Organometallic compounds with fused indenyl ligands

• US 6,613,713 B2
• Filed: 01/23/2001
• Issued: 09/02/2003
• Est. Priority Date: 01/28/2000
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Weiss, Thomas, Lang, Heinrich, Becke, Sigurd
• Primary Examiner(s): Harlan, Robert D.
• Application Number:
  US09/767,491
• Publication Number:
  US 20010014725A1
• Time in Patent Office: 952 Days
• Field of Search: 556/11, 556/12, 556/13, 556/20, 556/43, 556/53, 586/54, 526/127, 526/128, 526/160, 526/943, 502/117, 502/152
• US Class Current: 502/104
• CPC Class Codes: C07C 17/10 of hydrogen atoms combined with addition of halogens to unsaturated hydrocarbons C07C17/06
• CPC Class Codes: C07C 17/23 by dehalogenation
• CPC Class Codes: C07C 23/18 Polycyclic halogenated hydrocarbons
• CPC Class Codes: C07C 49/683 having unsaturation outside the aromatic rings
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C07F 7/12 Organo silicon halides
• 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 110/06 Propene
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 236/20 unconjugated
• CPC Class Codes: C08F 2500/15 Isotactic
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 2500/21 Rubbery or elastomeric properties
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

The present invention relates to transition metal organometallic compounds with an indenyl ligand attached in position 2 and fused in position 5,6, to a process for the production thereof and to the use thereof as catalysts for the (co)polymerization of olefinic and/or diolefinic monomers.

Claims

1. A process for the production of transition metal organometallic compounds with 2-indenyl fused in position 5,6 as the first ligand of the formula

in which

Q¹, Q² are identical or different and, as a substituent of the 2-indenyl system fused in position 5,6, mean hydrogen, C₁-C₄ alkyl, C₆-C₁₄ aryl, C₇-C₁₀ aralkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, phenoxy, phenylthio, di-C₁-C₄-alkylamino, C₆-C₁₄-aryl-C₁-C₄-alkylamino, di-C₆-C₁₄-arylamino, dibenzylamino, tri-C₁-C₄-alkylsilyl, di-C₁-C₄-alkylboranyl, phenyl-C₁-C₄-alkylboranyl, diphenylboranyl, di-C₁-C₄-alkylphosphoryl, diphenylphosphoryl or phenyl-C₁-C₄-alkylphosphoryl,

Q³ represents an optionally substituted alkylene residue which, together with the two carbon atoms of the indenyl residue, forms a ring system in position 5 and 6,

M¹ is a transition metal from groups 4, 5 or 6 of the IUPAC 1985 periodic system of elements,

X means an anion,

n is a number from zero to four, which is determined by the valency and bond state of M¹,

Y represents a bridge from the group of —

C(R¹R²)—

, —

Si(R¹R²)—

, —

Ge(R¹R²)—

, —

C(R¹R²)—

C(R³R⁴)—

, —

C(R¹R²)—

Si(R³R⁴)—

or —

Si(R¹R²)—

Si(R³R⁴)—

, in which R¹, R², R³ and R⁴ mutually independently mean hydrogen, halogen, linear or branched C₁-C₁₀ alkyl, C₅-C₈ cycloalkyl, C₆-C₁₄ aryl or C₇-C₁₀ aralkyl and

Z is a second ligand from the group of open-chain and cyclic, optionally anionic π

-systems, —

N(R⁵)—

, P(R⁶)—

, |N(R⁵R⁷)—

, |P(R⁶R⁸)—

, —

O—

, —

S—

, |OR⁵—

—

or |SR⁵—

, wherein the horizontal line to the left of the element symbol N, P, O or S represents a covalent bond between Z and M¹, wherein the vertical line to the left of the element symbol N, P, O or S means an electron pair and the bond between Z and M¹ is of a coordinative not covalent nature and in which R⁵, R⁶, R⁷ and R⁸ mutually independently have the range of meaning of R¹ to R⁴ and R⁵ and R⁷ may additionally mean —

Si(R¹R²R³) and R⁶ and R⁸ may additionally mean —

Si(R¹R²R³), —

OR¹, —

SR¹ or —

N(R¹R²),

comprising the step of reacting a haloindene fused in position 5,6 of the formula

in which Hal¹ denotes Cl, Br or I and Q¹, Q² and Q³ have the above meaning, with an elemental metal selected from group 1, 2 or 12 of the IUPAC 1985 periodic system or a corresponding metal compound in a quantity in the range from 1 to 100 mol of elemental metal/metal compound per mol of (II) and with a dihalide of the bridge Y of the formula

2. A process according to claim 1, wherein Y is a bridge selected from the group consisting of —

Si(R¹R²)—

, —

Ge(R¹R²)— and

—

Si(R¹R²)—

Si(R³R⁴)—

, and the reaction of (II) with (i) an elemental metal/metal compound and (ii) with (III) to yield the reaction product proceeds simultaneously.

