Process for preparing a cycloolefin copolymer

• US 6,020,444 A
• Filed: 06/04/1998
• Issued: 02/01/2000
• Est. Priority Date: 12/13/1995
• Status: Expired due to Term

• Current Assignee: Ticona GmbH (Celanese Corporation)
• Original Assignee: Mitsui Petrochemical Industries, Ltd., Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Weller, Thomas, Riedel, Michael, Jacobs, Alexandra
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US09/090,855
• Time in Patent Office: 607 Days
• Field of Search: 526/160, 526/170, 526/281, 526/161, 526/943, 526/126, 526/127, 526/308
• US Class Current: 526/170
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 232/00 Copolymers of cyclic compounds containing 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 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/61927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

The present invention relates to a process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula I, ##STR1## where L is a π-ligand, L'"'"' is a π-ligand, T is a bridge between L and L'"'"', M is a tetravalent transition metal, m is 1 or 2 and R¹, R², R³ and R⁴ are, independently of one another, identical or different and are each a hydrogen atom or a C₁ -C₂₀ -hydrocarbon radical.

Claims

1. A process for preparing a cycloolefin copolymer, comprising:

co-polymerizing at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula I ##STR9## where m is 1 or 2;

L is a monocyclic, fused bicyclic, or fused tricyclic π

-ligand, L'"'"' is a monocyclic, fused bicyclic, or fused tricyclic π

-ligand, and, when m is 1, L and L'"'"' are different from each other, at least one of L and L'"'"' being monocyclic when the other is fused bi- or fused tricyclic, and at least one of L and L'"'"' being fused bicyclic when the other is monocyclic or fused tricyclic;

T is a bridge between L and L'"'"';

M is a tetravalent transition metal; and

R¹, R², R³ and R⁴ are, independently of one another, identical or different and are each a hydrogen atom or a C₁ -C₂₀ -hydrocarbon radical.

2. The process as claimed in claim 1, wherein the catalyst further comprises at least one cocatalyst.

3. The process as claimed in claim 1, wherein L and L'"'"' are substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, or substituted or unsubstituted fluorenyl.

4. The process as claimed in claim 1, wherein m is 2.

5. The process as claimed in claim 1, wherein M of the formula I is titanium, zirconium, hafnium, vanadium, niobium, tantalum, scandium, yttrium or a rare earth metal, L is a substituted or unsubstituted cyclopentadienyl group, L'"'"' is a substituted or unsubstituted cyclopentadienyl group which is identical to or different from L;

and, when m is 1, T is 1 to 4 bridging units of the formula (R⁵ R⁶ X), where the X radicals of each of the bridging units are, independently of one another, identical or different and are carbon, silicon, germanium or tin, the radicals R⁵ and R⁶ are, independently of one another, identical or different and are each a hydrogen atom or a C₁ -C₃₀ -hydrocarbon radical;

and, when m is 2, T is carbon, silicon, germanium, or tin.

6. The process as claimed in claim 5, wherein M is titanium, zirconium, or hafnium;

R⁵ and R⁶ are identical or different and are C₁ -C₂₀ -alkyl or C₆ -C₂₀ -aryl, and R¹, R², R³, and R⁴ are identical or different and are C₁ -C₂₀ -alkyl or C₆ -C₁₄ -aryl.

7. The process as claimed in claim 1, wherein a metallocene compound of the formula I has been converted into a cationic or labile coordination form of said metallocene compound with a cocatalyst having Lewis acidity.

8. The process as claimed in claim 7, wherein said cocatalyst is an aluminum compound, a boron compound, or a combination thereof.

9. The process as claimed in claim 7, wherein the resulting cycloolefin copolymer is resistant to decomposition at a temperature of 300°

C. and has the following properties;

yield stress, as measured by DIN 53457, of 50 to 100 MPa, and a refractive index ranging from 1.520 to 1.555.

10. A method of using a metallocene compound of the formula I ##STR10## where:

m is 1 or 2,

L is a mono-cyclic fused bi-cyclic or tri-cyclic π

-ligand

L'"'"' is a mon-cyclic fused bi-cyclic or fused tri-cyclic π

-ligand, and, when m is 1, L and L'"'"' are different from each other, at least one of L and L'"'"' being monocyclic when the other is fused bi-cyclic or fused tri-cyclic, and at least one of L and L'"'"' being fused bicyclic when the other is mono- or fused tri-cyclic,

T is a bridge between L and L'"'"',

M is a tetravalent transition metal,

m is 1 or 2, and

R¹, R², R³ and R⁴ are, independently of one another, identical or different and are each a hydrogen atom or a C₁ -C₂₀ -hydrocarbon radical, comprising;

co-polymerizing a co-polymerizable monomeric composition containing at least one cyclic olefin in the presence of said metallocene compound or a cation or labile coordination form thereof.