solid.

(7) Synthesis of 2-bis(2,6-methoxyphenyl)phosphanyl-4-(2-hydroxyethoxy)methyl)-6-pentafluorophenylphenol Ligand (B-304)

(40) An ethyl acetate solution of hydrogen chloride (2M, 30 mL) was added dropwise to a methylene chloride (30 mL) solution of the compound (B-304_12, 4.00 g, 5.22 mmol) at 0 C. under an argon atmosphere, followed by stirring for another 15 minutes. A saturated sodium hydrogen carbonate solution (60 mL) was added to the reaction mixture, followed by extraction with ethyl acetate (60 mL2). The extraction liquid was washed with a saturated sodium chloride solution (60 mL) and then dehydrated over anhydrous sodium sulfate. A crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (petroleum ether/ethyl acetate=1/1) to obtain the objective compound (B-304) (1.00 g, 1.57 mmol, 30% yield) as a white solid.

(41) .sup.1H-NMR (C.sub.6D.sub.6, , ppm): 8.20 (dd, J=13.6, 2.0 Hz, 1H), 7.96 (br(s), 1H), 7.21 (s, 1H), 7.07 (t, J=8.4 Hz, 2H), 6.27 (dd, J=8.4, 2.8 Hz, 4H), 4.30 (s, 2H), 3.56 (br, 2H), 3.32 (t, J=4.0 Hz, 2H), 3.23 (s, 12H), 1.75 (br(s), 1H); .sup.31P-NMR (C.sub.6D.sub.6, , ppm): 58.6 (s).

Synthetic Example 6: Synthesis of B-27DM and B-111

(42) Synthesis of B-27DM and is preformed with reference to WO2010/050256 and JP-A-2013-043871.

(43) 3. Preparation of Olefin Polymerization Catalyst

(44) The following operations are all conducted under a nitrogen atmosphere.

(45) Solvent: toluene and n-hexane are used as deoxygenated and dehydrated ones.

(46) TiBA: triisobutylaluminum, BHT: dibutylhydroxytoluene, Et; ethyl group, iBu: isobutyl group, iPr: isopropyl group, Ni(COD).sub.2: bis(cyclooctadiene)nickel, AliBu.sub.2BHT: (2,6-di-t-butyl-4-methylphenoxy)diisobutylaluminum

(47) <Preparation of Polymerization Catalyst 1>

(48) Preparation of solid carrier 1: Silica calcinated at 600 C. (1.03 g) (Grace 948) was collected and toluene (4 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2BHT (0.25M, 6.2 mL, 1.5 mmol) was added at room temperature with stirring, followed by reaction at 70 C. for 1 hour. The toluene solution of AliBu.sub.2BHT was prepared by adding a toluene solution of BHT (0.47M, 14.0 mL, 6.6 mmol) to a toluene solution of TIBA (0.51M, 13.0 mL, 6.6 mmol) dropwise at room temperature over a period of 5 minutes and stirring the whole at room temperature for 10 minutes and for another 1 hour after heating to 100 C. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.18 g of the solid carrier 1.

(49) Preparation of metal catalyst component 1: Ni(COD).sub.2 (51.3 mg, 0.187 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.047M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-195 (114.6 mg, 0.181 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 1.

(50) Preparation of polymerization catalyst 1: The metal catalyst component 1 (4 mL) was added to the solid carrier 1 (1.18 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.28 g of the polymerization catalyst 1.

(51) <Preparation of Polymerization Catalyst 2>

(52) Preparation of solid carrier 2: Silica calcinated at 600 C. (1.05 g) (Grace 948) was collected and toluene (8 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2BHT (0.25M, 2.1 mL, 0.5 mmol) was added at room temperature with stirring, followed by a reaction at 70 C. for 1 hour. The toluene solution of AliBu.sub.2BHT was prepared in the same manner as in Example 1 to be mentioned later. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.18 g of the solid carrier 2.

(53) Preparation of metal catalyst component 2: Ni(COD).sub.2 (48.5 mg, 0.176 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.044M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-200 (135.3 mg, 0.192 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 2.