3. A process according to claim 2, wherein Y is a bridge —

Si(R¹R²)—

.

4. A process according to claim 1, wherein said elemental metal is Mg or Zn or a mixture of Mg and Zn.

5. A process according to claim 1, wherein M¹ is a transition metal selected from the group consisting of Ti, Zr, Hf, V, Nb.

6. A process according to claim 5, wherein M¹ is a transition metal selected from the group consisting Ti, Zr and Hf.

7. A process according to claim 6, wherein M¹ is a transition metal selected from the group consisting Ti and Zr.

8. A process according to claim 1, wherein 1 to 10 mol of elemental metal/metal compound per mol of (II) and 1 to 10 mol of (III) per mol of (II) are used.

9. Transition metal organometallic compounds with 2-indenyl fused in position 5,6 as the first ligand of the formula

in which

Q¹, Q² are identical or different and, as a substituent of the 2-indenyl system fused in position 5,6, mean hydrogen, C₁-C₄ alkyl, C₆-C₁₄ aryl, C₇-C₁₀ aralkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, phenoxy, phenylthio, di-C₁-C₄-alkylamino, C₆-C₁₄-aryl-C₁-C₄-alkylamino, di-C₆-C₁₄-arylamino, dibenzylamino, tri-C₁-C₄-alkylsilyl, di-C₁-C₄-alkylboranyl, phenyl-C₁-C₄-alkylboranyl, diphenylboranyl, di-C₁-C₄-alkylphosphoryl, diphenylphosphoryl or phenyl-C₁-C₄-alkylphosphoryl,

Q³ represents an optionally substituted alkylene residue which, together with the two carbon atoms of the indenyl residue, forms a ring system in position 5 and 6,

M¹ is a transition metal from groups 4, 5 or 6 of the IUPAC 1985 periodic system of elements,

X means an anion,

n is a number from zero to four, which is determined by the valency and bond state of M¹,

Y represents a bridge from the group of —

C(R¹R²)—

, —

Si(R¹R²)—

, —

Ge(R¹R²)—

, —

C(R¹R²)—

C(R³R⁴)—

, —

C(R¹R²)—

Si(R³R⁴)—

or —

Si(R¹R²)—

Si(R³R⁴)—

, in which R¹, R², R³ and R⁴ mutually independently mean hydrogen, halogen, linear or branched C₁-C₁₀ alkyl, C₅-C₈ cycloalkyl, C₆-C₁₄ aryl or C₇-C₁₀ aralkyl and

Z is a second ligand from the group of open-chain and cyclic, optionally anionic π

-systems, —

N(R⁵)—

, P(R⁶)—

, |N(R⁵R⁷)—

, IP(R⁶R⁸)—

, —

O—

, —

S—

, |OR⁵—

or |SR⁵—

, wherein the horizontal line to the left of the element symbol N, P, O or S represents a covalent bond between Z and Ml, wherein the vertical line to the left of the element symbol N, P, O or S means an electron pair and the bond between Z and M¹ is of a coordinative not covalent nature and in which R⁵, R⁶, R⁷ and R⁸ mutually independently have the range of meaning of R¹ to R⁴ and R⁵ and R⁷ may additionally mean —

Si(R¹R²R³) and R⁶ and R⁸ may additionally mean —

Si(R¹R²R³), —

OR¹, —

SR¹ or —

N(R¹R²).

10. Transition metal organometallic compounds according to claim 9, in which, in the formula (I), Z is replaced by the second ligand Z′

, which has the meaning of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted 1-indenyl, substituted or unsubstituted 2-indenyl, substituted or unsubstituted fluorenyl, —

N(R⁵)—

, —

P(R⁶)—

, |N(R⁵R⁷)—

, |P(R⁶R⁸)—

, —

O—

, —

S—

, |OR⁵—

or |SR⁵—

.

11. Transition metal organometallic compounds according to claim 9, in which, in the formula (I), Z′

is replaced by the second ligand Z″

, which has the meaning of —

N(R⁵)—

or |N(R⁵R⁷)—

, wherein in the formula (I) Y furthermore means —

Si(R¹R²)— and

M¹ means Ti or Zr.

12. A transition metal organometallic compound according to claim 9, wherein said compound is tert.-butylamine-2-[5,6,7-tetrahydroindacenyl]dimethylsilyltitanium dichloride.