Process for producing crystalline poly-.alpha.-olefins with a monocyclopentadienyl transition metal catalyst system

• US 5,026,798 A
• Filed: 09/13/1990
• Issued: 06/25/1991
• Est. Priority Date: 09/13/1989
• Status: Expired

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Canich, Jo Ann M.
• Primary Examiner(s): Garvin, Patrick P.
• Application Number:
  US07/581,817
• Time in Patent Office: 285 Days
• Field of Search: 526/127, 526/132, 526/150, 526/160
• US Class Current: 526/127
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• 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 10/06 Propene
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 232/08 having condensed rings coumarone-indene polymers C08F244/00
• CPC Class Codes: C08F 236/20 unconjugated
• CPC Class Codes: C08F 2500/01 High molecular weight, e.g. >800,000 Da.
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/10 Short chain branches
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/24 Polymer with special particle form or size
• CPC Class Codes: C08F 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 : in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 : supported on a carrier, e.g. silica, MgCl2, polymer
• 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 invention is a catalytic process using a Group IV B transition metal component and an alumoxane component to polymerize α-olefins to produce high crystallinity and high molecular weight poly-α-olefins.

Claims

1. A process for producing crystalline poly-α

-olefins comprising the steps of

(i) contacting an α

-olefin monomer at a temperature and pressure sufficient to polymerize such monomer with a catalyst system comprising;

(A) an alumoxane, and

(B) a group IV-B transition metal component of the formula ##STR12## wherein M is Zr, Hf or Ti in its highest formal oxidation state;

R is a substituent group with "x" denoting the degree of substitution (x=0, 1, 2, 3 or

     4) and each R is, independently, a radical selected from a group consisting of C₁ -C₂₀ hydrocarbyl radicals, substituted C₁ -C₂₀ hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing a Lewis acidic or basic functionality, C₁ -C₂₀ hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements, and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or a radical containing Lewis acidic or basic functionality, or at least two adjacent R-groups are joined forming C₄ -C₂₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

(JR'"'"'_z-2) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, and each R'"'"' is, independently a radical selected from a group consisting of C₁ -C₂₀ hydrocarbyl radicals, substituted C₁ -C₂₀ hydrocarbyl radicals where one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, and alkoxy radical or a radical containing a Lewis acidic or basic functionality, and "z" is the coordination number of the element J;

each Q is, independently, any univalent anionic ligand or two Q'"'"'s are a divalent anionic chelating ligand;

T is a covalent bridging group containing a Group IV A or V A element;

L is a neutral Lewis base where "w" denotes a number from 0 to 3;

(ii) recovering a crystalline poly-α

-olefin.

2. The process of claim 1, wherein the Group IV-B transition metal component is of the formula:

##STR13## wherein R¹ and R² are, independently, a C₁ to C₂₀ hydrocarbyl radicals, substituted C₁ to C₂₀ hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom;

R¹ and R² may also be joined forming a C₃ to C₂₀ ring.

3. The processes of claims 1 or 2 wherein J is nitrogen.

4. The process of claim 3 wherein R is a C₁ to C₂₀ hydrocarbyl radical, "x" is 1 and R'"'"' is a C₆ to C₂₀ cyclohydrocarbyl radical or an aromatic radical.

5. The process of claim 1 wherein the Group IV-B transition metal component is of the formula:

##STR14## wherein R¹ and R² are independently a C₁ to C₂₀ hydrocarbyl radicals, substituted C₁ to C₂₀ hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom;

R¹ and R² may also be joined forming a C₃ to C₂₀ ring.

6. The process of claim 5 where J is nitrogen.

7. The process of claim 6 wherein R'"'"' is an alkyl radical or cyclic radical.

8. The process of claim 1 wherein the Group IV-B transition metal component is of the formula ##STR15## wherein R¹ and R² are independently a C₁ to C₂₀ hydrocarbyl radicals, substituted C₁ to C₂₀ hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom;

R¹ and R² may also be joined forming a C₃ to C₂₀ ring.

9. The process of claim 8 wherein J is nitrogen.

10. The process of claim 9 wherein R'"'"' is a cycloalkyl radical.

11. The process of claim 2, 5, or 8 wherein M is titanium.

12. The process of claims 2 or 5 wherein M is hafnium or zirconium.

13. The process of claim 1 wherein T is silicon, J is nitrogen and when R is an alkyl radical, R'"'"' is a cyclohydrocarbyl or aromatic radical, and when "x" is 2 or 4 and the R substituents form a polycyclic ring system, R'"'"' is an alkyl or cyclohydrocarbyl radical.