# US 5,707,914 A · Catalyst components for polymerization of olefins

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- Number: US 5,707,914 A
- Document ID: US5707914A
- Status: Granted
- Kind: A
- Application number: 08/461,095
- Filed: 1995-06-05
- Granted: 1998-01-13
- Earliest claimed: 1991-11-12
- Assignees: Nippon Oil Co., Ltd.
- Inventors: Naoki Kataoka; Yosuke Numao; Takashi Seki; Yoshio Tajima; Kazuo Matsuura
- Web page: https://patentgrep.com/patent/US5707914A

## CPC

- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- Y10S 526/901: Monomer polymerized in vapor state in presence of transition metal containing catalyst
- Y10S 526/943: Polymerization with metallocene catalysts
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A process for the polymerization of olefinic hydrocarbons is carried out in the presence of a catalyst comprising a catalyst component derived from reacting a compound of the formula Me.sup.1 R.sup.1.sub.n X.sup.1.sub.4-n, a compound of the formula Me.sup.2 R.sup.2.sub.m X.sup.2.sub.z-m, an organocyclic compound having two or more conjugated double bonds and a carrier of inorganic or polymeric material, and a modified organoaluminum compound having Al--O--Al bonds, the resulting polyolefins having a relatively wide molecular weight distribution, a relatively narrow composition distribution and increased bulk density.

## Claims

### Claim 1

A catalyst component for use in the manufacture of polyolefins which is a reaction product of reaction compounds consisting essentially of;
a compound (i) of the formula
Me.sup.1 R.sub.4.sup.1
wherein R.sup.1 is selected from the group consisting of an alkyl, alkenyl, aryl, alkoxy, aryloxy, and aralkyloxy moiety of 1-24 carbon atoms, and Me.sup.1 is zirconium or hafnium;
a compound (ii) of formula
Me.sup.2 R.sub.m.sup.2 X.sup.2.sub.z-m
wherein R.sup.2 is a hydrocarbon group of 1-24 carbon atoms, X.sup.2 is a halogen atom, Me.sup.2 is an element of Group III in the Periodic Table, z is the valence of Me.sup.2, and m is a number such that 0.ltoreq.m.ltoreq.3;
a cyclic hydrocarbon compound (iii) having two or more conjugated double bonds; and
a carrier (iv) selected from the group consisting of inorganic carriers, particulate polymer carriers and mixtures thereof.

### Claim 2 (depends on 1)

A catalyst composition as claimed in claim 1 wherein R.sup.1 is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, vinyl, allyl, phenyl, tolyl, xylyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, phenoxy, tolyloxy and benzyloxy.

### Claim 3 (depends on 1)

A catalyst component as claimed in claim 1 wherein R.sup.2 is an alkyl, alkenyl, aryl or aralkyl group.

### Claim 4 (depends on 1)

A catalyst component as claimed in claim 1 wherein R.sup.2 is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, vinyl, allyl, phenyl, tolyl, xylyl, benzyl, phenethyl and styryl.

### Claim 5 (depends on 1)

A catalyst component as claimed in claim 1 wherein said compound (ii) is an organoaluminum compound of the formula
R.sub.3 Al, .sub..theta. R.sub.2 AlX, RAlX.sub.2 or R.sub.3 Al.sub.2 X.sub.3
wherein R is a hydrocarbon group of 1-5 carbon atoms and X is a halogen atom.

### Claim 6 (depends on 1)

A catalyst component as claimed in claim 1 wherein said cyclic hydrocarbon compound (iii) has 2-4 conjugated double bonds and a carbon number of 4-24 in the molecule.

### Claim 7 (depends on 1)

A catalyst component as claimed in claim 1 wherein said cyclic hydrocarbon compound (iii) is selected from the group consisting of an aralkylene of 7-24 carbon atoms, cyclopentadiene, cyclopentadiene substituted with an alkyl or aralkyl group of 1-12 carbon atoms, indene, indene substituted with an alkyl or aralkyl group of 1-12 carbon atoms, fluorene, fluorene substituted with an alkyl or aralkyl group of 1-12 carbon atoms, cycloheptatriene, cycloheptatriene substituted with an alkyl or aralkyl group of 1-12 carbon atoms, cyclooctatetraene, cyclooctatetraene substituted with an alkyl or aralkyl group of 1-12 carbon atoms and derivatives thereof cross-linked with an alkylene group.

### Claim 8 (depends on 7)

A catalyst component as claimed in claim 7 wherein said alkylene group has 2-8 carbon atoms.

### Claim 9 (depends on 1)

A catalyst component as claimed in claim 1 wherein said cyclic hydrocarbon compound (iii) is selected from the group consisting of cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene, fluorene, methylfluorene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene, bis-indenylethane, bis(4,5,6,7-tetrahydro-1-indenyl)ethane, 1,3-propanedinyl-bis-indene, 1,3-propanedinyl-bis(4,5,6,7-tetrahydro)indene, propylene-bis(1-indene), isopropyl(1-indenyl) cyclopentadiene, diphenylmethylene(9-fluorenyl) cyclopentadiene and isopropylcyclopentadienyl-1-fluorene.