(54) Preparation of polymerization catalyst 2: The metal catalyst component 2 (4 mL) was added to the solid carrier 2 (1.18 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.27 g of the polymerization catalyst 2.

(55) <Preparation of Polymerization Catalyst 3>

(56) Preparation of solid carrier 3: Silica calcinated at 600 C. (1.06 g) (Grace 948) was collected and toluene (4 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2BHT (0.25M, 6.5 mL, 1.6 mmol) was added at room temperature with stirring, followed by a reaction at 70 C. for 1 hour. The toluene solution of AliBu.sub.2BHT was prepared in the same manner as in Example 1. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.21 g of the solid carrier 3.

(57) Preparation of metal catalyst component 3: Ni(COD).sub.2 (57.6 mg, 0.209 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.052M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (156.7 mg, 0.207 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 3.

(58) Preparation of polymerization catalyst 3: The metal catalyst component 3 (4 mL) was added to the solid carrier 3 (1.21 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.35 g of the polymerization catalyst 3.

(59) <Preparation of Polymerization Catalyst 4>

(60) Preparation of solid carrier 4: Silica calcinated at 600 C. (1.02 g) (Grace 948) was collected and toluene (4 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2BHT (0.25M, 6.2 mL, 1.5 mmol) was added at room temperature with stirring, followed by a reaction at 70 C. for 1 hour. The toluene solution of AliBu.sub.2BHT was prepared in the same manner as in Example 1. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.18 g of the solid carrier 4.

(61) Preparation of metal catalyst component 4: Ni(COD).sub.2 (52.2 mg, 0.190 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.048M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-302 (114.3 mg, 0.187 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 4.

(62) Preparation of polymerization catalyst 4: The metal catalyst component 4 (4 mL) was added to the solid carrier 4 (1.18 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.26 g of the polymerization catalyst 4.

(63) <Preparation of Polymerization Catalyst 5>

(64) Preparation of solid carrier 5: Silica calcinated at 600 C. (1.01 g) (Grace 948) was collected and toluene (4 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2BHT (0.25M, 6.2 mL, 1.5 mmol) was added at room temperature with stirring, followed by a reaction at 70 C. for 1 hour. The toluene solution of AliBu.sub.2BHT was prepared in the same manner as in Example 1. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.15 g of the solid carrier 5.

(65) Preparation of metal catalyst component 5: Ni(COD).sub.2 (58.9 mg, 0.214 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.054M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-304 (131.7 mg, 0.206 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 5.

(66) Preparation of polymerization catalyst 5: The metal catalyst component 5 (4 mL) was added to the solid carrier 5 (1.15 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.21 g of the polymerization catalyst 5.

(67) <Preparation of Polymerization Catalyst 6>

(68) Preparation of solid carrier 6: Silica calcinated at 600 C. (0.98 g) (Grace 948) was collected and toluene (5 mL) was added thereto. Thereafter, a toluene solution of Al(OiPr).sub.3 (0.46M, 4.2 mL, 1.9 mmol) was added at room temperature with stirring, followed by a reaction at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.10 g of the solid carrier 6.

(69) Preparation of metal catalyst component 6: Ni(COD).sub.2 (58.2 mg, 0.212 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.053M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (155.7 mg, 0.205 mmol) and the whole was stirred at room temperature for 30 minutes to obtain a toluene solution containing the metal catalyst component 6.

(70) Preparation of polymerization catalyst 6: The metal catalyst component 6 (4 mL) was added to the solid carrier 6 (1.10 g) at room temperature and they were brought into contact with each other at 40 C. for 2 hours. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.14 g of the polymerization catalyst 6.

(71) <Preparation of Polymerization Catalyst 7>

(72) Preparation of solid carrier 7: Silica calcinated at 600 C. (1.00 g) (Grace 948) was collected and toluene (6 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2(OEt) (0.47M, 4.3 mL, 2.0 mmol) was added at room temperature with stirring, followed by a reaction at 70 C. for 1 hour. The toluene solution of AliBu.sub.2(OEt) was prepared by adding a toluene solution of Al(OEt).sub.3 (0.40M, 10.0 mL, 4.0 mmol) to a toluene solution of TIBA (0.51M, 16.0 mL, 8.2 mmol) dropwise at 80 C. over a period of 3 minutes and stirring the whole at 80 C. for 1 hour. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.13 g of the solid carrier 7.

