Solid catalyst for polymerizing an olefin

Claim 2

A solid catalyst for polymerizing an olefin or co-polymerizing olefins produced by the process comprising contacting an α-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, a fine-particle carrier, and a transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 3

The solid catalyst according to claim 1, wherein M is zirconium.

Claim 4

The solid catalyst according to claim 1 wherein the α-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 5

The solid catalyst according to claim 1 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 6

The solid catalyst according to claim 4 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 7

The solid catalyst according to claim 1 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 8

The solid catalyst according to claim 6 wherein said organic polymer comprises a polyolefin.

Claim 9

The solid catalyst according to claim 1 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR8## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 10

The solid catalyst according to claim 1 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 11

The solid catalyst according to claim 1 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium chloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.

Claim 12

A solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 13

A solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 14

The solid catalyst according to claim 11 wherein the fine-particle carrier and the organoaluminum compound are mixed before the addition of the aluminoxane.

Claim 15

The solid catalyst according to claim 11 wherein M is zirconium.

Claim 16

The solid catalyst according to claim 11 wherein the α-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 17

The solid catalyst according to claim 11 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 18

The solid catalyst according to claim 15 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 19

The solid catalyst according to claim 11 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 20

The solid catalyst according to claim 17 wherein said organic polymer comprises a polyolefin.

Claim 21

The solid catalyst according to claim 11 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR9## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 22

The solid catalyst according to claim 11 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 23

The process according to claim 11 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium, chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.

Claim 24

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins produced by the process comprising contacting an α-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, a fine-particle carrier, and a transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 25

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins produced by the process comprising contacting an α-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, a fine-particle carrier, and a transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 26

The process according to claim 22, wherein M is zirconium.

Claim 27

The process according to claim 22 wherein the α-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 28

The process according to claim 22 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 29

The process according to claim 25 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 30

The process according to claim 22 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 31

The process according to claim 27 wherein said organic polymer comprises a polyolefin.

Claim 32

The process according to claim 22 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR10## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 33

The process according to claim 22 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 34

The process according to claim 22 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium, chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium chloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.

Claim 35

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to the mixture to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 36

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to the mixture to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 37

The process according to claim 32 wherein the fine-particle carrier and the organoaluminum compound are mixed before the addition of the aluminoxane.

Claim 38

The process according to claim 32 wherein M is zirconium.

Claim 39

The process according to claim 32 wherein the α-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 40

The process according to claim 32 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 41

The process according to claim 36 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 42

The process according to claim 32 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 43

The process according to claim 38 wherein said organic polymer comprises a polyolefin.

Claim 44

The solid catalyst according to claim 32 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR11## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 45

The process according to claim 32 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 46

The process according to claim 32 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium, chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.

Claim 47

A solid catalyst for polymerizing an olefin or co-polymerizing olefins produced by the process comprising contacting an α-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, a fine-particle carrier, and a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 48

A solid catalyst for polymerizing an olefin or co-polymerizing olefins produced by the process comprising contacting an α-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, a fine-particle carrier, and a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 49

The solid catalyst according to claim 43, wherein M is zirconium.

Claim 50

The solid catalyst according to claim 43 wherein the ≢-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 51

The solid catalyst according to claim 43 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 52

The solid catalyst according to claim 46 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 53

The solid catalyst according to claim 43 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 54

The solid catalyst according to claim 48 wherein said organic polymer comprises a polyolefin.

Claim 55

The solid catalyst according to claim 43 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR12## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 56

The process according to claim 43 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 57

The solid catalyst according to claim 43 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium, chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.

Claim 58

A solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to the mixture to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 59

A solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to the mixture to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 60

The solid catalyst according to claim 53 wherein the fine-particle carrier and the organoaluminum compound are mixed before the addition of the aluminoxane.

Claim 61

The solid catalyst according to claim 53 wherein M is zirconium.

