# US 5,710,224 A · Method for producing polymer of ethylene

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- Number: US 5,710,224 A
- Document ID: US5710224A
- Status: Granted
- Kind: A
- Application number: 08/399,119
- Filed: 1995-03-03
- Granted: 1998-01-20
- Earliest claimed: 1991-07-23
- Assignees: Phillips Petroleum Company
- Inventors: Helmut G. Alt; Syriac J. Palackal; M. Bruce Welch; David C. Rohlfing; Jay Janzen
- Web page: https://patentgrep.com/patent/US5710224A

## CPC

- C08F 10/02: Ethene
- B01J 31/143: {of aluminium}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- C07C 13/567: with a fluorene or hydrogenated fluorene ring system
- C07C 51/31: of cyclic compounds with ring-splitting
- C07C 51/373: by introduction of functional groups containing oxygen only in doubly bound form
- C07C 51/377: by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)}
- C07F 5/068: {preparation of alum(in)oxanes}
- C07F 17/00: Metallocenes
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- B01J 31/1608: {the ligands containing silicon}
- B01J 2531/48: Zirconium
- C07B 2200/11: Compounds covalently bound to a solid support
- C07C 2601/10: the ring being unsaturated
- C07C 2603/18: Fluorenes; Hydrogenated fluorenes
- C08F 4/61912: {in combination with an organoaluminium compound}
- C08F 4/61916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/61927: {two cyclopentadienyl rings being mutually bridged}
- C08F 4/63912: {in combination with an organoaluminium compound}
- C08F 4/63922: {containing at least two cyclopentadienyl rings, fused or not}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 110/02: Ethene
- C08F 110/06: Propene
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

A process for preparing a polymer of ethylene having a flow activation energy higher than that of a substantially linear ethylene polymer of the same molecular weight involving using bridged sandwich-bonded fluorenyl-containing metallocenes and the polymers resulting therefrom.

## Claims

### Claim 1

A process for preparing a polymer of ethylene having a flow activation energy of at least about 25 kJ/mol, comprising contacting ethylene in a liquid diluent with a catalyst system comprising:
(1) a catalyst comprising 1-(9-fluorenyl)-2-(indenyl) ethane zirconium dichloride, and
(2) a cocatalyst for said metallocene.

### Claim 2 (depends on 1)

A process according to claim 1 wherein said cocatalyst comprises an aluminoxy co-catalyst having repeating units of the formula ##STR4## wherein, R is a hydrocarbyl group.

### Claim 3 (depends on 2)

A process according to claim 2 which produces a polymer of ethylene having a density of less than 0.92 g/cc and a flow activation energy of at least 35 kJ/mol.

### Claim 4 (depends on 1)

A process according to claim 1 wherein said polymerization is conducted at a temperature in the range of about 60.degree. C. to about 111.degree. C. in a liquid diluent consisting essentially of isobutane.

### Claim 5 (depends on 4)

A process according to claim 4 wherein ethylene is polymerized in the absence of comonomer to produce a polymer having a flow activation energy of at least about 30, weight average molecular weight of at least 30,000, an HI in the range of 2 to 20, and a density of at least about 0.94 cc/g.

### Claim 6 (depends on 4)

A process according to claim 4 wherein ethylene is polymerized in the presence of an acyclic comonomer having 4 to 12 carbon atoms.

### Claim 7 (depends on 4)

A process according to claim 4 wherein ethylene is copolymerized with hexene-1.

### Claim 8 (depends on 7)

A process according to claim 7 wherein said cocatalyst is a solid hydrocarbyl aluminoxy cocatalyst prepared by reacting methylaluminoxane and an organoboroxine.

### Claim 9

A process for preparing a polymer of ethylene having a flow activation energy of at least about 25 kJ/mol comprising contacting ethylene in the presence of an acyclic olefinic comonomer having 4 to 12 carbon atoms in a liquid diluent wherein the molar ratio of the comonomer employed to the ethylene employed is in the range of from about 0.025/1 to about 0.5/1 and the resulting copolymer has a density in the range of 0.88 to about 0.96 g/cc using a catalyst system comprising:
(1) a fluorenyl-containing metallocene selected from compounds of the formula (Z)--R'--(Z')MeQ.sub.2 wherein R' is selected from --CH.sub.2 CH.sub.2 --, --CH.sub.2 --, and dimethylsilylene, and each Q is a halide, Z is a substituted or unsubstituted fluorenyl radical, Z' is a substituted or unsubstituted fluorenyl radical, a substituted or unsubstituted indenyl radical, a substituted or unsubstituted cyclopentadienyl radical, a tetrahydroindenyl radical, or an octahydrofluorenyl radical; Me is selected from Zr and Hf, and
(2) a cocatalyst for said metallocene.

### Claim 10 (depends on 9)

A process according to claim 9 wherein said cocatlyst comprises an aluminoxy co-catalyst having repeating units of the formula ##STR5## wherein R is a hydrocarbyl group.

### Claim 11 (depends on 9)

A process according to claim 9 wherein Me is Zr.

### Claim 12 (depends on 11)

A process according to claim 11 wherein R' is dimethylsilylene.

### Claim 13 (depends on 9)

A process according to claim 9 wherein said catalyst comprises 1-(9-fluorenyl)-1-(cyclopentadienyl) methane zirconium dichloride.

### Claim 14 (depends on 9)

A process according to claim 9 wherein said catalyst comprises 1-(9-fluorenyl)-2-(indenyl) ethane zirconium dichloride.

### Claim 15 (depends on 9)

A process according to claim 9 wherein said catalyst comprises 1-(9-fluorenyl)-1-(indenyl) dimethyl silane zirconium dichloride.

### Claim 16 (depends on 9)

A process according to claim 9 wherein said catalyst comprises bis 1,2-(9-fluorenyl) ethane zirconium dichloride.

### Claim 17 (depends on 9)

A process according to claim 9 wherein said catalyst comprises 1-(9-fluorenyl)-1-(3-prop-1-enyl indenyl) dimethyl silane zirconium dichloride.

### Claim 18 (depends on 9)

A process according to claim 9 wherein Z' is selected from substituted or unsubstituted indenyl.

### Claim 19 (depends on 11)

A process according to claim 11 wherein Z' is selected from substituted or unsubstituted indenyl.

### Claim 20 (depends on 9)

A process according to claim 9 wherein the molar ratio of comonomer employed to ethylene employed is in the range of from about 0.025/1 to about 0.5/1 and the resulting copolymer has a molecular weight of at least about 30,000 and a density in the range of from about 0.88 to about 0.96 g/cc.

### Claim 21 (depends on 9)

A process according to claim 9 wherein ethylene is copolymerized with hexene-1.

### Claim 22 (depends on 21)

A process according to claim 21 wherein said copolymerization is conducted at a temperature in the range of about 60.degree. C. to about 111.degree. C. and the liquid diluent consists essentially of isobutane.

### Claim 23 (depends on 22)

A process according to claim 22 which produces a polymer of ethylene having a flow activation energy in the range of about 30 to about 60 kJ/mol and a density of less than 0.92 g/cc.

### Claim 24 (depends on 23)

A process according to claim 23 which produces a polymer of ethylene having an HI of 6 or less.

### Claim 25 (depends on 23)

A process according to claim 23 which produces a polymer of ethylene having an HI greater than 6 and less than 20.