### Claim 10 (depends on 1)

A catalyst component as claimed in claim 1 wherein said inorganic carrier (iv) is formed of a porous inorganic compound selected from the group consisting of a carbonaceous material, metal, metal oxide, metal chloride, metal carbonate and mixtures thereof, said inorganic carrier having a maximum length of 5-200 .mu.m, the maximum length referring to the distance between those two points on the surface of the carrier that are furthest from each other, a surface area of 50-1,000 m.sup.2 /g and a pore volume of 0.05-3 cm.sup.3 /g.

### Claim 11 (depends on 10)

A catalyst component as claimed in claim 10 wherein said carrier (iv) is treated with an agent selected from the group consisting of an active hydrogen-containing compound, an electron-donative compound and an alkoxide-containing compound.

### Claim 12 (depends on 11)

A catalyst component as claimed in claim 11 wherein said active hydrogen-containing compound is an alcohol or an aldehyde, said electron-donative compound is an ester or an ether, and said alkoxide-containing compound is a tetraalkoxysilicate, a trialkoxyaluminum or a transition metal tetraalkoxide.

### Claim 13 (depends on 1)

A catalyst component as claimed in claim 1 wherein said particulate polymer carrier (iv) is formed of a thermoplastic or thermosetting resin having an average particle size of 5-2,000 .mu.m.

### Claim 14 (depends on 1)

A catalyst component as claimed in claim 1 wherein at least one of R.sup.1 is selected from the group consisting of an alkoxy, aryloxy and aralkyloxy moiety of 1-8 carbon atoms.

### Claim 15 (depends on 1)

A catalyst component as claimed in claim 1 wherein the molar ratio of said compound (ii) to said compound (i) is in the range of 0.1:1 to 100:1, and the molar ratio of said compound (iii) to said compound (i) is in the range of 0.1:1 to 10:1.

### Claim 16 (depends on 1)

A catalyst component as claimed in claim 1 wherein the molar ratio of said compound (ii) to said compound (i) is in the range of 1:1 to 10:1, and the molar ratio of said compound (iii) to said compound (i) is in the range of 1:1 to 5:1.

### Claim 17 (depends on 1)

A catalyst component as claimed in claim 1 wherein the ratio of said compound (i) to said carrier (iv) is in the range of 0.01 to 500 millimoles of said compound (i) per 100 g of said carrier (iv).

### Claim 18 (depends on 1)

A catalyst component as claimed in claim 1 wherein the ratio of said compound (i) to said carrier (iv) is in the range of 0.1 to 20 millimoles of said compound (i) per 100 g of said carrier (iv).

### Claim 19

A catalyst composition for use in the manufacture of polyolefins which is comprised of a first component (I) and a second component (II), where said first component (I) is a reaction product of reaction compounds consisting essentially of:
a compound (i) of formula
Me.sup.1 R.sub.4.sup.1
wherein R.sup.1 is selected from the group consisting of an alkyl, alkenyl, aryl, alkoxy, aryloxy, and aralkyloxy moiety of 1-24 carbon atoms, and Me.sup.1 is zirconium or hafnium;
a compound (ii) of the formula
Me.sup.2 R.sub.m.sup.2 X.sub.z-m.sup.2
wherein R.sup.2 is a hydrocarbon group of 1-24 carbon atoms, X.sup.2 is a halogen atom, Me.sup.2 is an element of Group III in the Periodic Table, z is the valence of Me.sup.2, and m is a number such that 0.ltoreq.m.ltoreq.3;
a cyclic hydrocarbon (iii) having two or more conjugated double bonds; and
a carrier (iv) selected from the group consisting of inorganic carriers, particulate polymer carriers and mixtures thereof;
said second component (II) being a modified organoaluminum compound having at least one Al--O--Al bond derived from the reaction of an organoaluminum compound and water.

### Claim 20 (depends on 19)

A catalyst composition as claimed in claim 19 wherein the modified organoaluminum compound has 1-100 Al--O--Al bonds in the molecule.

### Claim 21 (depends on 19)

A catalyst composition as claimed in claim 19 wherein the modified organoaluminum compound has 1-50 Al--O--Al bonds in the molecule.

### Claim 22 (depends on 19)

A catalyst composition as claimed in claim 19 wherein the organoaluminum compound of component (II) is a compound of the formula
R.sub.v.sup.5 AlX.sub.3-v.sup.5
wherein R.sup.5 is an alkyl, alkenyl, aryl or aralkyl group having a carbon number of 1-18, X.sup.5 is a hydrogen or halogen atom, and 1.ltoreq.v.ltoreq.3.

### Claim 23 (depends on 19)

A catalyst composition as claimed in claim 19 wherein the molar ratio of the organoaluminum compound to water is in the range of 1:0.25 to 1:1.2.

### Claim 24 (depends on 19)

A catalyst composition as claimed in claim 19 wherein the atomic ratio of aluminum in the second component (II) to the transition metal in the first component (I) is in the range of 1:1 to 100,000:1.

### Claim 25 (depends on 19)

A catalyst composition as claimed in claim 19 wherein the atomic ratio of aluminum in the second component (II) to the transition metal in the first component (I) is in the range of 5:1 to 1,000:1.