(73) Preparation of metal catalyst component 7: Ni(COD).sub.2 (58.0 mg, 0.211 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.053M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (157.4 mg, 0.208 mmol) and the whole was stirred at room temperature for 30 minutes to obtain a toluene solution containing the metal catalyst component 7.

(74) Preparation of polymerization catalyst 7: The metal catalyst component 7 (4 mL) was added to the solid carrier 7 (1.13 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.22 g of the polymerization catalyst 7.

(75) <Preparation of Polymerization Catalyst 8>

(76) Preparation of solid carrier 8: Silica calcinated at 600 C. (1.04 g) (Grace 948) was collected and a toluene solution of AliBu(OEt).sub.2 (0.29M, 5.3 mL, 1.60 mmol) was added thereto at room temperature, followed by stirring at 70 C. for 1 hour. The toluene solution of AliBu(OEt).sub.2 was prepared by adding a toluene solution of TIBA (0.51M, 3.6 mL, 1.8 mmol) to a toluene solution of Al(OEt).sub.3 (0.24M, 15.0 mL, 3.6 mmol) at room temperature and stirring the whole for 1 hour after heating to 105 C. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.23 g of the solid carrier 8.

(77) Preparation of metal catalyst component 8: Ni(COD).sub.2 (55.8 mg, 0.203 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.051M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (147.8 mg, 0.195 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 8.

(78) Preparation of polymerization catalyst 8: The metal catalyst component 8 (4 mL) was added to the solid carrier 8 (1.23 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.24 g of the polymerization catalyst 8.

(79) <Preparation of Polymerization Catalyst 9>

(80) Preparation of solid carrier 9: Silica calcinated at 600 C. (1.05 g) (Grace 948) was collected and toluene (9 mL) was added thereto. Thereafter, a toluene solution of AlEt.sub.2(OEt) (0.50M, 1.0 mL, 0.5 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) twice and then dried under reduced pressure to obtain 1.10 g of the solid carrier 9.

(81) Preparation of metal catalyst component 9: Ni(COD).sub.2 (59.8 mg, 0.217 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.054M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (161.0 mg, 0.212 mmol) and the whole was stirred at room temperature for 25 minutes to obtain a toluene solution containing the metal catalyst component 9.

(82) Preparation of polymerization catalyst 9: The metal catalyst component 9 (4 mL) was added to the solid carrier 9 (1.10 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.19 g of the polymerization catalyst 9.

(83) <Preparation of Polymerization Catalyst 10>

(84) Preparation of solid carrier 10: Silica calcinated at 600 C. (0.98 g) (Grace 948) was collected and toluene (5 mL) was added thereto. Thereafter, a toluene solution of Al(OEt).sub.3 (0.08M, 6.4 mL, 0.5 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) twice and then dried under reduced pressure to obtain 1.04 g of the solid carrier 10.

(85) Preparation of metal catalyst component 10: Ni(COD).sub.2 (50.7 mg, 0.184 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.046M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (140.0 mg, 0.185 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 10.

(86) Preparation of polymerization catalyst 10: The metal catalyst component 10 (4 mL) was added to the solid carrier 10 (1.04 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.07 g of the polymerization catalyst 10.

(87) <Preparation of Polymerization Catalyst 11>

(88) Preparation of solid carrier 11: Silica calcinated at 600 C. (1.05 g) (Grace 948) was collected and toluene (7.3 mL) was added thereto. Thereafter, a toluene solution of B(OnBu).sub.3 (0.20M, 2.7 mL, 0.5 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) twice and then dried under reduced pressure to obtain 1.09 g of the solid carrier 11.

(89) Preparation of metal catalyst component 11: Ni(COD).sub.2 (56.6 mg, 0.206 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.052M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (153.1 mg, 0.202 mmol) and the whole was stirred at room temperature for 30 minutes to obtain a toluene solution containing the metal catalyst component 11.