Claim 62

The solid catalyst according to claim 53 wherein the α-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 63

The solid catalyst according to claim 53 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 64

The solid catalyst according to claim 57 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 65

The solid catalyst according to claim 53 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 66

The solid catalyst according to claim 59 wherein said organic polymer comprises a polyolefin.

Claim 67

The solid catalyst according to claim 53 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR13## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 68

The solid catalyst according to claim 53 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 69

The process according to claim 53 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium, chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.

Claim 70

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins produced by the process comprising contacting an α-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, a fine-particle carrier, and a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 71

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins produced by the process comprising contacting an α-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, a fine-particle carrier, and a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 72

The process according to claim 64, wherein M is zirconium.

Claim 73

The process according to claim 64 wherein the α-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 74

The process according to claim 64 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 75

The process according to claim 67 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 76

The process according to claim 64 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 77

The process according to claim 69 wherein said organic polymer comprises a polyolefin.

Claim 78

The process according to claim 64 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR14## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 79

The process according to claim 64 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 80

The process according to claim 64 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium, chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium chloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.

Claim 81

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to the mixture to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 82

A process for producing a solid catalyst for polymerizing an olefin or co-polymerizing olefins, wherein said solid catalyst is prepared by the process comprising contacting an α-olefin with a composition obtained by mixing together an organoaluminum compound having a branched alkyl radical, an aluminoxane, with the proviso that a ratio of the aluminum content in the aluminoxane to the aluminum content in the organoaluminum compound is in the range of 1.25 to 5.0, and a fine-particle carrier, in an arbitrary order, and then adding a metallocene, as the only transition metal compound, represented by the formula (III): R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m R.sup.4.sub.n M (III) to the mixture to pre-polymerize the α-olefin and produce said solid catalyst; wherein M is selected from the group consisting of titanium, zirconium, and hafnium; R 1 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon; R 2 , R 3 and R 4 are independently selected from the group consisting of a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon, an aryl, an alkyl, a cycloalkyl, an aralkyl, a halogen, hydrogen, OR a , SR b , NR c 2 and PR d 2 , wherein R a , R b , R c and R d are independently a hydrocarbon radical selected from the group consisting of an alkyl, a cycloalkyl, an aryl and an aralkyl or silyl, with the proviso that R c and R d may, taken together, form a ring; k is at least 1; and the sum of k, l, m, and n equals 4; and wherein R 1 and R 2 may be bonded by an intervening lower alkylene radical when R 2 is a cyclopentadienyl radical optionally substituted with at least one C 1-4 hydrocarbon.

Claim 83

The process according to claim 74 wherein the fine-particle carrier and the organoaluminum compound are mixed before the addition of the aluminoxane.

Claim 84

The process according to claim 74 wherein M is zirconium.

Claim 85

The process according to claim 74 wherein the α-olefin is contacted with the mixture in the presence of a hydrocarbon solvent.

Claim 86

The process according to claim 74 wherein the fine-particle carrier comprises an inorganic oxide having an average particle diameter in the range of from 1 to 300 micrometers.

Claim 87

The process according to claim 78 wherein said oxide comprises at least an oxide selected from the group consisting of SiO 2 , Al 2 O 3 , and MgO.

Claim 88

The process according to claim 74 wherein the fine-particle carrier comprises an organic polymer and has an average particle diameter in the range of from 1 to 300 micrometers.

Claim 89

The process according to claim 80 wherein said organic polymer comprises a polyolefin.

Claim 90

The solid catalyst according to claim 74 wherein said aluminoxane comprises a compound represented by the formula (I) or (II): ##STR15## wherein R is a C 1-20 hydrocarbon radical and m has a value of 2 to 50.

Claim 91

The process according to claim 74 wherein the cyclopentadienyl radical is selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, and tetrahydroindenyl radicals.

Claim 92

The process according to claim 74 wherein the transition metal compound is selected from the group consisting of ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monobromide, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)benzylzirconium monochloride, ethylenebis(indenyl)methylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dimethoxide, ethylenebis(indenyl)zirconium diethoxide, ethylenebis(indenyl)methoxyzirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)methylzirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide.