Process for preparing cycloolefin polymer

• US 5,733,991 A
• Filed: 10/15/1996
• Issued: 03/31/1998
• Est. Priority Date: 02/12/1993
• Status: Expired due to Term

• Current Assignee: Basell Polyolefine GmbH (Lyondellbasell Industries NV)
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Weller, Thomas, Rohrmann, Jurgen, Osan, Frank, Brekner, Michael-Joachim, Kuber, Frank
• Primary Examiner(s): Zitomer, Fred
• Application Number:
  US08/730,739
• Time in Patent Office: 532 Days
• Field of Search: 502/103, 502/232, 502/242
• US Class Current: 526/160
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 32/00 Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08F 32/08 having two condensed rings coumarone-indene polymers C08F244/00
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

Cycloolefin polymers having a high viscosity number are obtained by polymerization of a polycyclic olefin and, if desired, an acyclic olefin and/or a monocyclic olefin in the presence of a catalyst system which comprises an aluminoxane and a metallocene compound of the formula ##STR1## in which R¹⁶ is fluorenyl or indenyl and R¹⁷ is cyclopentadienyl and the bridge R¹⁸ contains silicon.

Claims

1. A process for preparing a cycloolefin homopolymer or copolymer by polymerization of from 0.1 to 100% by weight, based on the total amount of monomers, of at least one polycyclic olefin of the formulae I, II, III, IV, V or VI ##STR15## ##STR16## in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and are a hydrogen atom or a C₆ -C₁₀ -aryl radical or a C₁ -C₈ -alkyl radical, with the same radicals in the various formulae being able to have a different meaning, from 0 to 99.9% by weight, based on the total amount of monomers, of a cycloolefin of the formula VII ##STR17## in which n is a number from 2 to 10, and from 0 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin of the formula VIII ##STR18## in which R⁹, R¹⁰, R¹¹ and R¹² are identical or different and are a hydrogen atom or a C₆ -C₁₀ -aryl radical or C₁ -C₈ -alkyl radical, at temperatures from 20°

to 150°

C. and a pressure from 0.01 to 64 bar, in the presence of a catalyst which comprises an aluminoxane of the formula IX ##STR19## for the linear type and/or of the formula X ##STR20## for the cyclic type, with, in the formulae IX and X, R¹³ being a C₁ -C₆ -alkyl group or phenyl or benzyl and n being an integer from 2 to 50, and a metallocene of the formula ##STR21## in which M¹ is titanium, zirconium or hafnium,

R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group or a C₈ -C₄₀ -arylalkenyl group,

R¹⁶ is a substituted fluorenyl group, bearing one or more radicals which are identical or different and are a C₁ -C₁₀ alkyl group, C₁ -C₁₀ -fluoroalkyl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -alkoxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₈ -C₄₀ -arylalkenyl group or a C₇ -C₄₀ -alkyl-aryl group, and R¹⁷ is a cyclopentadienyl group,

wherein

R¹⁸ is ##STR22## in which M² is silicon and

R¹⁹, R²⁰ and R²¹ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -fluoroalkyl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryl group, a C₁ -C₁₀ -alkoxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₈ -C₄₀ -arylalkenyl group or a C₇ -C₄₀ -alkylaryl group or R¹⁹ and R²⁰ or R¹⁹ and R²¹ in each case form a ring with the atoms connecting them.

2. The process as claimed in claim 1, wherein the polymerization is carried out in the liquid cycloolefin itself or in cycloolefin solution.

3. The process as claimed in claim 1, wherein the polycyclic olefin is norbornene or tetracyclododecene.

4. The process as claimed in claim 1, wherein a copolymer of norbornene and ethylene is prepared.

5. The process as claimed in claim 1, wherein at least one polycyclic olefin is of the formulas I or III, in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and are a hydrogen atom, a C₆ -C₁₀ -aryl radical or a C₁ -C₈ -alkyl radical where the same radicals can have different meaning in the various formulas.

6. The process as claimed in claim 5, wherein R⁹, R¹⁰, R¹¹ and R¹² are identical or different and are a hydrogen atom or C₁ -C₈ -alkyl group.

7. The process as claimed in claim 6, wherein R⁹, R¹⁰, R¹¹ and R¹² are identical or different and are ethylene or propylene.

8. The process as claimed in claim 1, wherein the temperature is from 20°

to 150°

C., n is an integer from 5 to 40, and wherein in the formulas IX and X, the radical R¹³ is identical or different and is methyl, ethyl, isobutyl, butyl, neopentyl, phenyl or benzyl and n is an integer from 5 to 40, and the metallocene is dimethylsilandiyl(9-(2,7-di-tert.butyl)fluorenyl)cyclopentadienylzirconium dichloride.

9. The process as claimed in claim 5, wherein the metallocene of formula XI is dimethylsilandiyl(9-2,7-di-tert.butyl)fluorenyl)cyclopentadienylzirconium dichloride.

10. The process as claimed in claim 1, wherein the cycloolefin of formula VII is a substituted or unsubstituted cyclopentene.

11. A metallocene compound of the formula XI ##STR23## in which M¹ is titanium, zirconium or hafnium

R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group or a C₈ -C₄₀ -arylalkenyl group,

R¹⁶ is a fluoroenyl group bearing one or more radicals which are identical or different and are a C₁ -C₁₀ alkyl group, C₁ -C₁₀ -fluoroalkyl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -alkoxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₈ -C₄₀ -arylalkenyl group or a C₇ -C₄₀ -alkyl-aryl group, and

R¹⁷ is a cyclopentadienyl group,

wherein

R¹⁸ is ##STR24## in which M² is silicon and

R¹⁹, R²⁰ and R²¹ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -fluoroalkyl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryl group, a C₁ -C₁₀ -alkoxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₈ -C₄₀ -arylalkenyl group or a C₇ -C₄₀ -alkylaryl group or R¹⁹ and R²⁰ or R¹⁹ and R²¹ in each case form a ring with the atoms connecting them.

12. The metallocene compound as claimed in claim 11, wherein M¹ is zirconium or hafnium.

13. The metallocene compound as claimed in claim 11, wherein R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a C₁ -C₃ -alkyl group, a C₁ -C₃ -alkoxy group, a C₆ -C₈ -aryl group, a C₆ -C₈ -aryloxy group, a C₂ -C₄ -alkenyl group, a C₇ -C₁₀ -arylalkyl group, a C₇ -C₁₂ -alkylaryl group, a C₈ -C₁₂ -arylalkenyl group or a chlorine atom.

14. The metallocene as claimed in claim 13, wherein M¹ is zirconium.

15. The metallocene as claimed in claim 11, wherein R¹⁸ is ##STR25##

16. The metallocene as claimed in claim 15, wherein R¹⁸ is ##STR26##

17. The metallocene as claimed in claim 11, wherein the metallocene is dimethylsilandiyl(9-(2,7-di-tert butyl)fluorenyl)cyclopentadienylzirconium dichloride.