(90) Preparation of polymerization catalyst 11: The metal catalyst component 11 (4 mL) was added to the solid carrier 11 (1.09 g) at room temperature and they were brought into contact with each other at 50 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.13 g of the polymerization catalyst 11.

(91) <Preparation of Polymerization Catalyst 12>

(92) Preparation of solid carrier 12: Silica calcinated at 600 C. (1.04 g) (Grace 948) was collected and toluene (4 mL) was added thereto. Thereafter, a toluene solution of B(OEt).sub.3 (0.26M, 6.1 mL, 1.6 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) twice and then dried under reduced pressure to obtain 1.09 g of the solid carrier 12.

(93) Preparation of metal catalyst component 12: Ni(COD).sub.2 (51.9 mg, 0.189 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.047M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (147.4 mg, 0.194 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 12.

(94) Preparation of polymerization catalyst 12: The metal catalyst component 12 (4 mL) was added to the solid carrier 12 (1.09 g) at room temperature and they were brought into contact with each other at 60 C. for 30 minutes. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.10 g of the polymerization catalyst 12.

(95) <Preparation of Polymerization Catalyst 13>

(96) Preparation of solid carrier 13: Silica calcinated at 600 C. (1.03 g) (Grace 948) was collected and toluene (9 mL) was added thereto. Thereafter, a toluene solution of Et.sub.2Zn (0.50M, 0.5 mL, 0.3 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.05 g of the solid carrier 13.

(97) Preparation of metal catalyst component 13: Ni(COD).sub.2 (58.9 mg, 0.214 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.054M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (147.6 mg, 0.195 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 13.

(98) Preparation of polymerization catalyst 13: The metal catalyst component 13 (4 mL) was added to the solid carrier 13 (1.05 g) at room temperature and they were brought into contact with each other at 30 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.16 g of the polymerization catalyst 13.

(99) <Preparation of Polymerization Catalyst 14>

(100) Preparation of solid carrier 14: Silica calcinated at 600 C. (1.01 g) (Grace 948) was collected and toluene (7 mL) was added thereto. Thereafter, a toluene solution of nBuLi (0.50M, 3.0 mL, 1.5 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.13 g of the solid carrier 14.

(101) Preparation of metal catalyst component 14: Ni(COD).sub.2 (55.1 mg, 0.200 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.050M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (143.0 mg, 0.189 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 14.

(102) Preparation of polymerization catalyst 14: The metal catalyst component 14 (4 mL) was added to the solid carrier 14 (1.13 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.07 g of the polymerization catalyst 14.

(103) <Preparation of Polymerization Catalyst 15>

(104) Preparation of solid carrier 15: An aqueous solution of LiOH (0.0072 wt %, 100 g) was added to 6.0 g of granulated Montmorillonite (Mizusawa Industrial Chemicals, Ltd.) and the whole was stirred and mixed at room temperature to react them at room temperature for 1 hour. After the resultant one was washed with water and then dried at 100 C., it was further dried at 200 C. under reduced pressure for 1 hour. A toluene solution of B(OEt).sub.3 (0.25M, 6.0 mL, 1.5 mmol) was added to 0.98 g of the dried product at room temperature, followed by reaction at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) twice to obtain 1.03 g of the solid carrier 15.

(105) Preparation of metal catalyst component 15: Ni(COD).sub.2 (56.0 mg, 0.204 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.050M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-195 (154.6 mg, 0.204 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 15.

(106) Preparation of polymerization catalyst 15: The metal catalyst component 15 (4 mL) was added to the solid carrier 15 (1.03 g) at room temperature and they were brought into contact with each other at 60 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.06 g of the polymerization catalyst 15.

(107) <Preparation of Polymerization Catalyst 16>

(108) Preparation of solid carrier 16: Silica (1.02 g) (Grace 948) was collected and toluene (8 mL) was added thereto. Thereafter, a toluene solution of B(OEt).sub.3 (0.26M, 2.0 mL, 0.5 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.02 g of the solid carrier 16.

(109) Preparation of metal catalyst component 16: Ni(COD).sub.2 (57.7 mg, 0.210 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.053M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (157.2 mg, 0.207 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 16.

(110) Preparation of polymerization catalyst 16: The metal catalyst component 16 (4 mL) was added to the solid carrier 16 (1.02 g) at room temperature and they were brought into contact with each other at 50 C. for 2 hours. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.08 g of the polymerization catalyst 16.

(111) <Preparation of Polymerization Catalyst 16>

(112) Preparation of solid carrier 16: Silica calcinated at 600 C. (1.02 g) (Grace 948) was collected and toluene (8 mL) was added thereto. Thereafter, a toluene solution of B(OEt).sub.3 (0.26M, 2.0 mL, 0.5 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.02 g of the solid carrier 16.

(113) Preparation of metal catalyst component 16: Ni(COD).sub.2 (57.7 mg, 0.210 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.053M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-203 (157.2 mg, 0.207 mmol) and the whole was stirred at room temperature for 20 minutes to obtain a toluene solution containing the metal catalyst component 16.

(114) Preparation of polymerization catalyst 16: The metal catalyst component 16 (4 mL) was added to the solid carrier 16 (1.02 g) at room temperature and they were brought into contact with each other at 50 C. for 2 hours. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.08 g of the polymerization catalyst 16.

(115) <Preparation of Polymerization Catalyst 17>

(116) Preparation of solid carrier 17: Silica calcinated at 600 C. (0.99 g) (Grace 948) was collected and toluene (8 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2(OEt) (0.50M, 3.0 mL, 1.5 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. The toluene solution of AliBu.sub.2(OEt) was prepared in the same manner as in the case of the polymerization catalyst 7. The solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.08 g of the solid carrier 17.

(117) Preparation of metal catalyst component 17: Ni(COD).sub.2 (59.9 mg, 0.218 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.055M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-195 (128.9 mg, 0.203 mmol) and the whole was stirred at room temperature for 30 minutes to obtain a toluene solution containing the metal catalyst component 17.

(118) Preparation of polymerization catalyst 17: The metal catalyst component 17 (4 mL) was added to the solid carrier 17 (1.08 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.16 g of the polymerization catalyst 17.

(119) <Preparation of Polymerization Catalyst 18>

(120) Preparation of solid carrier 18: Silica calcinated at 600 C. (1.01 g) (Grace 948) was collected and toluene (4 mL) was added thereto. Thereafter, a toluene solution of AliBu.sub.2BHT (0.25M, 4.1 mL, 1.0 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. The toluene solution of AliBu.sub.2BHT was prepared in the same manner as in Example 1. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.18 g of the solid carrier 18.

(121) Preparation of metal catalyst component 18: Ni(COD).sub.2 (52.3 mg, 0.190 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.048M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-111 (130.9 mg, 0.190 mmol) and the whole was stirred at room temperature for 30 minutes to obtain a toluene solution containing the metal catalyst component 18.

(122) Preparation of polymerization catalyst 18: The metal catalyst component 18 (4 mL) was added to the solid carrier 18 (1.18 g) at room temperature and they were brought into contact with each other at 40 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.19 g of the polymerization catalyst 18.

(123) <Preparation of Polymerization Catalyst 19>

(124) Preparation of solid carrier 19: Silica calcinated at 600 C. (1.01 g) (Grace 948) was collected and toluene (6 mL) was added thereto. Thereafter, a toluene solution of B(OEt).sub.3 (0.26M, 4.0 mL, 1.0 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.05 g of the solid carrier 19.

(125) Preparation of metal catalyst component 19: Ni(COD).sub.2 (27.8 mg, 0.101 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.025M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-27DM (57.1 mg, 0.101 mmol) and the whole was stirred at room temperature for 30 minutes to obtain a toluene solution containing the metal catalyst component 19.

(126) Preparation of polymerization catalyst 19: The metal catalyst component 19 (4 mL) was added to the solid carrier 19 (1.05 g) at room temperature and they were brought into contact with each other at 50 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 0.96 g of the polymerization catalyst 19.

(127) <Preparation of Polymerization Catalyst 20>

(128) Preparation of solid carrier 20: Silica calcinated at 600 C. (1.17 g) (Grace 948) was collected and toluene (6.5 mL) was added thereto. Thereafter, a toluene solution of nBuLi (0.50M, 3.5 mL, 1.8 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. Thereafter, the mixture was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.23 g of the solid carrier 20.

(129) Preparation of metal catalyst component 20: Ni(COD).sub.2 (27.3 mg, 0.100 mmol) was dissolved in 4 mL of toluene to prepare a toluene solution of 0.025M Ni(COD).sub.2. The prepared toluene solution of Ni(COD).sub.2 (4 mL) was added to B-27DM (62.5 mg, 0.111 mmol) and the whole was stirred at room temperature for 30 minutes to obtain a toluene solution containing the metal catalyst component 20.

(130) Preparation of polymerization catalyst 20: The metal catalyst component 20 (4 mL) was added to the solid carrier 20 (1.23 g) at room temperature and they were brought into contact with each other at 50 C. for 1 hour. The mixture was washed with toluene (20 mL) four times and with n-hexane (20 mL) twice and then dried under reduced pressure to obtain 1.25 g of the polymerization catalyst 20.

(131) <Preparation of Polymerization Catalyst 21>

(132) Preparation of solid carrier 21: Silica calcinated at 600 C. (1.00 g) (Grace 948) was collected and a toluene solution of AliBu.sub.3 (0.50M, 4.0 mL, 2.0 mmol) was added at room temperature, followed by stirring for 1 hour. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.12 g of a solid carrier 21_1. A toluene solution of BHT (0.48M, 4.2 mL, 2.0 mmol) was added to the resultant solid carrier 21_1 at room temperature, followed by stirring at 70 C. for 1 hour. The toluene solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.14 g of a solid carrier 21_2.

(133) Preparation of polymerization catalyst 21: A toluene solution of B-195 (4.0 mL, 0.20 mmol) was added to the solid carrier 21_2 and the whole was stirred at room temperature for 60 minutes, followed by drying under reduced pressure. Thereto was added 4.0 mL of a toluene solution of Ni(COD).sub.2 (55.0 mg, 0.20 mmol), followed by stirring at 60 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with hexane (20 mL) twice and then dried under reduced pressure to obtain 1.22 g of the polymerization catalyst 21.

(134) <Preparation of Polymerization Catalyst 22>

(135) Preparation of solid carrier 22: Silica calcinated at 600 C. (1.00 g) (Grace 948) was collected and a toluene solution of AliBu.sub.3 (0.40M, 5.0 mL, 2.0 mmol) was added at room temperature, followed by stirring for 1 hour. The solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.13 g of a solid carrier 22_1. Toluene (5 mL) was added to the resultant solid carrier 22_1 and a toluene solution of Al(OiPr).sub.3 (0.39M, 5.2 mL, 2.0 mmol) was added at room temperature, followed by stirring at 70 C. for 1 hour. The solution containing silica was washed with toluene (20 mL) three times and then dried under reduced pressure to obtain 1.12 g of a solid carrier 22_2.

(136) Preparation of polymerization catalyst 22: A toluene solution of B-195 (5.0 mL, 0.20 mmol) was added to the solid carrier and the whole was stirred at room temperature for 30 minutes. Thereto was added 5.0 mL of a toluene solution of Ni(COD).sub.2 (55.0 mg, 0.20 mmol), followed by stirring at 70 C. for 1 hour. The mixture was washed with toluene (20 mL) three times and with hexane (20 mL) twice and then dried under reduced pressure to obtain 1.22 g of the polymerization catalyst 22.

(137) Preparation of prepolymerization catalyst 22: Dry hexane (200 mL), a hexane solution of tri-n-octylaluminum (0.1M, 1 mL, 0.1 mmol), and nBA (0.2 mmol) were introduced into an induction-stirring-type autoclave having an inner volume of 2 L. After heating to 40 C., ethylene (0.05 MPa) was introduced and the polymerization catalyst 22 (1.0 g) was added. Ethylene was introduced up to a pressure of 0.05 MPa at every time when the pressure of ethylene decreased to 0 and the work was repeated (five times in total). By the operations, there was obtained the prepolymerization catalyst 22 containing 6.35 g of polyethylene per g of the polymerization catalyst.

(138) 4. Olefin Polymerization

Examples 1 to 23

(139) Homopolymerization of Ethylene and Copolymerization of Ethylene Acrylate Ester Using Polymerization Catalysts 1 to 17, 21, and 22

(140) (1) Homopolymerization of Ethylene

Examples 1 to 15, 20, and 21

(141) Dry hexane (1 L) and a hexane solution of tri-n-octylaluminum (0.01 mL, 1 mL) were introduced into an induction-stirring-type autoclave having an inner volume of 2 L. After the autoclave was heated to 70 C. with stirring, ethylene was supplied to the autoclave up to 3.0 MPa. After completion of the adjustment, a hexane slurry of each polymerization catalyst obtained in the above-described 3. Preparation of olefin polymerization catalyst was supplied to initiate polymerization. After polymerization was performed for 1 hour, an unreacted gas was purged, then the autoclave was opened, and filtration, washing with a solvent, and drying under heating were performed to obtain a polymer.

(142) Table 6 shows polymerization catalysts and polymerization conditions used and physical properties of the obtained polymers. In Table 6, Activity represents polymer yield (g) per g of the polymerization catalyst used for the polymerization per hour of polymerization time. BD represents bulk density and is an apparent density in the case where a powder is placed in the loosest state in a vessel whose volume is known. Table 6 also describes weight-average molecular weight (Mw) and molecular weight distribution (Mw/Mn) obtained from the results of GPC measurement on the obtained polymers.

(143) (2) Copolymerization of Ethylene/Acrylate Ester

Examples 16 to 19, 22, and 23

(144) Dry toluene (0.6 L) and a predetermined amount of an acrylate ester as a comonomer were introduced into an induction-stirring-type autoclave having an inner volume of 2 L. After the autoclave was heated to 90 C. with stirring, ethylene was supplied to the autoclave up to 3.0 MPa. After completion of the adjustment, a hexane slurry of each polymerization catalyst obtained in the above-described 3. Preparation of olefin polymerization catalyst was supplied to initiate copolymerization. After polymerization was performed for 1 hour, an unreacted gas was purged, then the autoclave was opened, and filtration, washing with a solvent, and drying under heating were performed to obtain a copolymer.

(145) Table 6 shows polymerization catalysts and polymerization conditions used, kinds and amounts of comonomers used for the copolymerization, and physical properties of the obtained polymers. Incidentally, the comonomers were used after they were purified at room temperature under a highly pure argon atmosphere using a column packed with AldrichInhibitorRemover manufactured by Aldrich Inc.

(146) In Table 6, tBA represents t-butyl acrylate, nBA represents n-butyl acrylate, and PA-1 represents 4-acryloyloxy-2,2,6,6-tetramethylpiperidine.

Comparative Examples 1 to 3

(147) Homopolymerization of Ethylene Using Polymerization Catalysts 18 to 20

(148) (3) Homopolymerization of Ethylene

(149) Dry hexane (1 L) and a hexane solution of tri-n-octylaluminum (0.01 mL, 1 mL) were introduced into an induction-stirring-type autoclave having an inner volume of 2 L. After the autoclave was heated to 70 C. with stirring, ethylene was supplied to the autoclave up to 3.0 MPa. After completion of the adjustment, a hexane slurry of each polymerization catalyst obtained in the above-described 3. Preparation of olefin polymerization catalyst was supplied to initiate polymerization. After polymerization was performed for 1 hour, an unreacted gas was purged, then the autoclave was opened, and filtration, washing with a solvent, and drying under heating were performed to obtain a polymer. Table 6 shows polymerization catalysts and polymerization conditions used and physical properties of the obtained polymers.

(150) TABLE-US-00006 TABLE 6 Catalyst Polymerization Carrier-treating Pre- amount catalyst compound Ligand polymerization (mg) Comonomer Example 1 1 AliBu2BHT B-195 No 56 absent Example 2 2 AliBu2BHT B-200 No 53 absent Example 3 3 AliBu2BHT B-203 No 57 absent Example 4 4 AliBu2BHT B-302 No 60 absent Example 5 5 AliBu2BHT B-304 No 75 absent Example 6 6 Al(OiPr)3 B-203 No 136 absent Example 7 7 AliBu2(OEt) B-203 No 119 absent Example 8 8 AliBu(OEt)2 B-203 No 216 absent Example 9 9 AlEt2(OEt) B-203 No 62 absent Example 10 10 Al(OEt)3 B-203 No 136 absent Example 11 11 B(OnBu)3 B-203 No 141 absent Example 12 12 B(OEt)3 B-203 No 220 absent Example 13 13 Et2Zn B-203 No 74 absent Example 14 14 nBuLi B-203 No 188 absent Example 15 15 B(OEt)3 B-195 No 212 absent Example 16 7 AliBu2(OEt) B-203 No 219 tBA Example 17 16 B(OEt)3 B-203 No 378 nBA Example 18 17 AliBu2(OEt) B-195 No 260 nBA Example 19 16 B(OEt)3 B-203 No 459 PA-1 Example 20 21 AliBu3/BHT B-195 No 82 absent Example 21 22 AliBu3/Al(OiPr)3 B-195 Yes 32 absent Example 22 21 AliBu3/BHT B-195 No 214 nBA Example 23 22 AliBu3/Al(OiPr)3 B-195 Yes 130 nBA Comparative 18 AliBu2BHT B-111 No 232 absent Example 1 Comparative 19 B(OEt)3 B-27DM No 199 absent Example 2 Comparative 20 nBuLi B-27DM No 265 absent Comonomer amount Activity BD Comonomer (mmol) (g/g .Math. h) Mw (g/mol) Mw/Mn (g/cc) (mol %) Example 1 2,130 1,509,000 5.2 0.33 Example 2 4,260 1,626,000 5.2 0.25 Example 3 6,320 1,693,000 6.3 0.26 Example 4 3,480 1,634,000 5.3 0.25 Example 5 3,330 n.d. n.d. 0.25 Example 6 650 2,848,000 5.9 0.33 Example 7 3,480 1,330,000 4.6 0.28 Example 8 720 n.d. n.d. 0.39 Example 9 1,330 2,217,000 4.8 0.39 Example 10 350 1,478,000 3.4 0.4 Example 11 580 1,530,000 3.9 0.41 Example 12 760 1,608,000 4.0 0.39 Example 13 580 n.d. n.d. 0.4 Example 14 270 1,695,000 4.8 0.36 Example 15 230 n.d. n.d. n.d. Example 16 42 25 404,000 5.3 0.31 0.25 Example 17 42 23 121,000 5.9 n.d. 1.36 Example 18 42 110 930,000 3.5 0.38 0.29 Example 19 16 110 660,000 3.7 0.26 0.03 Example 20 5,830 995,000 4.1 0.280 Example 21 5,810 n.d. n.d. 0.316 Example 22 42 280 n.d. n.d. 0.267 0.18 Example 23 42 430 n.d. n.d. 0.376 0.05 Comparative 1 n.d. n.d. n.d. Example 1 Comparative 2 n.d. n.d. n.d. Example 2 Comparative 4 n.d. n.d. n.d. Example 3 *n.d.: not determined
[Consideration of Comparative Results of Examples and Comparative Examples]

(151) As is apparent from Table 6, when Examples 1 to 23 are compared to Comparative Examples 1 to 3, it is understood that the polymerization catalysts of the invention exhibit high activity and particulate polymers are obtained. The bulk density BD is used as an index for representing particle properties, and particulate polymers for which BD can be measured have been obtained in Examples 1 to 23.

(152) While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. The present application is based on Japanese Patent Application No. 2014-150452 filed on Jul. 24, 2014, and the contents are incorporated herein by reference.

INDUSTRIAL APPLICABILITY

(153) By using the present invention, a particulate olefin (co)polymer can be produced at high activity without using a large amount of an expensive cocatalyst, so that the olefin (co)polymer can be produced at low costs. Accordingly, the invention is industrially extremely valuable.